DICHROIC DYE COMPOSITION

Abstract

The present invention relates to compositions comprising a combination of benzothiadiazole and thiadiazoloquinoxaline derivatives, to liquid-crystalline media containing the compositions, and to the use of the compositions and the media in optical, electronic and electro-optical devices, in particular in devices for regulating the passage of energy from an outside space into an inside space, for example in switchable windows.

Claims

1. A composition comprising one or more compounds of formula I ##STR00704## and one or more compounds of formula II ##STR00705## wherein R.sup.1 on each occurrence, identically or differently, denotes H, F, CN, N(R.sup.z).sub.2, Si(R.sup.z).sub.3, or a straight-chain or branched alkyl or alkoxy having 1 to 20 C atoms, in which, in addition, one or more non-adjacent CH.sub.2 groups may each be replaced, independently of one another, by —C(R.sup.z)═C(R.sup.z)—, —C≡C—, ##STR00706## —N(R.sup.z)—, —O—, —S—, —CO—, —CO—O—, —O—CO— or —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 be replaced by F or CN, X on each occurrence, identically or differently, denotes CR.sup.a or N, R.sup.a on each occurrence, identically or differently, denotes straight-chain or branched alkyl having 1 to 12 C atoms, F, Cl, N(R.sup.z).sub.2 or CN, R.sup.2 and R.sup.z on each occurrence, identically or differently, denote H, halogen, straight-chain, branched or cyclic alkyl having 1 to 12 C atoms, in which, in addition, one or more non-adjacent CH.sub.2 groups may be replaced by —O—, —S—, —CO—, —CO—O—, —O—CO— or —O—CO—C— 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 be replaced by F or Cl, Ar.sup.1 and Ar.sup.2 on each occurrence, identically or differently, denote an aryl or heteroaryl group, which may be substituted by one or more radicals L, L on each occurrence, identically or differently, denotes F, CO, CN, OH, SCN, SF.sub.5, N(R.sup.z).sub.2 or straight-chain or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, Z.sup.1 on each occurrence, identically or differently, denotes a single bond, —O—, —S—, —C(O)—, —CR.sup.y1R.sup.y2—, —CF.sub.2O—, —OCF.sub.2—, —C(O)—O—, —O—C(O)—, —OCH.sub.2—, —CH.sub.2O—, —CR.sup.x1═CR.sup.x2—, —C≡C—, —CR.sup.x1═CR.sup.x2—CO—, —CO—CR.sup.x1═CR.sup.x2—, —CR.sup.x1═CR.sup.x2—COO—, —OCO—CR.sup.x1═CR.sup.x2— or —N═N—, Z.sup.2 on each occurrence, identically or differently, denotes a single bond, —CF.sub.2O—, —OCF.sub.2— or —C≡C—, a, b, c and d independently of one another, denote 0 or 1, R.sup.x1, R.sup.x2 independently of one another, denote H, F, Cl, CN or alkyl having 1 to 12 C atoms, R.sup.y1 denotes H or alkyl having 1 to 12 C atoms, and R.sup.y2 denotes alkyl having 1 to 12 C atoms.

2. The composition according to claim 1, wherein two or more compounds of the formula I and two or more compounds of the formula II are comprised in the composition.

3. The composition according to claim 1, wherein Ar.sup.1 and Ar.sup.2 denote, independently of one another, 1,4-phenylene, 1,4-naphthylene, 2,6-naphthylene, thiazole-2,5-diyl, thiophene-2,5-diyl or thienothiophene-2,5-diyl, wherein one or more H atoms may be replaced by the group L as defined in claim 1.

4. The composition according to claim 1, wherein at least one of Ar.sup.1 is thiophene-2,5-diyl or thienothiophene-2,5-diyl, preferably is thiophene-2,5-diyl.

5. The composition according to claim 1, wherein R.sup.1 identically or differently, denotes a straight-chain or branched, preferably branched, alkyl or alkoxy having 1 to 15 C atoms or N(R.sup.b).sub.2, where R.sup.b is, independently of one another, a straight-chain alkyl having 1 to 9 C atoms, preferably ethyl, butyl, and hexyl, R.sup.2 identically or differently, denotes a straight-chain alkyl having 1 to 9 C atoms, preferably ethyl, a, b, c and d denote 1, Z.sup.1 is a single bond, and Z.sup.2 is a single bond.

6. The composition according to claim 1, wherein the composition comprises at least one purple dye, at least one blue dye, at least one yellow dye, at least one red dye and at least one near-infrared dye.

