POLYMERIZABLE DICHROIC DYES

Abstract

New dichroic dyes having a composition with slave materials. The dyes may be used for a dichroic polymer network, a dichroic liquid crystalline polymer film (LCP film) or a dichroic liquid crystalline polymer gel, which for instance find application as electro-optical or optical devices.

Claims

1. A dichroic dye of formula (I): ##STR00032## wherein X.sup.1 is NR or S, X.sup.2 is a single bond, NR, S or O, Y.sup.1, Y.sup.2 independently from each other are a single bond, NR, S or O, Z.sup.1, Z.sup.2 independently from each other are a single bond, NR, S or O, R represents hydrogen, unbranched or branched lower alkyl radical, W.sup.1, W.sup.2, W.sup.3, W.sup.4, W.sup.5, W.sup.6 independently from each other are H, unsubstituted or substituted, unbranched or branched C.sub.1-C.sub.30 alkyl radical, in which one or more CH or CH.sub.2 group may be replaced by a linking group, PG is a polymerizable group, n1, n2, n3, n4, n5, n6 independently from each other signifies 0, 1, 2, 3, 4, 5 or 6 whereby the sum of n1, n2, n3, n4, n5 and n6 is 1, with the proviso that if n1, n2, n3, n4, n5 or n6=0, the connected W.sup.1, W.sup.2, W.sup.3, W.sup.4, W.sup.5, W.sup.6 have to be saturated by hydrogen.

2. A dichroic dye of formula (I) according to claim 1, wherein the: linking group is selected from the group consisting of O, S, NR.sup.1, CHN, NN, CH(OR.sup.1), CO, CONR.sup.1, NR.sup.1CO, NR.sup.1COO, OCONR.sup.1, NR.sup.1CONR.sup.1, COO, OCO, OCOO, SO, SO.sub.2, Si(R.sup.1).sub.2, OSi(R.sup.1).sub.2, OSi(R.sup.1).sub.2O, CC, CC, an aromatic or alicyclic group which is unsubstituted or substituted by one or more straight chain or branched lower alkyl radical, halogens, OR.sup.1, SR.sup.1, NR.sup.1R.sup.2, CN, NO.sub.2, SOR.sup.1, SO.sub.2R.sup.1, SO.sub.3.sup. the negative charge of the SO.sub.3.sup. group being balanced by a cation or mixture of cations selected from the group consisting of H.sup.+, Li.sup.+, Na.sup.+, K.sup.+ and [NR.sup.1R.sup.2R.sup.3R.sup.4].sup.+, and wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 independently from each other represent hydrogen, straight chain or branched lower alkyl radical, with the proviso that oxygen atoms of the linking groups are not directly linked to each other.

3. A dichroic dye of formula (I) according to claim 1, wherein X.sup.2, X.sup.1 are independently from each other NR, R has the same meaning as mentioned above, Y.sup.1, Y.sup.2 independently from each other are a single bond, Z.sup.1 is O, Z.sup.2 is a single bond, n2 is 1, n1, n3, n4, n5, n6 are 0, W.sup.1, W.sup.4, W.sup.5, W.sup.6 are hydrogen W.sup.2, W.sup.3 are independently from each other are unsubstituted or substituted, straight chain or branched C.sub.1-C.sub.30 alkyl, in which one CH or CH.sub.2 group may be replaced by one or more linking group consisting of O, S, NR.sup.1, CH(OR.sup.1), CONR.sup.1, NR.sup.1CO, COO, OCO, SO.sub.2 or an aromatic group which is unsubstituted or substituted by one or more straight chain or branched lower alkyl radical, F, Cl or OR.sup.1, and wherein R.sup.1 having the same meaning as mentioned above, PG is a polymerizable group consisting of CH.sub.2CQ-COO, wherein Q is hydrogen or methyl; or a dichroic dye of formula (I), wherein X.sup.1 is S X.sup.2 is single bond or NR, R has the same meaning as mentioned above, Y.sup.1 is S, Y.sup.2 is a single bond or NR, Z.sup.1, Z.sup.2 are single bond, n1, n6 are 1, n2, n3, n4, n5, are 0, W.sup.2, W.sup.3, W.sup.4, W.sup.5 are hydrogen W.sup.1, W.sup.6 are independently from each other are unsubstituted or substituted, straight chain or branched C.sub.1-C.sub.30 alkyl, in which one CH or CH.sub.2 group may be replaced by one or more linking group consisting of O, S, NR.sup.1, CH(OR.sup.1), CONR.sup.1, NR.sup.1CO, COO, OCO, SO.sub.2 or an aromatic group which is unsubstituted or substituted by one or more straight chain or branched lower alkyl radical, F, Cl or OR.sup.1, and wherein R.sup.1 having the same meaning as mentioned above, PG is a polymerizable group consisting of CH.sub.2CQ-COO, wherein Q is hydrogen or methyl; or a dichroic dye of formula (I), wherein X.sup.1, X.sup.2 are independently from each other NR Y.sup.1, Y.sup.2 are independently from each other NR, R has the same meaning as mentioned above, Z.sup.1, Z.sup.2 are independently from each other a single bond or O n2, n5 are 1, n1, n3, n4, n6, are 0, W.sup.1, W.sup.6 are hydrogen W.sup.2, W.sup.3, W.sup.4, W.sup.5 are independently from each other unsubstituted or substituted, straight chain or branched C.sub.1-C.sub.30 alkyl, in which one CH or CH.sub.2 group may be replaced by one or more linking group consisting of O, S, NR.sup.1, CH(OR.sup.1), CONR.sup.1, NR.sup.1CO, COO, OCO, SO.sub.2 or an aromatic group which is unsubstituted or substituted by one or more straight chain or branched lower alkyl radical, F, Cl or OR.sup.1, and wherein R.sup.1 having the same meaning as mentioned above, PG is a polymerizable group consisting of CH.sub.2CQ-COO, wherein Q is hydrogen or methyl.

