GB2090274A - Dichroic dyestuff - Google Patents

Abstract

5,6-Di-substituted benzothiazyl polyazo compounds of the formula <IMAGE> wherein:- A is a polyazo group; Q is a 5,6-di-substituted benzothiazyl group; and Z is selected from substituted naphthalene, permidine or jujolidene groups are found to be dichroic dyes which form guest-host combinations with nematic liquid crystals. These combinations are of value in electro-optical display devices. These combinations along with certain additional dichroic dyes are useful to provide an electro-optical display which changes from clear to a neutral black color or vice versa when an electric field is applied to the electro- optical display.

Description

SPECIFICATION Novel dichroic dyestuff Technical Field This invention relates to novel dichroic dyes and to guest-host combinations thereof with nematic liquid crystals. The novel dichroic dyes are 5,6-di-substituted benzothiazyl polyazo compounds having absorption maxima at wavelengths greater than about 600 nanometers (nm) and transmitting less than 50 percent of incident light having wavelengths between about 600 and 700 nm. This invention further relates to electro-optical devices employing such guest-host combinations. Use of the novel dichroic dyes with additional well-known dichroic dyes having absorption maxima between about 400 and 600 nm, in liquid crystal devices provide displays which alternate generally between a neutral black and a clear state when an electric field is present, or absent, respectively.

Background Art The use of dichroic dyes in solution with various liquid crystal materials, and liquid crystal display devices incorporating such mixtures are well known in the art. These dichroic dye-liquid crystal mixtures may be used in "guest-host" type liquid crystal displays or, when an optically active additive is employed, in "phase-change" type liquid crystal displays. In both types of displays the host liquid crystal material has its orientation controlled by the application of electric fields and in turn interacts with the guest dichroic dye to induce a cooperative conforming alignment. The dichroic dye manifests low or high absorbence of incident light depending upon its molecular orientation with respect to the light wave vector.Thus, generally when an electric field is applied to the display, the area between the electrodes appears clear, i.e., all the dyes exhibit minimum absorption, and in the absence of an electric field the display appears characteristically dye colored, i.e., the dyes are in a high absorbing state.

It is desired to provide a liquid crystal display which appears neutral black in the absence of an electric field and clear or non-black in the presence of an electric field. In order to provide such neutral black appearing displays a plurality of dichroic dyes which together absorb strongly throughout the region between about 400 nm and 700 nm are required. Suitable dichroic dyes which have absorption maxima between about 400 and 600 nm are readily found in U.S. 4,145,114; U.S. 4,128,497; U.S.

4,179,395 and in Applicants' copending U.S. Serial No. 70,421. However, suitable dichroic dyes which absorb strongly between 600 and 700 nm are not so easily obtained. While there are available in the prior art dichroic dyes which absorb light having wavelengths in excess of 600 nanometers, they are deficient in one or more properties required for optimal performance in a liquid crystal display, i.e., they have inadequate solubilities in liquid crystal material, they are chemically, photochemically or electrochemically unstable, e.g., they are degraded by ultraviolet radiation, they have relatively low extinction coefficients, i.e., less than 2 x 104, or they have relatively low optical order parameters, i.e., less than 0.6a. For example, U.S. 3,960,751; U.S. 4,154,746; and U.K.Patent Application GB 2,011,940 A disclose a number of anthraquinone type pleochroic dyes which have absorption maxima very close to about 600 nanometers. However, anthraquinone type dyes have optical order parameters generally less than 0.65. The optical order parameters are measures of the efficiency with which the dichroic dye is oriented by the liquid crystal material and is directly related to the contrast one observes when viewing the device. In general, dyes having optical order parameters close to 1 are desired since they produce guest-host displays having high contrast, i.e. approximately 10 to 1 and greater.

U.S. 4,128,497 and U.S. 4,145,114 disclose polyazo type pleochroic dyes having absorption maxima at wavelengths in the range of from about 590 nanometers to about 620 nanometers. 'while these dyes have optical order parameters in excess of 0.5, in general they lack stability, i.e., they are degraded by ultraviolet radiation, and they have solubilities in iiquid crystal materials of less than 1% by weight.

Masanobu Wåda and Tatsuo Ochida in "CH-LCDs Make Bright Color Displays Possible," Japan Journal of Electronic Engineering, November, 1 979, disclose several substituted benzothiazyl polyazo dichroic dyes for use in guest-host liquid crystal displays. These dyes have, in general, lower optical order parameters, i.e., less than 0.65, lower absorption between 6GO and 700 nm, i.e., less than 0.3, and lower extinction coefficients, i.e., less than 2 x 1 G4, than the dyes of the present invention.