7. The composition according to claim 1, wherein the composition comprises at least one compound, preferably two or more compounds, selected from the compounds of formulae I-1, I-2, I-3 and I-4 ##STR00707## and at least one compound, preferably two or more compounds, selected from the compounds of formulae II-1, II-2, II-3, II-4 and II-5 ##STR00708## ##STR00709##

8. A liquid-crystalline medium comprising the composition according to claim 1 and one or more mesogenic compounds.

9. The liquid-crystalline medium according to claim 8, wherein the medium comprises one or more compounds selected from the group of compounds of formulae CY, PY and AC ##STR00710## wherein ##STR00711## denotes ##STR00712## denote ##STR00713## denotes ##STR00714## R.sup.1, R.sup.2, R.sup.AC1, R.sup.AC2 each, independently of one another, denote alkyl having 1 to 12 C atoms, where, in addition, one or two non-adjacent CH.sub.2 groups may be replaced by —O—, —CH═CH—, —CO—, —OCO— or —COO— in such a way that O atoms are not linked directly to one another, Z.sup.x, Z.sup.y, Z.sup.AC each, independently of one another, denote —CH.sub.2CH.sub.2—, —CH═CH—, —CF.sub.2O—, —OCF.sub.2—, —CH.sub.2O—, —OCH.sub.2—, —CO—O—, —O—CO—, —C.sub.2F.sub.4—, —CF═CF—, —CH═CH—CH.sub.2O— or a single bond, L.sup.1, L.sup.2, L.sup.3, L.sup.4 each, independently of one another, denote F, Cl, CN, OCF.sub.3, CF.sub.3, CH.sub.3, CH.sub.2F, CHF.sub.2. a is 1 or 2, b is 0 or 1, c is 0, 1 or 2, d is 0 or 1.

10. The liquid-crystalline medium according to claim 8, wherein the medium comprises one or more compounds selected from the group of compounds of formulae IIA to VIII ##STR00715## wherein ##STR00716## each, independently of one another, denote ##STR00717## R.sup.20 identically or differently, denotes a halogenated or unsubstituted alkyl or alkoxy radical having 1 to 15 C atoms, where, in addition, one or more CH.sub.2 groups in these radicals may each be replaced, independently of one another, by —C≡C—, —CF.sub.2O—, —CH═CH—, ##STR00718## —O—, —CO—O— or —O—CO— in such a way that O atoms are not linked directly to one another, X.sup.20 identically or differently, denotes F, Cl, CN, SF.sub.5, SCN, NCS, a halogenated alkyl radical, a halogenated alkenyl radical, a halogenated alkoxy radical or a halogenated alkenyloxy radical, each having 1 to 6 C atoms, and Y.sup.20, Y.sup.21, Y.sup.22, Y.sup.23, Y.sup.24 each, identically or differently, denote H or F, Z.sup.20 denotes —C.sub.2H.sub.4—, —(CH.sub.2).sub.4—, —CH═CH—, —CF═CF—, —C.sub.2F.sub.4—, —CH.sub.2CF.sub.2—, —CF.sub.2CH.sub.2—, —CH.sub.2O—, —OCH.sub.2—, —COO— or —OCF.sub.2—, in formulae V and VI also a single bond, in formulae V and VIII also —CF.sub.2O—, r denotes 0 or 1, and s denotes 0 or 1.

11. The liquid-crystalline medium according to claim 8, wherein the medium additionally comprises one or more compounds selected from the group of compounds of formulae DK and O ##STR00719## wherein R.sup.5, R.sup.6, R.sup.O1 and R.sup.O2 each, independently of one another, denote alkyl having 1 to 12 C atoms, where, in addition, one or two non-adjacent CH.sub.2 groups may be replaced by —O—, —CH═CH—, —CO—, —OCO— or —COO— in such a way that O atoms are not linked directly to one another, ##STR00720## denotes ##STR00721## denotes ##STR00722## denotes ##STR00723## denotes ##STR00724## Z.sup.O1 denotes —CH.sub.2CH.sub.2—, —CF.sub.2CF.sub.2—, —C═C— or a single bond, Z.sup.O2 denotes CH.sub.2O, —C(O)O—, —CH.sub.2CH.sub.2—, —CF.sub.2CF.sub.2—, or a single bond, o is 1 or 2, and e is 1 or 2.

12. The liquid-crystalline medium according to claim 1, wherein the medium additionally comprises one or more compounds selected from the group of compounds of formulae O3 to O5 ##STR00725## wherein R.sup.O1 and R.sup.O2, identically or differently, denote straight-chain alkyl having 1 to 6 C atoms or straight-chain alkenyl having 2 to 6 C atoms.

13. The liquid-crystalline medium according to claim 8, wherein the medium additionally comprises one or more compounds selected from the group of compounds of formulae DK1 to DK12: ##STR00726## in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1 to 6 C atoms, and alkenyl denotes a straight-chain alkenyl radical having 2 to 6 C atoms.

14. A device for regulating the passage of energy from an outside space into an inside space, wherein the device contains a switching layer comprising the liquid-crystalline medium according to claim 8.

15. A window comprising the device according to claim 14.

16. An electro-optical display, a device for regulating the passage of energy from an outside space into an inside space, an electrical semiconductor, an organic field-effect transistor, a printed circuit, a radio frequency identification element, an organic light-emitting diode, a lighting element, a photovoltaic device, an optical sensor, an effect pigment, a decorative element or as a dye for colouring polymers, which comprises a composition according to claim 1.