4. A composition comprising at least one dichroic dye (I) as described in claim 1 and at least one slave material.

5. A composition according to claim 4, wherein the slave material is a liquid crystal or polymerizable liquid crystal.

6. A composition according to claim 4, wherein said compositions in addition comprises at least one chiral polymerizable liquid crystalline compound or at least one chiral component.

7. Use of the composition according to claim 4, for the preparation of a dichroic polymer network, a dichroic liquid crystalline polymer film (LCP film) or a dichroic liquid crystalline polymer gel.

8. A process for the preparation of a dichroic polymer network, a dichroic liquid crystalline polymer film (LCP film) or a dichroic liquid crystalline polymer gel, which process comprises polymerizing a dichroic dye (I) as described in claim 1.

9. A dichroic polymer network, a dichroic liquid crystalline polymer film (LCP film) or a dichroic liquid crystalline polymer gel comprising a dichroic dye as described in claim 1.

10. Use of a composition according to claim 4 for the preparation of electro-optical and optical devices.

11. An electro-optical or optical device, comprising a dichroic polymer network a dichroic liquid crystalline polymer film (LCP film) or a dichroic liquid crystalline polymer gel according to claim 9.

12. An electro-optical or optical device according to claim 11, which is represented by a polarizer, an optical film, a security or an authentication device.

13. A dichroic dye of formula (I) according to claim 2, wherein X.sup.2, X.sup.1 are independently from each other NR, R has the same meaning as mentioned above, Y.sup.1, Y.sup.2 independently from each other are a single bond, Z.sup.1 is O, Z.sup.2 is a single bond, n2 is 1, n1, n3, n4, n5, n6 are 0, W.sup.1, W.sup.4, W.sup.5, W.sup.6 are hydrogen W.sup.2, W.sup.3 are independently from each other are unsubstituted or substituted, straight chain or branched C.sub.1-C.sub.30 alkyl, in which one CH or CH.sub.2 group may be replaced by one or more linking group consisting of O, S, NR.sup.1, CH(OR.sup.1), CONR.sup.1, NR.sup.1CO, COO, OCO, SO.sub.2 or an aromatic group which is unsubstituted or substituted by one or more straight chain or branched lower alkyl radical, F, Cl or OR.sup.1, and wherein R.sup.1 having the same meaning as mentioned above, PG is a polymerizable group consisting of CH.sub.2CQ-COO, wherein Q is hydrogen or methyl; or a dichroic dye of formula (I), wherein X.sup.1 is S X.sup.2 is single bond or NR, R has the same meaning as mentioned above, Y.sup.1 is S, Y.sup.2 is a single bond or NR, Z.sup.1, Z.sup.2 are single bond, n1, n6 are 1, n2, n3, n4, n5, are 0, W.sup.2, W.sup.3, W.sup.4, W.sup.5 are hydrogen W.sup.1, W.sup.6 are independently from each other are unsubstituted or substituted, straight chain or branched C.sub.1-C.sub.30 alkyl, in which one CH or CH.sub.2 group may be replaced by one or more linking group consisting of O, S, NR.sup.1, CH(OR.sup.1), CONR.sup.1, NR.sup.1CO, COO, OCO, SO.sub.2 or an aromatic group which is unsubstituted or substituted by one or more straight chain or branched lower alkyl radical, F, Cl or OR.sup.1, and wherein R.sup.1 having the same meaning as mentioned above, PG is a polymerizable group consisting of CH.sub.2CQ-COO, wherein Q is hydrogen or methyl; or a dichroic dye of formula (I), wherein X.sup.1, X.sup.2 are independently from each other NR Y.sup.1, Y.sup.2 are independently from each other NR, R has the same meaning as mentioned above, Z.sup.1, Z.sup.2 are independently from each other a single bond or O n2, n5 are 1, n1, n3, n4, n6, are 0, W.sup.1, W.sup.6 are hydrogen W.sup.2, W.sup.3, W.sup.4, W.sup.5 are independently from each other unsubstituted or substituted, straight chain or branched C.sub.1-C.sub.30 alkyl, in which one CH or CH.sub.2 group may be replaced by one or more linking group consisting of O, S, NR.sup.1, CH(OR.sup.1), CONR.sup.1, NR.sup.1CO, COO, OCO, SO.sub.2 or an aromatic group which is unsubstituted or substituted by one or more straight chain or branched lower alkyl radical, F, Cl or OR.sup.1, and wherein R.sup.1 having the same meaning as mentioned above, PG is a polymerizable group consisting of CH.sub.2CQ-COO, wherein Q is hydrogen or methyl.

14. A process for the preparation of a dichroic polymer network, a dichroic liquid crystalline polymer film (LCP film) or a dichroic liquid crystalline polymer gel, which process comprises polymerizing a composition as described in claim 4.

15. Use of a dichroic polymer network, a dichroic liquid crystalline polymer film (LCP film) or a dichroic liquid crystalline polymer gel according to claim 9 for the preparation of electro-optical and optical devices.

16. A dichroic polymer network, a dichroic liquid crystalline polymer film (LCP film) or a dichroic liquid crystalline polymer gel comprising a composition as defined claim 4.

17. A dichroic polymer network, a dichroic liquid crystalline polymer film (LCP film) or a dichroic liquid crystalline polymer gel comprising a composition as defined claim 5.

18. A dichroic polymer network, a dichroic liquid crystalline polymer film (LCP film) or a dichroic liquid crystalline polymer gel comprising a composition as defined claim 6.