Disclosure of Invention The novel dichroic dyes of the present invention are useful in providing black/clear liquid crystal displays since they have absorption maxima at wavelengths greater than 600 nanometers and transmit less than 50% of incident light having a wavelength of from 600 up to 700 nanometers. Additionally, the dichroic dyes of the present invention suffer from none of the deficiencies referred to hereinabove in connection with the dichroic dyes of the prior art. The dyes of the present invention have optical order parameters greater than about 0.72. they have extinction coefficients greater than about 5.5 x 1 04; they have solubilities in nematic liquid crystal materials in excess of about 2 percent by weight; and they have good chemical, photochemical and electrochemical stability.For example, they are resistant to ultraviolet radiation, they are resistant to degradation produced by electric currents, and they are not degraded by liquid crystal materials.

Brief Description of the Drawings Figure 1 is a graphic presentation comparing absorbance characteristics of a dichroic dye of the present invention with a closely related dichroic dye of the prior art.

Figure 2 illustrates the absorbance characteristics of a blackiclear "phase-change" type liquid crystal display device utilizing one of the dichroic dyes of the present invention.

Detailed Description The novel dichroic dyes of the present invention are 5,6-di-substituted benzothiazyl polyazo dichroic dyes. The preferred compounds can be represented by the general formula: Q-A-Z wherein: A is a polyazo group, having at least two-N=N-groups; Q is a 5,6-di-substituted benzothiazyl group; and Z is selected from the group consisting of substituted naphthalene, permidene or jujolidene groups.

Preferred polyazo groups for inclusion in the above formula are of the formula

wherein m is O or an intager between about 0-6, R is independently selected from aikyl or alkoxy groups having from about 1 to 8 carbon atoms, and x is independently 0,2 or 4, provided that when x is 2, the two R groups are not substituted on adjacent ring carbon atoms. Alternatively, when any x is 2, the two R groups are combined in the group -C=CH-CH=CH- which is substituted on two adjacent ring carbon atoms, so that the aromatic nucleus is a naphthalene group. It is preferred that there be no more than m naphthalene groups in the molecule.

Preferred 5,6-di-substituted benzothiazyl groups, 0, are of the formula

wherein B and B' are independently selected from the group consisting of H, CnH2n+" OCnH2n+, phenyl or phenoxy, wherein n is an integer from about 1 to 8. Alternatively, B and B' together represent the group -CH2-CH2-CH2-,to form a fused cycloaliphatic five membered ring.

Preferred substituted naphthalene Z groups include

wherein R1 is H or CnH2n+" and R2 is CnH2n+" wherein n is an integer from about 1 to 6.

Preferred permidene Z groups include

wherein R3 and R4 are independently selected from the group consisting of lower alkyl groups having about 1-6 carbon atoms.

Alternatively, R3 and R4 are combined in a cyclopentyl or cyclohexyl group to provide a permidene Z group having the formula:

The cyclopentyl and cyclohexyl groups may be substituted in available positions by lower alkyls having about 1-8 carbon atoms.

Preferred jujolidene Z groups include

Exemplary of the preferred dichroic dyes are the following:

Dye No. Dye Structure CH3 1 H3CN. N=N /H H3CQ N=NO;=N - NN CH2CH3 NC3 H 2 =N- N=NN CH3 CH2CH3 CH H3CN3 3 QN=NQ NSf N=N Q CH3 CH3 CH3 H5C20 H 4 ::N=N N=N N CH3 3 H CH2CH3 C H3 C4H9 51, N=N QC{N In the particularly preferred dichroic dyes, the polyazo groups, A, is of the formula

wherein R is defined as it was hereinabove xis 2 or 4, and m is at least 1 such that there are at least three -N=N- groups and at least two substituted aromatic rings lying in the plane of the molecule.