17. An architectural window or a car sunroof, which comprises a liquid crystalline medium according to claim 8.

Description

EXAMPLES

[0436] In the Examples, [0437] V.sub.o denotes threshold voltage, capacitive [V] at 20° C., [0438] n.sub.e denotes extraordinary refractive index at 20° C. and 589 nm, [0439] n.sub.o denotes ordinary refractive index at 20° C. and 589 nm, [0440] Δn denotes optical anisotropy at 20° C. and 589 nm, [0441] ε.sub.∥ denotes dielectric permittivity parallel to the director at 20° C. and 1 kHz, [0442] ε.sub.⊥ denotes dielectric permittivity perpendicular to the director at 20° C. and 1 kHz, [0443] Δε denotes dielectric anisotropy at 20° C. and 1 kHz, [0444] cl.p., T(N,I) denotes clearing point [° C.], [0445] γ.sub.1 denotes rotational viscosity measured at 20° C. [mPa-s], determined by the rotation method in a magnetic field, [0446] K.sub.1 denotes elastic constant, “splay” deformation at 20° C. [pN], [0447] K.sub.2 denotes elastic constant, “twist” deformation at 20° C. [pN], [0448] K.sub.3 denotes elastic constant, “bend” deformation at 20° C. [pN],

[0449] The term “threshold voltage” for the present invention relates to the capacitive threshold (V.sub.0), unless explicitly indicated otherwise. In the Examples, as is generally usual, the optical threshold can also be indicated for 10% relative contrast (V.sub.10).

Reference Example 1

[0450] A liquid-crystal base mixture B-1 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

TABLE-US-00008 CPG-3-F 8.00% clearing point [° C.]: 114 CPG-5-F 8.00% Δn [589 nm, 20° C.]: 0.130 CPU-5-F 14.00%  n.sub.e [589 nm, 20° C.]: 1.62 CPU-7-F 11.00%  Δε [1 kHz, 20° C.]: 10.0 CP-5-N 18.00%  ε.sub.⊥ [1 kHz, 20° C.]: 4.0 CP-7-N 13.00%  CCGU-3-F 7.00% CC-3-O3 2.00% CBC-33F 4.00% CBC-53F 4.00% CBC-55F 3.00% CCZPC-3-3 3.00% CCZPC-3-4 3.00% CCZPC-3-5 2.00% Σ 100.00% .sup.  

Reference Example 2

[0451] A liquid-crystal base mixture B-2 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

TABLE-US-00009 CPG-3-F 5.00% clearing point [° C.]: 114.5 CPG-5-F 5.00% Δn [589 nm, 20° C.]: 0.135 CPU-3-F 15.00%  n.sub.e [589 nm, 20° C.]: 1.63 CPU-5-F 15.00%  Δε [1 kHz, 20° C.]: 11.3 CP-3-N 16.00%  ε.sub.⊥ [1 kHz, 20° C.]: 4.2 CP-5-N 16.00%  K.sub.1 [pN, 20° C.]: 13.4 CCGU-3-F 7.00% K.sub.3 [pN, 20° C.]: 18.5 CBC-33F 4.00% V.sub.0 [V, 20° C.]: 1.15 CBC-53F 4.00% CBC-55F 4.00% CCZPC-3-3 3.00% CCZPC-3-4 3.00% CCZPC-3-5 3.00% Σ 100.00% .sup.  

[0452] A host mixture H-2 is prepared by mixing 99.97% of mixture B-2 with 0.03% of the compound of formula

##STR00691##

[0453] A mixture C-2 is prepared by mixing 99.95% of mixture H-2 with 0.05% of the compound of formula S-811 as described in Table F above.

Reference Example 3

[0454] A liquid-crystal base mixture B-3 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

TABLE-US-00010 CPG-3-F 8.00% CPG-5-F 8.00% CPU-5-F 14.00%  CPU-7-F 11.00%  CP-3-N 18.00%  CP-7-N 13.00%  CCGU-3-F 7.00% CC-3-O3 2.00% CBC-33F 4.00% CBC-53F 4.00% CBC-55F 3.00% CCZPC-3-3 3.00% CCZPC-3-4 3.00% CCZPC-3-5 2.00% Σ 100.00% .sup.  

Reference Example 4

[0455] A liquid-crystal base mixture B-4 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

TABLE-US-00011 CCU-1-F 5.00% clearing point [° C.]: 85 CCU-2-F 8.00% Δn [589 nm, 20° C.]: 0.071 CCU-3-F 10.00%  n.sub.e [589 nm, 20° C.]: 1.55 CCQU-3-F 11.00%  Δε [1 kHz, 20° C.]: 4.2 CCQU-5-F 9.00% ε.sub.⊥ [1 kHz, 20° C.]: 3.2 CCZC-3-3 3.00% CCZC-4-5 3.00% CCZPC-3-5 3.00% CC-3-O1 11.00%  CP-3-O1 12.00%  CC-3-V1 6.00% CCP-V-1 10.00%  CC-5-V 9.00% Σ 100.00% .sup.  

Reference Example 5

[0456] A liquid-crystal base mixture B-5 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

TABLE-US-00012 PGIGI-3-F 10.00%  clearing point [° C.]: 105 CPG-2-F 6.00% Δn [589 nm, 20° C.]: 0.160 CPG-3-F 7.00% n.sub.e [589 nm, 20° C.]: 1.66 CPG-5-F 5.00% Δε [1 kHz, 20° C.]: 11.4 CPU-5-F 10.00%  ε.sub.⊥ [1 kHz, 20° C.]: 4.3 CPG-7-F 10.00%  PGU-3-F 4.00% PGU-5-F 7.00% CCGU-3-F 8.00% CPP-3-2 4.00% CBC-33F 3.00% CBC-53F 3.00% CBC-55F 3.00% CPGU-3-OT 5.00% CP-5-N 15.00%  Σ 100.00% .sup.  