Description

EXAMPLES

Abbreviations

[0120] DMSO=Dimethylsulfoxide

[0121] CDCl.sub.3=deuterated chloroform

[0122] BOPP=biaxially oriented polypropylen

Example 1

[0123] ##STR00002##

[0124] 1-aminoanthraquinone (46.0 parts) commercial available such as from Sigma Aldrich, is dissolved in concentrated sulfuric acid (98%, 200 mL) at 60 C. When the product is completely dissolved, the temperature is decreased to room temperature before slow addition of ice (800.0 parts) with efficient stirring. To the resulting slurry at 0-5 C. is then added drop wise bromine (72.4 parts) over a period of 3 hours. The resulting mixture is stirred at room temperature for 20 hours. Excess bromine is then removed by bubbling nitrogen in the reaction mixture. The precipitate is then filtered and washed with water (1000 mL). The wet press-cake is stirred in 8 wt % aqueous sodium hydroxide solution (1000 mL) for one hour, filtered, successively washed with water (1000 mL), 20 wt % aqueous sodium bisulfite solution (400 mL), water (1000 mL) and finally dried overnight at 50 C. under vacuum to afford 70.0 parts of compound (1) as a red solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 8.2 (s, 1H), 8.2-8.1 (m, 2H), 7.8 (m, 2H).

Example 2

[0125] ##STR00003##

[0126] Compound (1) (68.6 parts), tosylamine (62.9 parts), potassium acetate (22.3 parts) and anhydrous copper acetate (1.7 parts) in amyl alcohol (750 mL) are stirred and refluxed for 10 hours. Temperature is decreased to room temperature and methanol (375 mL) is added. The precipitate is filtered, successively washed with methanol (500 mL) and water (1000 mL). The obtained press-cake is dried overnight at 50 C. under vacuum to afford 84.8 parts of compound (2) as a dark brown solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 11.9 (s, 1H), 8.2-8.1 (m, 3H), 7.9 (m, 2H), 7.7 (d, 2H), 7.3 (d, 2H), 2.3 (s, 3H).

Example 3

[0127] ##STR00004##

[0128] 6-chlorohexan-1-ol (20.0 parts) (commercial available such as from Sigma Aldrich), dicyclohexylcarbodiimide (36.2 parts) and methacrylic acid (15.2 parts) are dissolved in tetrahydrofurane (200 mL). 4-Dimethylaminopyridine (2.0 parts) is added and the mixture is stirred 24 hours at room temperature. The reaction mixture is then filtered over celite and the filtrate is evaporated to dryness. The residue is then purified by column chromatography (SiO.sub.2; eluent: toluene) to afford 30.0 parts of compound (3) as a colorless oil. NMR-.sup.1H (CDCl.sub.3, 300 MHz, ppm): 6.1 (s, 1H), 5.5 (s, 1H), 4.1 (t, 2H), 3.5 (t, 2H), 1.9 (s, 3H), 1.8-1.6 (m, 4H), 1.5-1.3 (m, 4H).

Example 4

[0129] ##STR00005##

[0130] Compound (3) (30.0 parts), Hydroquinone (60.0 parts), potassium iodide (3.0 parts) and potassium carbonate (30.0 parts) are stirred in dimethylformamide (100 mL) and heated to 100 C. for 10 hours. Temperature is decreased to room temperature, ethyl acetate (250 ml) is added and the mixture is successively washed with 1 wt % aqueous hydrochloric acid solution (3250 ml) and saturated aqueous sodium chloride solution (2200 ml). The organic layer is dried over sodium sulfate, filtered and evaporated. The product is further purified by column chromatography (SiO.sub.2; eluent: toluene then toluene/ethyl acetate: 95/5) to afford 31.4 parts of compound (4) as a colorless oil which solidify upon standing. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 8.8 (s, 1H), 6.7 (d, 2H), 6.6 (d, 2H), 6.0 (s, 1H), 5.6 (s, 1H), 4.1 (t, 2H), 3.8 (d, 2H), 1.9 (s, 3H), 1.7-1.5 (m, 4H), 1.5-1.3 (m, 4H).

Example 5

[0131] ##STR00006##

[0132] Compound (4) (5.0 parts) is dissolved in N-methyl-2-pyrrolidone (50 mL) at room temperature. Sodium hydride (60% dispersion in mineral oil, 0.54 part) is added and the resulting mixture is stirred 30 minutes at room temperature. Compound (2) (4.2 parts) and 2,6-di-tert-butyl-4-methylphenol (0.01 part) are then added and the resulting mixture is heated at 135 C. for 8 hours under nitrogen. Temperature is decreased to room temperature, ethyl acetate (250 mL) is added and the mixture is successively washed with 1 wt % aqueous hydrochloric acid solution (2250 mL) and saturated aqueous sodium chloride solution (2200 mL). The organic layer is dried over sodium sulfate, filtered and evaporated. The product is further purified by column chromatography (SiO.sub.2; eluent: toluene/ethyl acetate: 95/5) to afford 3.7 parts of compound (5) as a dark reddish-pink solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 12.9 (s, 1H), 8.2 (d, 2H), 7.9 (m, 2H), 7.4 (d, 2H), 7.3 (d, 2H), 7.2 (m, 4H), 6.9 (s, 1H), 6.0 (s, 1H), 5.6 (s, 1H), 4.1 (m, 4H), 2.3 (s, 3H), 1.9 (s, 3H), 1.8 (m, 2H), 1.7 (m, 2H), 1.5-1.3 (m, 4H).

Example 6

[0133] ##STR00007##

[0134] Compound (5) (3.6 parts) is mixed with methanesulfonic acid (30 mL) and stirred 24 hours at room temperature. The resulting solution is poured in a mixture of ice and water (300.0 parts) and the pH is slowly increased to 5-6 using an 8 wt % aqueous sodium hydroxide solution. Ethyl acetate (300 mL) is added, the organic phase is separated and successively washed with 5 wt % aqueous sodium carbonate (2200 mL) and saturated aqueous sodium chloride solution (2200 mL). The organic phase is dried over sodium sulfate, filtered and evaporated. The product is further purified by column chromatography (SiO.sub.2; eluent: toluene/ethyl acetate: 95/5) to afford 1.5 parts of compound (6) as a reddish-pink solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 8.2 (m, 2H), 7.8 (m, 2H), 7.2 (d, 2H), 7.1 (d, 2H), 6.4 (s, 1H), 6.0 (s, 1H), 5.6 (s, 1H), 4.1 (m, 2H), 4.0 (m, 2H), 1.9 (s, 3H), 1.7 (m, 2H), 1.6 (m, 2H), 1.5-1.3 (m, 4H).