Exemplary of the particularly preferred dichroic dyes are the following:

Dye No. Dye Structure H3C H3C CH3 6 < \ N-N XN-N--N < N CH3 3 zCH3 CH3 HCN - H N=N--ce) y 7 H3CS CH3 N=N-ce, CHIN3 C H N H3 N=N < > N=N N=N--( N=N CH3 OCH3 CH 3 OCH 3 3 H5 C2ON.3 oc;;H H 9 > N=NW N=NW N=N e HNXCH3 CH3 3 (9 | 2C 3 C N H3N H H3C N=NN=N N N7 10 H3C S - \cH3 CH3 CH3 CH3 CH3 11 fN=NXN=NXN=NXN=N CTI3 CH3 N CH3 CE13 CH3 The dichroic dyes of this invention may be synthesized using methods of diazotization normally employed to synthesize polyazo dyes. The literature abounds with methods of diazotization and specific organic synthetic procedures relating to diazotization and coupling reaction schemes.A preferred synthetic scheme is direct diazotization of the appropriate substituted 2-amino-benzothiazole in strong mineral acid, followed by coupling the resultant diazo compound to the appropriate substituted aniline.

Diazotization and coupling are repeated as desired and the intermediate product is recovered from a buffered aqueous solution as the free base. The free base is subsequently diazotized and coupled with the desired Z group in acid. The resultant dichroic dye is recovered from the neutralized solution by filtration and is purified by column chromatography.An example of this method is illustrated below:

B < Rf NH2 Diazotization with H2SO4, NaNO2 B'' with H2S041 NaNO2 Couple to ;NH2 X NH2 E' D' \ / X \ > N=N7 NH2 B-t D Diazotization with H2S04 and NaNO2 D E Couple to NH2 E' D' \ / H '; N=N))N=N ONH2 Eg D' E' D' l

Diazotization with H2SO4 and NaNO2 /R1 to 12 D E D E t / D E D E S \ > N N ss N--N ss N=N t N B' D, E, D', and E' represent substituents independently selected from the group consisting of H, Cn2n+1 and OCnH2n+" wherein n is an integer from about 1 to 8. B, B', R, and R2 are defined hereinabove.

The 5,6-di-substituted banzothiazyl polyazo dichroic dyes of the present invention are blue in color, have absorption maxima at wavelengths greater than about 600 nanometers, and transmit less than about 50% of incident light having wavelengths from 600 nm up to about 700 nanometers. The preferred dichroic dyes have absorption maxima at wavelengths greater than about 610 nm. The absorption maxima for several of the preferred dyes (Dye Numbers 1-6) are shown in Table I, hereinbelow. The particularly preferred dyes have absorption maxima at wavelengths greater than about 620 nm and transmit less than about 40% of incident light having wavelengths from about 600 nm up -to about 700 nm.Absorption maxima and percent transmission of light having a wavelength of 700 nm for several of the particularly preferred dyes (Dye Numbers 6-11) are shown in Table II, hereinbelow.

The following azo and polyazo dyes, including several benzothiazyl azo and polyazo dyes are known in the art.

Prior Art Dye No. Dry Structure Disclosing Dye N C2H5 12 ( \N=N > N/C22N5 U.S. 2,785,151 13 g 5 eNH2 U.S. 2,149,051 H5C2O H H5 2 Y \ N&commat; N U.S. 2,785,154 CH2CH3 15 NH2 \ N=N > NH2 U.S, 2,145,051 rro 0 Is o,NY N, /CH3 16 U.S. 4,145,114 3 H 17 5 > > N(CH2CH3 U.S. 2,785,237 17=N-(Slt " 18 H5 C2 N CH2CH3 Japan Journal of N""'N O Electronic Engine S \~ - \ ering Nov. 1979. CH2CH3 p. 26. 19 0 N N=N /CH2CH3 Japan Journal of N=N N Electronic Journal CH2CH3 ering Nov. 1979, p. \J z CH2CH3 p. 26

Absorption maxima and percent transmission of 700 nm wavelength light for these prior art dyes are shown in Table Ill, hereinbelow. Absorption maxima for these closely related dyes are less than about 600 nm. Additionally the percent transmission of 700 nm wave length light is greater than about 75%.

Figure 1 compares the absorbance characteristics of Dye Number 2,

with a closely related dye, Dye Number 15,

Curve A is the spectra of Dye Number 2, at a concentration of 0.4 percent by weight in an eutectic mixture of biphenyl pyrimidine liquid crystals commercially available as "ROTN 404" from Hoffman LaRoche. Curve B is the spectra of Dye Number 15, at a concentration of 0.7 percent by weight in "ROTN 404". While Dye Number 15 has an absorption maximum close to 600 nm, its percent transmission at 625 nm increases to more than about 50%, with a percent transmission at 700 nm of about 80%. Dichroic dyes which have percent transmissions of more than about 50% at wavelengths beyond 625 nm are not useful for providing black/clear liquid crystal displays.