Reference Example 6

[0457] A liquid-crystal host mixture B-6 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

TABLE-US-00013 CP-5-N 15.00%  clearing point [° C.]: 92 CP-7-N 14.00%  Δn [589 nm, 20° C.]: 0.163 CPG-2-F 6.00% n.sub.e [589 nm, 20° C.]: 1.67 CPG-3-F 6.00% CPG-5-F 5.00% PGU-2-F 9.00% PGU-3-F 9.00% PGU-5-F 9.00% CPP-3-2 7.00% CBC-33F 3.00% CBC-53F 3.00% CBC-55F 3.00% CBC-33 4.00% PGIGI-3-F 7.00% Σ 100.00% .sup.  

Reference Example 7

[0458] A liquid-crystal base mixture B-7 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

TABLE-US-00014 CP-1V-N 10.00%  clearing point [° C.]: 113 PZG-3-N 4.00% Δn [589 nm, 20° C.]: 0.297 PZG-4-N 13.00%  n.sub.e [589 nm, 20° C.]: 1.82 PTP-1-O2 4.00% Δε [1 kHz, 20° C.]: 13.6 PTP-2-O1 5.00% ε.sub.⊥ [1 kHz, 20° C.]: 4.5 PTP-3-O1 5.00% CPTP-3-O1 4.00% PPTUI-3-2 20.00%  PPTUI-3-4 35.00%  Σ 100.00% .sup.  

[0459] A host mixture H-7 is prepared by mixing 98.41% of mixture B-7 with 1.59% of the compound of formula R-5011 as described in Table F above.

Reference Example 8

[0460] A liquid-crystal base mixture B-8 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

TABLE-US-00015 CC(CN)-4-7 14.00%  clearing point [° C.]: 114.6 CC(CN)-5-5 14.00%  Δn [589 nm, 20° C.]: 0.045 CC(CN)-3-3 6.00% n.sub.e [589 nm, 20° C.]: 1.52 CCZC-3-3 3.00% Δε [1 kHz, 20° C.]: −5.2 CCZC-3-5 3.00% ε.sub.⊥ [1 kHz, 20° C.]: 8.5 CCZC-4-3 3.00% CCZC-4-5 3.00% CC-3-O1 11.00%  CC-5-O1 4.00% CC-5-O2 4.00% CC(CN)C-3-5 10.00%  CC(CN)C-5-5 12.00%  CC(CN)C-5-3 10.00%  CCZPC-3-3 3.00% Σ 100.00% .sup.  

Reference Example 9

[0461] A liquid-crystal base mixture B-9 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

TABLE-US-00016 CY-3-O2 9.00% clearing point [° C.]: 110.5 CY-3-O4 9.00% Δn [589 nm, 20° C.]: 0.132 CY-5-O2 12.00%  n.sub.e [589 nm, 20° C.]: 1.62 CY-5-O4 8.00% Δε [1 kHz, 20° C.]: −4.9 CCY-3-O2 5.00% ε.sub.⊥ [1 kHz, 20° C.]: 8.8 CCY-3-O3 5.00% K.sub.1 [pN, 20° C.]: 16.8 CCY-4-O2 5.00% K.sub.3 [pN, 20° C.]: 20.4 CPY-2-O2 7.00% V.sub.0 [V, 20° C.]: 2.14 CPY-3-O2 6.00% PYP-2-3 12.00%  CCP-V-1 6.00% CCZPC-3-3 3.00% CCZPC-3-4 3.00% CBC-33F 5.00% CBC-53F 5.00% Σ 100.00% .sup.  

[0462] A host mixture H-9 is prepared by mixing 99.97% of mixture B-9 with 0.03% of the compound of formula

##STR00692##

Reference Example 10

[0463] A liquid-crystal base mixture B-10 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

TABLE-US-00017 CY-3-O4 25.00%  clearing point [° C.]: 75.4 CCY-3-O2 6.00% Δn [589 nm, 20° C.]: 0.100 CCY-3-O3 7.00% n.sub.e [589 nm, 20° C.]: 1.58 CPY-2-O2 8.00% Δε [1 kHz, 20° C.]: −3.0 CPY-3-O2 8.00% ε.sub.⊥ [1 kHz, 20° C.]: 6.4 PYP-2-3 3.00% K.sub.1 [pN, 20° C.]: 12.8 CC-3-V1 9.00% K.sub.3 [pN, 20° C.]: 14.4 CC-3-V 25.00%  V.sub.0 [V, 20° C.]: 2.32 BCH-32 9.00% Σ 100.00% .sup.  