Example 7

[0135] ##STR00008##

[0136] Compound (2) (9.5 parts) and hydroquinone (11.1 parts) are added to N-methyl-2-pyrrolidone (80 mL) and stirred at room temperature. Potassium carbonate (3.1 parts) is added and the reaction mixture is heated to 130 C. for 20 hours. Temperature is decreased to room temperature and the resulting mixture is poured in 5 wt % aqueous hydrochloric acid solution (650 mL) with efficient stirring. The precipitate is filtered, successively washed with 1 wt % aqueous hydrochloric acid solution (300 mL), water (1000 mL) and finally dried overnight at 50 C. under vacuum to afford 9.0 parts of compound (7) as a reddish-pink solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 12.9 (s, 1H), 9.8 (s, 1H), 8.2 (m, 2H), 7.9 (m, 2H), 7.4 (d, 2H), 7.3 (d, 2H), 7.0 (m, 4H), 6.9 (s, 1H), 2.3 (s, 3H).

Example 8

[0137] ##STR00009##

[0138] Compound (7) (4.5 parts), 4-(6-acryloyloxy-hexyl-1-oxy)benzoic acid (4.0 parts; synthesized according to U.S. Pat. No. 6,258,974 or EP-1174411), dicyclohexylcarbodiimide (2.8 parts) and 2,6-di-tert-butyl-4-methylphenol (0.01 part) are dissolved in tetrahydrofurane (75 mL). 4-Dimethylaminopyridine (0.4 part) is added and the mixture is stirred 24 hours at room temperature. The reaction mixture is then filtered over celite and the n-heptane (200 mL) is added to the filtrate. Tetrahydrofurane is evaporated under vacuum and the resulting precipitate is filtered and successively washed with n-heptane (200 mL). The resulting product is finally dried overnight at 50 C. under vacuum to afford 5.3 parts of compound (8) as a dark reddish-pink solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 12.8 (s, 1H), 8.3 (d, 2H), 8.2 (m, 2H), 7.9 (m, 2H), 7.5 (d, 2H), 7.4 (d, 2H), 7.3 (d, 2H), 7.2 (d, 2H), 7.1 (d, 2H), 6.9 (s, 1H), 6.4-5.9 (m, 3H), 4.1 (m, 4H), 2.3 (s, 3H), 1.8 (m, 2H), 1.6 (m, 2H), 1.4 (m, 4H).

Example 9

[0139] ##STR00010##

[0140] 1,8-dichloroanthraquinone (5.0 parts) (commercial available such as from Sigma Aldrich) and 4-hydroxybenzenethiol (9.1 parts) are added to N-methyl-2-pyrrolidone (100 mL) and stirred at room temperature. Potassium carbonate (3.0 parts) is added and the reaction mixture is heated to 100 C. for 4 hours. Temperature is decreased to room temperature and ethyl acetate (400 mL) is added. The organic phase is successively washed with 1 wt % aqueous hydrochloric acid solution (2200 mL) and saturated aqueous sodium chloride solution (2200 mL). The organic phase is dried over sodium sulfate, filtered, evaporated and the obtained solid is finally dried overnight at 50 C. under vacuum to afford 6.8 parts of compound (9) as a yellow-orange solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 10.0 (s, 2H), 7.9 (d, 2H), 7.6 (t, 2H), 7.4 (d, 4H), 7.1 (d, 2H), 6.9 (d, 4H).

Example 10

[0141] ##STR00011##

[0142] Compound (9) (2.6 parts), mono-2-(methacryloyl)ethyl succinate (3.3 parts), dicyclohexylcarbodiimide (3.0 parts) and 2,6-di-tert-butyl-4-methylphenol (0.01 part) are dissolved in dichloromethane (100 mL). 4-Dimethylaminopyridine (0.4 part) is added and the mixture is stirred 5 hours at room temperature. The reaction mixture is then filtered over celite and the filtrate poured in n-heptane (400 mL) with efficient stirring. The resulting precipitate is filtered, successively washed with a mixture composed of ethyl acetate/n-heptane (1/2; 300 mL), methanol (300 mL) and finally dried overnight at 50 C. under vacuum to afford 4.0 parts of compound (10) as an orange solid. NMR-.sup.1H (CDCl.sub.3, 300 MHz, ppm): 8.1 (d, 2H), 7.7 (d, 4H), 7.4 (t, 2H), 7.3 (d, 4H), 7.2 (d, 2H), 6.1 (s, 2H), 5.6 (s, 2H), 5.4 (m, 8H), 2.9 (m, 4H), 2.8 (m, 4H), 1.9 (s, 6H).

Example 11

[0143] ##STR00012##

[0144] 1,8-dichloroanthraquinone (10.0 parts) and 4-aminobenzenethiol (11.4 parts) are added to N-methyl-2-pyrrolidone (100 mL) and stirred at room temperature. Potassium carbonate (12.5 parts) is added and the reaction mixture is heated to 100 C. for 4 hours. Temperature is decreased to room temperature and methanol (250 mL) is added dropwise with efficient stirring. The resulting precipitate is filtered, successively washed with methanol (250 mL), water (500 mL) and finally dried overnight at 50 C. under vacuum to afford 15.1 parts of compound (11) as a yellow-orange solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 7.9 (d, 2H), 7.6 (m, 2H), 7.2 (d, 4H), 7.1 (d, 2H), 6.7 (d, 4H), 5.6 (s, 4H).