The dyes of the present invention have, in general, relatively high values of the optical order parameter S. This parameter is a measure of the efficiency with which the compound is oriented by the liquid crystal material and is diractly related to the contrast one observes when viewing the device. In general, dyes having high optical order parameters produce displays having high optical contrasts. The determination of the optical order parameter, S, is discussed in Journal of Applied Physics, Vol. 45, No.

11,471-8-23(1974).

Ao-A1 Ao+2A1 wherein Ao is the absorbence in the absence of an electric field and A1 is the absorbence in the presence of an electric field. S is a value something less than 1 and preferably is very close to 1. Values of S greater than 0.5 and preferably greater than 0.65 insure contrasts of between 5:1 and 10:1. The dyes of the present invention have values of S greater than about 0.72, insuring optical contrast ratios on the order of at least about 10:1. The preferred dyes have S values greater than about 0.75 and the particularly preferred dyes have S values greater than about 0.78. The S values for several of the preferred dyes (Dye Numbers 1-6) are shown in Table land the S values for several of the particularly preferred dyes (Dye Numbers 7-11) are shown in Table II.Closely related azo and polyazo dyes (Dye Numbers 12-19) have S values no greater than about 0.72. S values for several of the closely related dyes are shown in Table Ill hereinbelow.

The dyes of the present invention have relatively high extinction coefficients, when compared with similar azo and polyazo dyes of the prior art. The molar extinction coefficient is a measurement of the extent to which the dye absorbs light at any particular molar concentration. Therefore, the dyes of the present invention, with higher molar extinction coefficients provide displays with better brightness characteristics, at any particular molar concentration of dichroic dye, than do the dyes of the prior art which have relatively lower molar extinction coefficients. Additionally, the dyes of the present invention, due to their higher molar extinction coefficients, may be utilized in lower molar concentrations than the dichroic dyes of the prior art to produce liquid crystal displays having similar absorbences.For instance, the dichroic dyes of the prior art are in general required to be present in concentrations of from approximately 1 to 5% by weight of he guest-host composition. In contrast, the dichroic dyes of the present invention need be present in concentrations of only about 1/2 to 2% by weight to provide sufficient absorption in one of the oriented states to display its characteristic color.

The extinction coefficients of the dyes of the present invention are generally greater than about 5.5 x 104. The particularly preferred dyes have extinction coefficients generally greater than about 1 x 105. The extinction coefficients for several of the particularly preferred dyes (Dye Numbers 7-11) are shown in Table II, hereinbelow. Closely related azo and polyazo dyes (Dye Numbers 12-19) have extinction coefficients no greater than 5.5 x 104. The extinction coefficients for several of the closely related dyes are shown in Table Ill, hereinbelow.

The dyes of the present invention have been found to show improved stability, both chemical and photochemical stability, compared with known dichroic dyes containing chains of azo-linked phenyl rings. For example, when several of the particularly preferred dyes of the present invention (Dye Numbers 6-11) were present in a 20 m thick liquid crystal display test cell, at a concentration of 1% by weight in the liquid crystal material, "ROTN 404", and exposed to ultraviolet radiation supplied by a Type 509/10, 500 watt ultraviolet lamp, available from Hanovia, at 21 OC, the time required for the dyes to lose 50% of the value of their optical order parameters, S, was greater than 500 hours.When closely related azo and polyazo dichroic dyes (Dye Numbers 12-19) were tested in the identical manner the time required for their S values to be reduced one-half was always less than 350 hours, and in several cases was less than 200 hours (see Table Ill).

In order for dichroic dyes to be useful in liquid crystal display devices, the dye molecule, in addition to having a high optical order parameter and stability, must have suitable solubility in the host liquid crystal material. Solubilities of greater than about 1 percent by weight insure that the dye will have sufficient absorption in one of the oriented states to be useful in displaying its characteristic color. The dyes of the present invention have solubilities in nematic liquid crystals of greater than about 2 percent by weight. The particularly preferred dyes have solubilities in "ROTN 404" nematic liquid crystal material of greater than about 3 percent by weight. The solubilities in "ROTN 404" for several of the particularly preferred dichroic dyes of the present invention (Dye Numbers 6-11) are shown in Table II, hereinbelow.