Reference Example 11

[0464] A liquid-crystal base mixture B-11 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

TABLE-US-00018 CC-3-O1 10.00% clearing point [° C.]: 74.5 CC-3-4  8.00% Δn [589 nm, 20° C.]: 0.107 CC-3-5  7.00% n.sub.e [589 nm, 20° C.]: 1.59 CCP-3-1 11.00% Δε [1 kHz, 20° C.]: −3.3 CCY-3-O2 11.00% ε.sub.⊥ [1 kHz, 20° C.]: 7.0 CPY-3-O2 10.00% CY-3-O2 12.00% PY-1-O2  8.00% PY-3-O2 12.00% CC-3-V1  6.00% BCH-32  5.00% Σ 100.00%  .sup. 

Reference Example 12

[0465] A liquid-crystal base mixture B-12 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

TABLE-US-00019 CY-3-O2 12.00%  clearing point [° C.]: 91.5 CY-5-O2 12.00%  Δn [589 nm, 20° C.]: 0.078 CCY-3-O2 13.00%  n.sub.e [589 nm, 20° C.]: 1.55 CCY-5-O2 13.00%  Δε [1 kHz, 20° C.]: −3.7 CCY-3-1 8.00% ε.sub.⊥ [1 kHz, 20° C.]: 7.1 CCZC-3-3 4.00% CCZC-3-5 3.00% CCZC-4-3 3.00% CC-3-4 6.00% CC-3-5 6.00% CC-3-O3 8.00% CC-5-O1 4.00% CC-5-O2 4.00% CP-3-O2 4.00% Σ 100.00% .sup.  

Reference Example 13

[0466] A liquid-crystal base mixture B-13 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

TABLE-US-00020 APUQU-2-F 6.00% clearing point [° C.]: 79.5 APUQU-3-F 6.00% Δn [589 nm, 20° C.]: 0.110 CC-3-V 44.50%  n.sub.e [589 nm, 20° C.]: 1.59 CCP-V-1 12.50%  Δε [1 kHz, 20° C.]: 11.6 CPGU-3-OT 5.00% ε.sub.⊥ [1 kHz, 20° C.]: 3.6 DPGU-4-F 2.00% PGP-2-2V 1.50% PGUQU-3-F 4.50% PGUQU-4-F 8.00% PUQU-3-F 10.00%  Σ 100.00% .sup.  

Reference Example 14

[0467] A liquid-crystal base mixture B-14 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

TABLE-US-00021 CPG-3-F 7.00% clearing point [° C.]: 113.8 CPG-5-F 7.00% Δn [589 nm, 20° C.]: 0.118 CPU-5-F 12.00%  n.sub.e [589 nm, 20° C.]: 1.61 CPU-7-F 12.00%  CP-7-N 11.00%  CP-8-N 6.00% CP-9-N 6.00% CCGU-3-F 7.00% CC-3-O3 6.00% CC-5-O1 6.00% CBC-33F 4.00% CBC-53F 4.00% CBC-55F 4.00% CCZPC-3-3 3.00% CCZPC-3-4 3.00% CCZPC-3-5 2.00% Σ 100.00% .sup.  

Reference Example 15

[0468] A liquid-crystal base mixture B-15 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

TABLE-US-00022 CPG-3-F 8.00% clearing point [° C.]: 108 CPG-5-F 8.00% Δn [589 nm, 20° C.]: 0.125 CPU-5-F 14.00%  n.sub.e [589 nm, 20° C.]: 1.61 CPU-7-F 11.00%  CP-i7-N 18.00%  CP-7-N 13.00%  CCGU-3-F 7.00% CC-3-O3 2.00% CBC-33F 4.00% CBC-53F 4.00% CBC-55F 3.00% CCZPC-3-3 3.00% CCZPC-3-4 3.00% CCZPC-3-5 2.00% Σ 100.00% .sup.  

Reference Example 16

[0469] A liquid-crystal base mixture B-16 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

TABLE-US-00023 CPG-2-F 4.00% clearing point [° C.]: 121 CPG-3-F 8.00% Δn [589 nm, 20° C.]: 0.124 CPG-5-F 7.00% n.sub.e [589 nm, 20° C.]: 1.62 CPU-5-F 10.00%  CPU-7-F 10.00%  CP-6-N 10.00%  CP-7-N 12.00%  CCGU-3-F 9.00% CC-3-O3 5.00% CC-5-O1 4.00% CBC-33F 4.00% CBC-53F 4.00% CBC-55F 4.00% CCZPC-3-3 3.00% CCZPC-3-4 3.00% CCZPC-3-5 3.00% Σ 100.00% .sup.  

Reference Example 17

[0470] A liquid-crystal base mixture B-17 is prepared and characterized with respect to its general physical properties, having the composition and properties as indicated in the following table.

TABLE-US-00024 CPG-2-F 3.00% clearing point [° C.]: 114.5 CPG-3-F 8.00% Δn [589 nm, 20° C.]: 0.121 CPG-5-F 8.00% n.sub.e [589 nm, 20° C.]: 1.61 CPU-5-F 10.00%  CPU-7-F 10.00%  CP-6-N 10.00%  CP-7-N 12.00%  CCGU-3-F 7.00% CC-3-O3 6.00% CC-5-O1 6.00% CBC-33F 4.00% CBC-53F 4.00% CBC-55F 4.00% CCZPC-3-3 3.00% CCZPC-3-4 3.00% CCZPC-3-5 2.00% Σ 100.00% .sup.  