Example 12

[0145] ##STR00013##

[0146] Compound (11) (3.0 parts), mono-2-(methacryloyl)ethyl succinate (4.6 parts), dicyclohexylcarbodiimide (4.0 parts) and 2,6-di-tert-butyl-4-methylphenol (0.01 part) are dissolved in dichloromethane (150 mL). 4-Dimethylaminopyridine (0.5 part) is added and the mixture is stirred 24 hours at room temperature. The reaction mixture is then filtered over celite and the filtrate is concentrated under vacuum. The product is purified by column chromatography (SiO.sub.2; eluent: toluene/ethyl acetate: 50/50) to afford after drying overnight at 50 C. under vacuum 4.2 parts of compound (12) as an orange. NMR-.sup.1H (CDCl.sub.3, ppm): 8.1 (d, 2H), 7.9 (s, 2H), 7.7 (d, 4H), 7.6 (d, 4H), 7.4 (t, 2H), 7.1 (d, 2H), 6.2 (s, 2H), 5.6 (s, 2H), 4.4 (m, 8H), 2.8 (m, 4H), 2.6 (m, 2H), 1.9 (s, 6H).

Example 13

[0147] ##STR00014##

[0148] 1,8-Dichloroanthraquinone (104.0 parts), tosylamine (250.0 parts), potassium acetate (146.0 parts) and anhydrous copper acetate (5.0 parts) in amyl alcohol (1000 mL) are stirred and refluxed for 20 hours. Temperature is decreased to room temperature and methanol (1000 mL) is added. The precipitate is filtered, successively washed with methanol (1000 mL) and water (1000 mL). The obtained press-cake is dried overnight at 50 C. under vacuum to afford 185.0 parts of compound (13) as an orange solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 11.7 (s, 2H), 7.9 (d, 4H), 7.8 (m, 6H), 7.4 (d, 4H), 2.3 (s, 6H).

Example 14

[0149] ##STR00015##

[0150] Compound (13) (180.0 parts) is added portion-wise with efficient stirring to concentrated sulfuric acid (98%, 500 mL) at room temperature. The resulting mixture is heated to 60 C. for 2 hours. Temperature is decreased to room temperature and the obtained solution is slowly poured in a mixture of ice (1500 parts) and water (1000 mL). After 30 minutes of stirring, the resulting solid is filtered and washed with water (2000 mL). The filter cake is then slurried in 5 wt % aqueous Sodium hydroxide solution (500 mL) and stirred at room temperature for 1 hour. The precipitate is filtered, washed with water (1000 mL) and finally dried overnight at 50 C. under vacuum to afford 78.0 parts of compound (14) as a red solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 7.8 (broad, 4H), 7.6 (m, 2H), 7.3 (m, 2H), 7.1 (m, 2H).

Example 15

[0151] ##STR00016##

[0152] Compound (14) (10.0 parts) is dissolved in N-methyl-2-pyrrolidone (80 mL) and stirred at room temperature. N-bromosuccinimide (14.9 parts) dissolved in N-methyl-2-pyrrolidone (50 mL) is then added dropwise over a period of 30 minutes and the resulting mixture is stirred 2 hours at room temperature. Methanol (400 mL) is then added dropwise. The precipitate is filtered, successively washed with methanol (200 mL), water (200 mL) and finally dried overnight at 50 C. under vacuum to afford 15.8 parts of compound (15) as a brown solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 7.9 (broad, 4H), 7.6 (d, 2H), 6.9 (d, 2H).

Example 16

[0153] ##STR00017##

[0154] Compound (15) (2.7 parts) and 4-hydroxybenzenethiol (2.6 parts) are added to N-methyl-2-pyrrolidone (25 mL) and stirred at room temperature. Potassium carbonate (2.8 parts) is added and the reaction mixture is heated to 80 C. for 1 hour. Temperature is decreased to room temperature and a mixture composed of water (200 mL) and acetic acid (20 mL) is added dropwise with stirring. The precipitate is filtered, washed with water (1000 mL) and finally dried overnight at 50 C. under vacuum to afford 2.7 parts of compound (16) as a dark blue-violet solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 9.9 (s, 2H), 7.9 (broad, 4H), 7.4 (d, 4H), 7.0 (d, 2H), 6.9 (d, 4H), 6.7 (d, 2H).

Example 17

[0155] ##STR00018##

[0156] Compound (16) (2.5 parts), 10-bromodecyl-1-methacrylate (3.8 parts; synthesized from 10-bromodecan-1-ol in a similar way as compound (3)), potassium carbonate (1.7 parts) and 2,6-di-tert-butyl-4-methylphenol (0.01 part) are mixed in N-methyl-2-pyrrolidone (30 mL) and heated to 90 C. for 3 hours. Temperature is decreased to room temperature and ethyl acetate (300 mL) is added. The organic phase is successively washed with water (2150 mL) and saturated aqueous sodium chloride solution (2150 mL). The organic layer is dried over sodium sulfate, filtered and evaporated. The product is further purified by column chromatography (SiO.sub.2; eluent: toluene/ethyl acetate: 95/5) to afford 1.5 parts of compound (17) as a dark blue-violet solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 8.0 (broad, 4H), 7.5 (d, 4H), 7.1 (d, 4H), 7.0 (d, 2H), 6.7 (d, 2H), 6.0 (s, 2H), 5.6 (s, 2H), 4.1 (m, 4H), 4.0 (m, 4H), 1.9 (s, 6H), 1.7 (m, 4H), 1.6 (m, 4H), 1.4-1.2 (m, 24H).

Example 18

[0157] ##STR00019##

[0158] Compound (14) (58.0 parts) is dissolved in concentrated sulfuric acid (98%, 170 mL) at 60 C. When the product is completely dissolved, the temperature is decreased to room temperature before slow addition of ice (850.0 parts) with efficient stirring. To the resulting slurry at 0-5 C. is then added dropwise bromine (182.0 parts) over a period of 3 hours. The resulting mixture is stirred at room temperature for 20 hours. Excess bromine is then removed by bubbling nitrogen in the reaction mixture. The precipitate is then filtered, successively washed with water (1000 mL), 8 wt % aqueous sodium hydroxide solution (1000 mL), 20 wt % aqueous sodium bisulfite solution (400 mL), water (3000 mL) and finally dried overnight at 50 C. under vacuum to afford 119.0 parts of compound (18) as a reddish-brown solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 8.1 (s, 2H), 7.9 (broad, 4H).