TABLE I - Properties of Preferred Dyes ajax in Sin Dye No. E71 E71 1 625 + 5 nm 0.72 2 630 + 5 nm 0.76 3 620 + 5 nm 0.78 4 610+5nm 0.75 5 615 + 5 nm 0.72 "E7" is a eutectic mixture of lower alkyl and alkoxy cyanobiphenyls and terphenyl liquid crystals commercially available from E. Merck Co.

TABLE 11 Prcperties of Particularly Preferred Dyes Optical Order Parameter (S) Solubility Dye in in in in #max in dimethyl % T in ROTN 4044 Stability5 No. E71 E322 PCH 11322 ROTN 4044 in ROTN 4044 formamide 700 nm (percent by wt.) (hours) 6 0.78 0.78 0.80 0.78 620 # 5 nm 1.1 x 105 40 3.0 > 500 7 0.80 0.80 0.84 0.82 625 # 5 nm 2.0 x 105 32 4.0 > 500 8 0.80 0.82 0.85 0.85 625 # 5 nm 1.0 x 105 28 > 4.0 > 500 9 0.78 0.82 0.80 0.80 630 # 5 nm 2.5 x 105 25 2.2 > 500 10 0.80 0.83 0.85 0.85 625 # 5 nm 1.9 x 105 35 2.5 > 500 11 0.82 0.82 0.88 0.85 640 # 5 nm 3.3 x 105 12 1.9 > 500 1 "E7" is a eutectic mixture of lower alkyl and alkoxy cyanobiphenyls and terphenyl liquid crystals commerclally available from E. Merck Co.

2 "E38" is a eutectic mixture of lower alkyl and alkoxy cyanobiphenyls and terphenyl liquid crystals commercially available form E. Merck Co.

3 "PCH 1132" is a eutectic mixture comprising by weight approximately 14% trans-4-n-pentyl-(4'-cyanobiphenyl) cyclohexane, 26% trans-4-npropyl-(4'-cyanophenyl) cyclohexane, 36% trans-4-n-pentyl-(4'-cyanophenyl)cyclohexane, and 24% trans-4-heptuyl-(4'-cyanophenyl)-cyclohexane, commercially available from E. M. Laboratories, lnc.

4"ROTN 404" is a eutectic mixture of biphenylpyrimidine liquid' crystals commercially available from Hoffman LaRoche.

5 Time in hours required for a 1% by weight solution of the dye in "ROTN 404" ln a 20 m thick liquid crystal display test cell to lose 50 percent of the value of lts optical order parameter (S) when exposed to ultraviolet radiation supplied by a type 509/10, 500 watt ultravlolet lamp, available from Hanovia, at 21 C.

TABLE 111 Properties of Known Dyes Optical Order Parameter (S) Dye in in in in #max in dimethyl % T Stability5 No. E71 E382 PCH 11323 ROTN 4044 IN ROTN 4044 formamide 700 nm (hours) 12 0.58 0.59 0.60 0.60 545 # 5 nm 3.3 x 104 100 274 13 0.56 0.58 0.58 0.60 575 # 5 nm 2.5 x 104 90 325 14 0.64 0.64 0.67 0.67 580 # 5 nm 2.8 x 104 88 250 15 0.62 0.64 0.64 0.65 578 # 5 nm 2.0 x 104 80 300 16 0.72 0.70 0.72 0.74 585 # 5 nm 5.0 x 104 80 < 200 17 0.68 0.70 0.70 0.72 590 # 5 nm 4.8 x 104 90 250 18 0.72 0.74 0.72 0.75 580 # 5 nm 4.4 x 104 85 350 19 0.72 0.72 0.0 0.75 595 # 5 nm 5.5 x 104 85 275 1 "E7" is a eutectic mixture of lower alkyl and alkoxy cyanobiphenyls and terphenyl liquid crystals commerclally avallable from E. Merck Co.

2 "E38" is a eutectic mixture of lower alkyl and alkoxy cyanobiphenyls and terphenyl liquid crystals commercially available from E. Merck Co.

3 "PCH 1132" is a eutectic mixture comprising by weight approximately 14% trans-4-n-pentyl-(4'-cyanobiphenyl)cyclohexane, 26% trans-4-npropyl-(4'-cyanopyhenyl) cyclohexane, 36% trans-4-n-pentyl-(4'-cyanophenyl) cyclohexane, and 24% trans-4-n-heptyl-(4'-cyanophenyl)-cyclohexane, commercially avai@able from E. M. Laboratories, lnc.