Reference Example 18

[0471] The respective properties of the individual compounds of formulae I-1, I-2, I-3, I-4, II-1, II-4 and II-5 are determined.

[0472] The following Table shows the determined degree of anisotropy for the compounds.

TABLE-US-00025 Compound Degree of anisotropy I-1 0.77 I-2 0.73 I-3 0.73 I-4 0.73 II-1 0.71 II-4 0.66 II-5 0.65

[0473] Each of the compounds of formulae I-1, I-2, I-3, I-4, II-1, II-4 and II-5 on their own have adequate solubility in base mixture B-1 shown in Reference Example 1 and in base mixture B-8 shown in Reference Example 8.

[0474] For each of the compounds of formulae I-1, I-2, I-3, I-4, II-1, II-4 and II-5 the stability against exposure to light in the base mixtures B-1 and B-8 over time is investigated using a Suntest CPS+ from MTS-Atlas at black standard temperatures of 42° C. and 70° C. All compounds individually exhibit adequate stability, however the compounds of formulae II-1, II-4 and II-5 individually show a somewhat lesser stability compared to the performance of the respective compounds of formulae I-1, I-2, I-3 and I-4.

Comparative Example 1

[0475] A mixture CM-1 is prepared by mixing 99.007% of mixture H-2 as described in Reference Example 2 above with 0.195% of the compound of formula I-1, 0.064% of the compound of formula

##STR00693##

[0476] 0.100% of the compound of formula

##STR00694##

[0477] and 0.634% of the compound of formula

##STR00695##

[0478] The mixture CM-1 is filled into a test cell having antiparallel polyimide alignment layers and a cell gap of 23.7 μm. Strong residual fluorescence is visible by eye.

Comparative Example 2

[0479] A mixture CM-2 is prepared by mixing 96.350% of mixture B-1 as described in Reference Example 1 above with 0.050% of the compound of formula

##STR00696##

which in the following will be referred to as ST-1,

[0480] 1.460% of the compound of formula I-1, 1.644% of the compound of formula I-2 and 0.496% of the compound of formula I-3.

[0481] The mixture CM-2 is filled into a test cell having antiparallel polyimide alignment layers and a cell gap of 11.6 μm. Comparatively strong residual fluorescence is still observed.

[0482] In the following the compositions and media comprising the dyes according to the invention are investigated with respect to their physical properties and their suitability for use in devices for regulating energy transmission.

Example 1

[0483] A mixture M-1 is prepared by mixing 98.919% of mixture B-1 as described in Reference Example 1 above with 0.030% of the compound ST-1 shown in Comparative Example 2 above, 0.030% of the compound of formula I-1, 0.230% of the compound of formula I-2, 0.137% of the compound of formula I-4, 0.272% of the compound of formula II-1 and 0.382% of the compound of formula II-4.

[0484] The mixture M-1 is filled into a test cell having antiparallel polyimide alignment layers and a cell gap of 23.7 μm. Only a weak residual fluorescence is observed.

Example 2

[0485] A mixture M-2 is prepared by mixing 94.905% of mixture B-1 as described in Reference Example 1 above with 0.050% of compound ST-1 shown in Comparative Example 2 above, 0.434% of the compound of formula I-1, 0.997% of the compound of formula I-2, 0.849% of the compound of formula I-3, 1.300% of the compound of formula II-1 and 1.465% of the compound of formula II-4.

[0486] The dye compounds combined show excellent solubility and excellent stability against heat and light in the host mixture.

[0487] The mixture M-2 is filled into an electrically switchable test cell having antiparallel polyimide alignment layers, where the switching layer has a thickness of 25 μm. The performance for the bright state and the dark state are evaluated. Measurements are performed according to norm EN410.

[0488] The following values are determined:

[0489] light transmittance τ.sub.v (dark state): 18.4%

[0490] light transmittance τ.sub.v (bright state): 36.7%

[0491] chromaticity coordinate x (dark state): 0.321

[0492] chromaticity coordinate y (dark state): 0.355

[0493] chromaticity coordinate x (bright state): 0.321

[0494] chromaticity coordinate y (bright state): 0.355.

[0495] The chromaticity coordinates or colour coordinates are determined according to CIE 1931 2° standard observer.

[0496] Fluorescence measurements are performed using a spectrophotometer respectively with excitation wavelengths of 300 nm, 350 nm, 400 nm, 450 nm, 500 nm and 550 nm. No discernible residual fluorescence in the visible spectral range is observed.

[0497] The mixture M-2 is filled into an electrically switchable test cell having the Heilmeier configuration, using an ITOS XP-40HT polariser, antiparallel polyimide alignment layers and a switching layer thickness of 12 μm. The performance for the bright state and the dark state are evaluated. Measurements are performed according to norm EN410.

[0498] The following values are determined:

[0499] light transmittance τ.sub.v (dark state): 0.6%

[0500] light transmittance τ.sub.v (bright state): 24.6%

[0501] chromaticity coordinate x (dark state): 0.301

[0502] chromaticity coordinate y (dark state): 0.323

[0503] chromaticity coordinate x (bright state): 0.324

[0504] chromaticity coordinate y (bright state): 0.354.