Example 19

[0159] ##STR00020##

[0160] Compound (18) (119.0 parts), tosylamine (150.0 parts), potassium acetate (53.0 parts) and anhydrous copper acetate (4.0 parts) in amyl alcohol (1700 mL) are stirred and refluxed for 10 hours. Temperature is decreased to room temperature and methanol (850 mL) is added. The precipitate is filtered, successively washed with methanol (1000 mL) and water (2000 mL). The obtained press-cake is dried overnight at 50 C. under vacuum to afford 150.0 parts of compound (19) as a dark blue solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 11.0 (s, 2H), 8.0 (s, 2H), 7.9 (broad, 4H), 7.7 (d, 4H), 7.3 (d, 4H), 2.3 (s, 6H).

Example 20

[0161] ##STR00021##

[0162] Compound (4) (4.0 parts) is dissolved in N-methyl-2-pyrrolidone (25 mL) at room temperature. Sodium hydride (60% dispersion in mineral oil, 0.5 part) is added and the resulting mixture is stirred 30 minutes at room temperature. Compound (19) (3.0 parts) and 2,6-di-tert-butyl-4-methylphenol (0.01 part) are then added and the resulting mixture is heated at 135 C. for 24 hours under nitrogen. Temperature is decreased to room temperature, ethyl acetate (200 mL) is added and the mixture is successively washed with 1 wt % aqueous hydrochloric acid solution (3200 mL) and saturated aqueous sodium chloride solution (3200 mL). The organic layer is dried over sodium sulfate, filtered and evaporated. The product is further purified by column chromatography (SiO.sub.2; eluent: toluene/ethyl acetate: 98/2) to afford 2.0 parts of compound (20) as a dark blue-violet solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 12.3 (s, 2H), 7.4 (d, 4H), 7.3 (d, 4H), 7.2 (d, 4H), 7.1 (d, 4H), 6.8 (s, 2H), 6.0 (s, 2H), 5.6 (s, 2H), 4.1 (m, 8H), 2.3 (s, 6H), 1.9 (s, 6H), 1.8 (m, 4H), 1.6 (m, 4H), 1.4 (m, 8H).

Example 21

[0163] ##STR00022##

[0164] Compound (19) (10.0 parts) is added portion-wise with efficient stirring to concentrated sulfuric acid (98%, 60 mL) at room temperature. The resulting mixture is heated to 60 C. for 2 hours. Temperature is decreased to room temperature and the obtained solution is slowly poured in a mixture of ice (300 parts) and water (300 mL). After 30 minutes stirring, the resulting solid is filtered and washed with water (500 mL). The filter cake is then slurried in 5 wt % aqueous sodium hydroxyde solution (300 mL) and stirred at room temperature for 1 hour. The precipitate is filtered, washed with water (500 mL) and finally dried overnight at 50 C. under vacuum to afford 5.8 parts of compound (21) as a blue-violet solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 7.7 (broad, 8H), 7.5 (s, 2H).

Example 22

[0165] ##STR00023##

[0166] Compound (21) (5.0 parts), 4-hydroxyphenyl boronic acid (4.9 parts), potassium carbonate (5.0 parts) and tretakis-triphenylphosphine palladium (1.3 parts) are mixed in N-methyl-2-pyrrolidone (90 mL) and deionized water (10 mL) and heated to 100 C. for 3 hours under nitrogen. Temperature is decreased to room temperature and the reaction mixture is poured in deionized water (800 mL). The precipitate is filtered, washed with water (350 mL) and dried at 50 C. under vacuum. The resulting solid is dissolved in tetrahydrofurane (1000 mL) with heating and filtered over celite while still hot. To the filtrate is added toluene (500 mL) and tetrahydrofurane is evaporated under vacuum. The precipitate is filtered, washed with toluene (300 mL) and dried overnight at 50 C. under vacuum to afford 4.6 parts of compound (22) as a dark blue solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 9.7 (s, 2H), 7.7 (s, 4H), 7.4 (broad, 4H), 7.3 (d, 4H), 6.9 (s, 2H), 6.8 (d, 4H).

Example 23

[0167] ##STR00024##

[0168] Compound (22) (1.0 part), 10-bromodecyl-1-methacrylate (2.0 parts; synthesized from 10-bromodecan-1-ol according to example 3), potassium carbonate (0.76 part) and 2,6-di-tert-butyl-4-methylphenol (0.01 part) are mixed in N-methyl-2-pyrrolidone (25 mL) and heated to 80 C. for 3 hours. Temperature is decreased to room temperature and ethyl acetate (300 mL) is added. The organic phase is successively washed with 1 wt % aqueous hydrochloric acid solution (3150 mL) and saturated aqueous sodium chloride solution (3150 mL). The organic layer is dried over sodium sulfate, filtered and evaporated. The product is further purified by column chromatography (SiO.sub.2; eluent: toluene/ethyl acetate: 95/5) to afford 1.4 parts of compound (23) as a dark blue-violet solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 7.7 (broad, 4H), 7.4 (d, 4H), 7.3 (broad, 4H), 7.1 (d, 4H), 6.9 (s, 2H), 6.0 (s, 2H), 4.1 (m, 4H), 4.0 (m, 4H), 1.9 (s, 6H), 1.8 (m, 4H), 1.6 (m, 4H), 1.4-1.2 (m, 24H).