4 "ROTN 404" is a eutectic mixture of biphenylpyrimidine liquid crystals commercially available form Hoffman LaRoche.

5 Time in hours required for a 1% by weight solution of the dye in ROTN 404 in a 20 m thick liquid crystal display test cell to lose 50 percent of its S value when exposed to ultravlolet radiation supplied by a type 509/10, 50 watt ultraviolet lamp, avallable from Hanovia, at 21 C.

The dichroic dyes of the present invention are capable of being aligned by nematic liquid crystal materials and, thus, are suitable for use in electro-optic liquid crystal display devices.

The host liquid crystal material may be any liquid crystal compound or mixture of liquid crystal compounds which are per se known in the art. The nematic liquid crystals can have either a positive or negative dielectric anisotropy. As used herein the term "positive" or "negative" refers to the net dielectric anisotropy where mixtures are used. Generally liquid crystals having higher absolute values of dielectric constant are preferred. At this time the positive nematic materials having high dielectric constants are more readily available and for convenience are referred to for purposes of illustration herein. Mixtures of positive and negative materials are also useful, particularly those mixtures having a net positive dielectrric anisotropy.

Readily available positive nematic liquid crystal materials which have been found suitable are trans-4-n-pentyl-(4'-cya no-phenyl)-cyclohexane, trans-4-n-pentyl-(4'-cyano-biphenyl-4)-cyclohexane, p-n-hexylbenzylidene-p'-amino-benzonitrile, p-methoxybenzylidene-p'-a mino-benzonitrile, pethoxybenzylidene-p'-amino-benzonitrile, p-cyano-benzylidene-p'-n-butoxyaniline, p-cyanobenzylidene p'-octyloxyaniline, 4-cyano-4'-alkyl(or alkoxy)biphenyl, 4-cyanophenyl-4'-alkyl(or alkoxy)benzoate, 4alkyl(or alkoxy)phenyl-4'-cyanobenzoate and including the family of alkyl phenyi pyrimidines.

Eutectic mixtures and combinations of all the above are also useful. Illustrates are eutectic mixtures of 4'-substituted-4-cyanobiphenyl wherein the 4' substituents are alkyl or alkoxy of 3 to 8 carbon atoms, and terphenyl liquid crystals. Representative is the commercially available "E7" mixture from B.D.H. Ltd. Another useful mixture is commercially available from Hoffman LaRoche under the trade name "ROTN 404". "ROTN 404" is a eutectic mixture of biphenyl pyrimidine liquid crystals. Yet another useful mixture of compounds comprises mixtures of the phenylcyclohexanes referred to above such as mixtures comprising the 4-alkyl-(4'-cyanophenyl)cyclohexanes, mixtures comprising 4-alkyl (4'-cyanobiphenyl)cyclohexanes, and mixtures comprising both types of compounds.One useful commercial mixture is a four-component mixture available from EM Laboratories, Inc., identified as Nematic Phase 1132 TNC "Licristal" or "PCH 1132". This mixture comprises by weight approximately: 14% trans-4-n-pentyl-(4'-cyanobiphenyl)cyclohexane, 26% trans-4-n-propyl-(4'-cyanophenyl)cyclohexane, 36% trnns-4-n-pentyl-(4'-cyanophenyl)cyclohexane, and 24% trans-4-n-heptyl-(4'-cyanophenyl)cyclohexane.

Other positive nematic materials and compositions useful in the practice of the present invention are phenylbenzoate esters, available under the trade name "EK-1 1 650" from Eastman Organic Chemicals, Eastman Tennessee, and "ZLI" from E. Merck, Darmstadt, Germany; and compositions including these compounds in dominating amounts such that the compositions are provided with a net dielectrically positive anisotropy.

Representative of nematic liquid crystals having negative dielectric anisotropy which would be useful in the present invention is the liquid crystal "EN-1 8" available from Chisso Corporation.