[0505] The mixture M-2 is well suited for the use in devices for regulating the passage of energy from an outside space into an inside space, for example in windows.

Example 3

[0506] The following mixtures M-3-1, M-3-2, M-3-3, M-3-4 and M-3-5 are prepared by respectively mixing the base mixture B-1 with the additional compounds according to the following Table.

TABLE-US-00026 M-3-1 M-3-2 M-3-3 M-3-4 M-3-5 B-1 94.896% 94.691% 95.391% 95.855% 94.653% ST-1 0.050% 0.050% 0.050% 0.050% 0.050% I-1 0.704% 0.752% 0.500% 0.550% 0.360% I-2 0.765% 0.698% 0.945% 0.866% 1.252% I-3 0.919% 0.879% 0.840% 0.963% 0.734% II-1 1.406% 1.771% 1.428% 1.122% 1.669% II-4 1.260% 1.159% 0.846% 0.594% 1.282%

[0507] The mixtures M-3-1, M-3-2, M-3-3, M-3-4 and M-3-5 are respectively filled into electrically switchable devices having the Heilmeier configuration, using an ITOS XP-40HT polariser, antiparallel polyimide alignment layers and a switching layer thickness of 11.6 μm.

[0508] The performance for the bright state and the dark state is evaluated. Measurements are performed according to norm EN410.

TABLE-US-00027 M-3-1 M-3-2 M-3-3 M-3-4 M-3-5 light transmittance 0.6% 0.6% 0.6% 0.6% 0.5% τ.sub.v (dark state) light transmittance 24.7% 24.7% 25.1% 25.2% 24.2% τ.sub.v (bright state) chromaticity coordinate 0.286 0.260 0.287 0.288 0.313 x (dark state) chromaticity coordinate 0.363 0.373 0.287 0.256 0.305 y (dark state) chromaticity coordinate 0.321 0.317 0.321 0.320 0.325 x (bright state) chromaticity coordinate 0.355 0.356 0.345 0.339 0.350 y (bright state)

[0509] Fluorescence measurements are performed using a spectrophotometer respectively with excitation wavelengths of 300 nm, 350 nm, 400 nm, 450 nm, 500 nm and 550 nm. No discernible residual fluorescence in the visible spectral range is observed for the mixtures M-3-1, M-3-2, M-3-3, M-3-4 and M-3-5.

[0510] The mixtures M-3-1, M-3-2, M-3-3, M-3-4 and M-3-5 are well suited for the use in devices for regulating the passage of energy from an outside space into an inside space, for example in windows.

Example 4

[0511] A mixture M-4 is prepared by mixing 94.367% of mixture B-1 as described in Reference Example 1 above with 0.369% of the compound of formula I-1, 1.192% of the compound of formula I-2, 0.699% of the compound of formula I-4, 1.636% of the compound of formula II-1, 1.187% of the compound of formula II-4, 0.150% of compound ST-1 shown in Comparative Example 2 above, 0.150% of the compound of formula

##STR00697##

[0512] and 0.250% of the compound of formula

##STR00698##

[0513] The mixture M-4 is filled into a test cell having a cell gap of 23.6 μm. The stability of M-4 against exposure to light over time is investigated using a Suntest CPS+ from MTS-Atlas at a black standard temperature of 70° C. No colour change is observed for a time period of over 26 weeks.

Example 5

[0514] A mixture M-5 is prepared by mixing 94.667% of mixture B-1 as described in Reference Example 1 above with 0.369% of the compound of formula I-1, 1.192% of the compound of formula I-2, 0.699% of the compound of formula I-4, 1.636% of the compound of formula II-1, 1.187% of the compound of formula II-4, 0.150% of compound ST-1 shown in Comparative Example 2 above and 0.100% of the compound of formula

##STR00699##

[0515] The mixture M-5 is filled into a test cell having a cell gap of 23.1 μm. The stability of M-5 against exposure to light over time is investigated using a Suntest CPS+ from MTS-Atlas at a black standard temperature of 70° C. No colour change is observed for a time period of over 39 weeks.

Example 6

[0516] A mixture M-6 is prepared by mixing 94.767% of mixture B-1 as described in Reference Example 1 above with 0.369% of the compound of formula I-1, 1.192% of the compound of formula I-2, 0.699% of the compound of formula I-3, 1.636% of the compound of formula II-1, 1.187% of the compound of formula II-4 and 0.150% of the compound of formula

##STR00700##

[0517] The mixture M-6 is filled into a test cell having a cell gap of 22.5 μm. The stability of M-6 against exposure to light over time is investigated using a Suntest CPS+ from MTS-Atlas at a black standard temperature of 70° C. No colour change is observed for a time period of over 26 weeks.

Examples 7 to 14

[0518] Mixtures M-7 to M-14 are prepared analogous to mixture M-2 described in Example 2, wherein instead of base mixture B-1 respectively the mixtures B-2, C-2, B-3, B-4, B-5, B-6, B-7 and H-7 described in Reference Examples 2 to 7 above are used as the host mixtures.