Example 24

[0169] ##STR00025##

[0170] Compound (19) (11.0 parts) and hydroquinone (16.0 parts) are added to N-methyl-2-pyrrolidone (80 mL) and stirred at room temperature. Potassium carbonate (4.5 parts) are added and the reaction mixture is heated to 120-130 C. for 5 hours. Temperature is decreased to room temperature and the resulting mixture is poured in 5 wt % aqueous hydrochloric acid (400 mL) with efficient stirring. The precipitate is filtered, successively washed with 1 wt % aqueous hydrochloric acid solution (200 mL), water (1000 mL) and finally dried overnight at 50 C. under vacuum to afford 11.0 parts of compound (24) as a dark blue-violet solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 12.4 (s, 2H), 9.7 (s, 2H), 7.4 (d, 4H), 7.3 (d, 4H), 7.0 (m, 8H), 6.9 (s, 2H), 2.3 (s, 6H).

Example 25

[0171] ##STR00026##

[0172] Compound (24) (7.0 parts), 4-(6-acryloyloxy-hexyl-1-oxy)benzoic acid (7.7 parts; synthesized according to U.S. Pat. No. 6,258,974 or EP-1174411), dicyclohexylcarbodiimide (5.3 parts) and 2,6-di-tert-butyl-4-methylphenol (0.01 part) are dissolved in dichloromethane (200 mL). 4-Dimethylaminopyridine (0.5 part) is added and the mixture is stirred 5 hours at room temperature. The reaction mixture is then filtered over celite and the filtrate poured in methanol (400 mL) with efficient stirring. The resulting precipitate is filtered, washed with methanol (300 mL) and purified by column chromatography (SiO.sub.2; eluent: toluene/ethyl acetate: 90/10). The resulting product is finally dried overnight at 50 C. under vacuum to afford 9.0 parts of compound (25) as a dark blue-violet solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 12.3 (s, 2H), 8.1 (d, 4H), 7.5 (m, 8H), 7.4 (d, 4H), 7.2 (d, 4H), 7.1 (d, 4H), 6.9 (s, 2H), 6.4-5.9 (m, 6H), 4.1 (m, 8H), 2.3 (s, 6H), 1.8 (m, 4H), 1.6 (m, 4H), 1.4 (m, 8H).

Example 26

[0173] ##STR00027##

[0174] Compound (24) (2.0 parts), mono-2-(methacryloyl)ethyl succinate (1.5 parts), dicyclohexylcarbodiimide (1.3 parts) and 2,6-di-tert-butyl-4-methylphenol (0.01 part) are dissolved in dichloromethane (75 mL). 4-Dimethylaminopyridine (0.4 part) is added and the mixture is stirred 20 hours at room temperature. The reaction mixture is then filtered over celite and the filtrate poured in n-heptane (250 mL) with efficient stirring. The resulting precipitate is filtered, successively washed with n-heptane (250 mL), methanol (250 mL) and finally dried overnight at 50 C. under vacuum to afford 2.7 parts of compound (26) as a dark blue-violet solid. NMR-.sup.1H (CDCl.sub.3, 300 MHz, ppm): 12.3 (s, 2H), 7.5 (d, 4H), 7.3-7.0 (m, 14H), 6.1 (s, 2H), 5.6 (s, 2H), 4.4 (m, 8H), 2.9 (m, 4H), 2.8 (m, 4H), 2.4 (s, 6H), 1.9 (s, 6H).

Example 27

[0175] ##STR00028##

[0176] Compound (19) (2.0 parts) and 4,4-dihydroxybiphenyl (5.0 parts) are added to N-methyl-2-pyrrolidone (25 mL) and stirred at room temperature. Potassium carbonate (0.8 part) is added and the reaction mixture is heated to 140 C. for 5 hours. Temperature is decreased to room temperature and the resulting mixture is poured in 5 wt % aqueous hydrochloric acid solution (300 mL) with efficient stirring. The precipitate is filtered and washed with water (300 mL). The solid is then stirred in hot methanol (300 mL), filtered, washed with methanol (200 mL) and finally dried overnight at 50 C. under vacuum to afford 2.3 parts of compound (27) as a dark blue-violet solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 12.3 (s, 2H), 9.6 (s, 2H), 7.8 (d, 4H), 7.7 (d, 4H), 7.5 (d, 4H), 7.3 (d, 4H), 7.2 (d, 4H), 7.0 (d, 4H), 6.9 (s, 2H), 2.3 (s, 6H).

Example 28

[0177] ##STR00029##

[0178] Compound (27) (2.0 parts), 4-(6-acryloyloxy-hexyl-1-oxy)benzoic acid (2.0 parts; synthesized according to U.S. Pat. No. 6,258,974 or EP-1174411), dicyclohexylcarbodiimide (1.4 parts) and 2,6-di-tert-butyl-4-methylphenol (0.01 part) are dissolved in tetrahydrfurane (100 mL). 4-Dimethylaminopyridine (0.2 part) is added and the mixture is stirred 24 hours at room temperature. The reaction mixture is then filtered over celite and the filtrate is evaporated. The resulting solid is further purified by column chromatography (SiO.sub.2; eluent: toluene/ethyl acetate: 95/5) and finally dried overnight at 50 C. under vacuum to afford 2.1 parts of compound (28) as a dark blue-violet solid. NMR-.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 12.2 (s, 2H), 8.1 (d, 4H), 7.9 (m, 8H), 7.4 (m, 8H), 7.3 (m, 8H), 7.1 (d, 4H), 6.9 (s, 2H), 6.4-5.9 (m, 6H), 4.1 (m, 8H), 2.3 (s, 6H), 1.8 (m, 4H), 1.6 (m, 4H), 1.4-1.2 (m, 8H).