[0519] The mixtures M-7 to M-14 are treated and analysed analogous to M-2 described in Example 2 above. The mixtures are suitable for the use in devices for regulating the passage of energy from an outside space into an inside space, for example in windows.

Example 15

[0520] A mixture M-15 is prepared by mixing 96.364% of mixture B-8 as described in Reference Example 8 above with 0.566% of the compound of formula I-1, 0.847% of the compound of formula I-4, 0.730% of the compound of formula II-1, 0.962% of the compound of formula II-4, 0.030% of compound ST-1 shown in Comparative Example 2 above, and 0.501% of the compound of formula

##STR00701##

[0521] The mixture M-15 is filled into a test cell having a cell gap of 23.0 μm. The stability of M-15 against exposure to light over time is investigated using a Suntest CPS+ from MTS-Atlas at a black standard temperature of 70° C. No colour change is observed for a time period of over 10 weeks.

Example 16

[0522] A mixture M-16 is prepared by mixing 96.359% of mixture B-8 as described in Reference Example 8 above with 0.566% of the compound of formula I-1, 0.847% of the compound of formula I-4, 0.730% of the compound of formula II-1, 0.967% of the compound of formula II-4, 0.030% of compound ST-1 shown in Comparative Example 2 above, and 0.501% of the compound of formula

##STR00702##

[0523] The mixture M-16 is filled into a test cell having a cell gap of 23.0 μm. The stability of M-16 against exposure to light over time is investigated using a Suntest CPS+ from MTS-Atlas at a black standard temperature of 70° C. No colour change is observed for a time period of over 10 weeks.

[0524] The mixture M-16 is filled into an electrically switchable device having a switching layer thickness of 23.0 μm. The dye compounds combined show excellent solubility and excellent stability against heat and light in the host mixture and give an excellent switching contrast.

[0525] The mixture M-16 is well suited for the use in devices for regulating the passage of energy from an outside space into an inside space, for example in windows.

Examples 17 to 25

[0526] Mixtures M-17 to M-25 are prepared analogous to mixture M-16 described in Example 16, wherein instead of base mixture B-8 respectively the mixtures B-9, B-10, B-11, B-12, B-13, B-14, B-15, B-16 and B-17 described in Reference Examples 9 to 17 above are used as the host mixtures.

[0527] The mixtures are suitable for the use in devices for regulating the passage of energy from an outside space into an inside space, for example in windows.

Example 26

[0528] A mixture M-26 is prepared by mixing 95.596% of mixture B-1 as described in Reference Example 1 above with 0.050% of the compound ST-1 shown in Comparative Example 2 above, 0.450% of the compound of formula I-1, 0.924% of the compound of formula I-2, 0.780% of the compound of formula I-3, 1.550% of the compound of formula II-4 and 0.650% of the compound (182)

##STR00703##

[0529] The mixture is suitable for the use in devices for regulating the passage of energy from an outside space into an inside space, for example in windows.

Example 27

[0530] A mixture M-27 is prepared by mixing 95.646% of mixture B-1 as described in Reference Example 1 above with 0.450% of the compound of formula I-1, 0.924% of the compound of formula I-2, 0.780% of the compound of formula I-3, 1.550% of the compound of formula II-4 and 0.650% of the compound (182) shown in Example 26 above.

[0531] The mixture is suitable for the use in devices for regulating the passage of energy from an outside space into an inside space, for example in windows.

Example 28

[0532] A mixture M-28 is prepared by mixing 89.45% of mixture B-1 as described in Reference Example 1 above with 0.05% of the compound ST-1 shown in Comparative Example 2 above, 1.00% of the compound of formula I-1, 2.20% of the compound of formula I-2, 2.20% of the compound of formula I-3, 2.00% of the compound of formula II-4, 1.30% of the compound of formula II-5 and 1.80% of the compound (182) shown in Example 26 above.

[0533] The mixture is suitable for the use in devices for regulating the passage of energy from an outside space into an inside space, for example in windows.

Example 29

[0534] A mixture M-29 is prepared by mixing 89.45% of mixture B-8 as described in Reference Example 8 above with 0.05% of the compound ST-1 shown in Comparative Example 2 above, 1.00% of the compound of formula I-1, 2.20% of the compound of formula I-2, 2.20% of the compound of formula I-3, 2.00% of the compound of formula II-4, 1.30% of the compound of formula II-5 and 1.80% of the compound (182) shown in Example 26 above.

[0535] The mixture is suitable for the use in devices for regulating the passage of energy from an outside space into an inside space, for example in windows.

Example 30

[0536] A mixture M-30 is prepared by mixing 89.268% of mixture B-1 as described in Reference Example 1 above with 0.100% of the compound ST-1 shown in Comparative Example 2 above, 0.382% of the compound of formula R-5011 as described in Table F above, 0.950% of the compound of formula I-1, 1.900% of the compound of formula I-2, 2.300% of the compound of formula I-3, 1.800% of the compound of formula II-1, 2.200% of the compound of formula II-4 and 1.100% of the compound of formula II-5.

[0537] The mixture is suitable for the use in devices for regulating the passage of energy from an outside space into an inside space, for example in windows.