Preparation of Dichroic Mixtures M.SUB.LCP

[0179] Dichroic mixtures M.sub.LCP were prepared as illustrated in table 1:

TABLE-US-00001 TABLE 1 Mixture composition LCP Photo- Mixture Dichroic Dye component .sup.a) initiator .sup.b) Total Color M.sub.LCP1 Compound (6) 88 wt % 2 wt % 100 wt % Pink- 10 wt % Red M.sub.LCP2 Compound (8) 88 wt % 2 wt % 100 wt % Pink- 10 wt % Red M.sub.LCP3 Compound (10) 88 wt % 2 wt % 100 wt % Yellow 10 wt % M.sub.LCP4 Compound (12) 88 wt % 2 wt % 100 wt % Yellow 10 wt % M.sub.LCP5 Compound (17) 88 wt % 2 wt % 100 wt % Blue 10 wt % M.sub.LCP6 Compound (20) 88 wt % 2 wt % 100 wt % Blue 10 wt % M.sub.LCP7 Compound (23) 88 wt % 2 wt % 100 wt % Blue 10 wt % M.sub.LCP8 Compound (25) 88 wt % 2 wt % 100 wt % Blue 10 wt % M.sub.LCP9 Compound (26) 88 wt % 2 wt % 100 wt % Blue 10 wt % M.sub.LCP10 Compound (28) 88 wt % 2 wt % 100 wt % Blue 10 wt % M.sub.LCP11 Compound (12) 88 wt % 2 wt % 100 wt % Grey 5 wt % Compound (25) 4 wt % Compound (6) 1 wt % M.sub.LCP12 Compound (12) 88 wt % 2 wt % 100 wt % Green 6.7 wt % Compound (25) 3.3 wt % M.sub.LCP13 Compound (25) 88 wt % 2 wt % 100 wt % Violet 5 wt % Compound (6) 5 wt % M.sub.LCP14 Compound (10) 88 wt % 2 wt % 100 wt % Grey 5 wt % Compound (17) 3.3 wt % Compound (8) 1.7 wt % M.sub.LCP15 Compound (17) 88 wt % 2 wt % 100 wt % Violet 5 wt % Compound (8) 5 wt % M.sub.LCP16 Compound (10) 88 wt % 2 wt % 100 wt % Green 6 wt % Compound (17) 4 wt % wt % = weight %

[0180] a) LCP component used in the above mixtures is described in WO 2011003846, on page 29 and have the following structure:

##STR00030##

[0181] b) Photoinitiator is Irgacure 369 from BASF.

[0182] The mixtures M.sub.LCP1 to M.sub.LCP16 are used to produce oriented, dichroic liquid crystal samples on plastic substrates as described below.

Production of Dichroic LCP Layers

[0183] Sixteen samples P.sub.1 to P.sub.16 are prepared, whereby each single specimen comprised an alignment layer and a dichroic liquid crystal polymer layer. The alignment layers are manufactured using the linearly photo-polymerizable aligning (LPP) technique. The dichroic liquid crystal polymer layers are oriented by the adjacent LPP layers. The manufacturing processes of both layers are described in the following.

[0184] For the production of an LPP orientation layer, suitable LPP materials are described for example in patent publications EP 0 611 786, WO 96/10049, EP 0 763 552 and U.S. Pat. No. 6,107,427, and include cinnamic acid derivatives and ferulic acid derivatives. For the examples, the following LPP material is chosen, which is described in WO2012/08504, example 1:

##STR00031##

[0185] A 4 wt % solution of the above mentioned LPP material in a mixture of solvent composed of methylethylketone and cyclohexanone (80/20 w/w) is coated on a BOPP (50 m) substrate using a bar coater (KBar 0). The foil is then warmed for 30 seconds at 80 C. in an oven. The resulting layer has a thickness of approximately 100 nanometers.

[0186] The coated film is then exposed to linearly polarized UV light from a mercury high pressure lamp using an energy dose of 300 mJ/cm.sup.2 at room temperature.

[0187] The layer is then used as an orientation layer for a liquid crystal material comprising dichroic dyes.

[0188] For the production of the dichroic LCP layers, the mixtures M.sub.LCP1 to M.sub.LCP16 are dissolved in a mixture of solvent composed of methylethylketone and cyclohexanone (80/20 w/w) to give a 40 wt % solution. These LCP mixtures, which include dichroic dyes, are then coated on top of the photo-exposed LPP layers using a bar coater (KBar 2). The coated dichroic LCP layers are then dried at 60 C. for approximately 30 seconds in an oven. For photo-initiated cross-linking of the liquid crystals and dye components, the layers are exposed to isotropic light from a xenon lamp using an energy dose of 1500 mJ/cm.sup.2 at room temperature in an inert atmosphere. The resulting layer has a thickness of approximately 3 micrometers.

[0189] The procedure described above gives photo-aligned dichroic LCP layers on plastic substrates leading to sixteen different samples P1 to P16 derived from the sixteen dichroic LCP mixtures M.sub.LCP1 to M.sub.LCP16.

[0190] Order parameters of samples P.sub.1 to P.sub.16:

[0191] The order parameter S of a dichroic dye is given by the following expression:

S=D.sub.D.sub./D.sub.+2 D.sub.

wherein D.sub. and D.sub. are the optical densities of a dichroic dye in a liquid crystal measured for light polarizations parallel and perpendicular to the liquid crystal director.

[0192] Table 2 shows the order parameters S of samples P.sub.1 to P.sub.16 measured at the indicated wavelength.

TABLE-US-00002 TABLE 2 Samples M.sub.LCP (nm) S P.sub.1 M.sub.LCP1 584 0.47 P.sub.2 M.sub.LCP2 522 0.47 P.sub.3 M.sub.LCP3 452 0.45 P.sub.4 M.sub.LCP4 458 0.52 P.sub.5 M.sub.LCP5 616 0.55 P.sub.6 M.sub.LCP6 608 0.45 P.sub.7 M.sub.LCP7 672 0.55 P.sub.8 M.sub.LCP8 608 0.61 P.sub.9 M.sub.LCP9 574 0.43 P.sub.10 M.sub.LCP10 606 0.59 P.sub.11 M.sub.LCP11 582 0.57 P.sub.12 M.sub.LCP12 608 0.56 P.sub.13 M.sub.LCP13 584 0.46 P.sub.14 M.sub.LCP14 614 0.46 P.sub.15 M.sub.LCP15 614 0.49 P.sub.16 M.sub.LCP16 614 0.48

[0193] All samples P.sub.1 to P16 are cross-linked successfully. The surfaces are completely dry and are more or less resistant against scratches.