Liquid crystal display devices of the present invention are similar to liquid crystal display devices of the prior art in that they comprise two plates of glass of nominal thickness spaced from a few microns to a few tens of microns apart in a parallel configuration. A spacer or confining gasket material is placed between the two glass plates around the periphery in order to form an airtight, substantially water impermeable bond with the glass surfaces. The inner surfaces of each glass plate are coated with a thin film of, for example, indium/tin oxide to form a conductive electrode surface. The electrode pattern which is desired may be produced by silk-screan or photolithographic techniques which are well-known in the art.The surfaces of each inwardly facing electrode pattern are treated using techniques known in the art to insure that the fill mixture is homogeneously or homeotropically oriented. For "guest-host" displays using host positive nematic liquid crystal material homogeneous orientation is used. For "phasa-change" displays either homeogeneous or homeotropic alignment are useful. However, homeotropic alignment is preferred, i.e., that the molecules are aligned perpendicuiar to the electrode surfaces. Generally, methods of homeotropic orientation comprise coating of the cell inner walls with an agent such as an organosilane coupling agent, a polymer surfactant, or metal oxides, such as silicon monoxide, at angles of about 200 to 900 to the surface.

The dichroic dyes of the present invention may be utilized in both "guest-host" and "phasechange" type liquid crystal displays. The construction of "guest-host" liquid crystal displays is described in Applied Physics Letters, Vol. 13, pages 91-92(1968). "Phase-change" type displays are described in D. L. White and G. N. Taylor, "New Absorptive Mode Reflective Liquid Crystal Display Device," Journal of Applied Physics. Vol. 45, pp. 471 8-4723, (1974). Briefly both types of devices comprise a typical transmissive or reflective liquid crystal display cell having appropriate front and back electrode patterns and featuring a homogeneously or homeotropically oriented liquid crystal layer comprising host positive nematic liquid crystal, and a guest dichroic dye. In "phase-change" type displays an optically active additive is present in amounts sufficient to provide a cholesteric or helically ordered liquid crystal phase. The "host" liquid crystal material has its orientation controlled by the application of electrical fields and in turn interacts with "guest" dichroic dye molecules to induce a cooperative conforming alignment.

Normally, "guest-host" type displays in the "off" state require one polarizer to absorb one polarization of incident light while the guest dichroic material in the display absorbs the other polarization. In the "on" or "bright" state the host liquid crystal material, and thus the guest dye molecules, are oriented by the electric field so that the dichroic dye molecules assume their essentially nonabsorbing state.

In "phase-change" type displays the helical ordering of the host liquid crystal material is superimposed upon the dichroic dye. The helically ordered dichroic dye is thus able to absorb both polarizations of incident light thereby producing a brighter display since no auxiliary polarizers are required, as they are in the traditional "twist-nematic" or "guest-host" type displays. In the absence of an electric field across the display electrodes, the dichroic dye is oriented to absorb a substantial amount, e.g. 95%, of the unpolarized incident light and the display area exhibits a color characteristic of the dichroic dye.When an electric field is applied to the desired electrode, the liquid crystal layer in register with the electrode is caused to change from a cholesteric phase to a nematic phase in homeotropic alignment due to the positive dielectric anisotropy of the liquid crystal host material. In this state, the dichroic dye in the liquid crystal layer is oriented to absorb relatively little incident light and a "clear" area, corresponding to the electrode area on a colored background, is observed. By selective activation of the electrodes, information can be readily displayed.

The concentration of dichroic dye which is useful in "guest-host" and "phase-change" type liquid crystal displays is between about 0.5 and 5 percent by weight of the liquid crystal material. A preferred concentration is between 1 and 2 percent by weight in order to achieve optimal contrast and brightness.

Of course, the maximum amount of dichroic dye which can be present is dependent upon the solubility of the dye in the liquid crystal materials.

The dichroic dyes of the present invention when combined with various dichroic dyes of the prior art may be used to prepare mixtures which absorb throughout the visible spectrum between about 400 nm and 700 nm, resulting in neutral, black-appearing mixtures. When these mixtures are used in "guest-host" type or "phase-change" type liquid crystal devices a display which alternates between black (V=O) and clear (V > O) can be provided. It is preferred to select the various dichroic dyes so that when combined they absorb light uniformly throughout the region between 400 and 700 nm. It is also preferred that all of the dyes have optimal order parameters (S) of about 0.7 or higher in order to insure displays having high contrasts and brightness.

Suitable dichroic dyes of the prior art which have absorption maxima between about 400 and 600 nm are of the well-known azo, azomethine, anthraquinone and polyazo type. Exemplary dyes are disclosed in U.S. 4,145,114; U.S. 4,128,497; U.S. 4,179,395; and in Applicants' copending U.S. Serial No. 70,421 filed August 28, 1 979. It is preferred to have these known dyes present in concentrations which will cause absorption of light in the region between 400 and 600 nm at least equivalent to the absorption of light in the region between 600 and 700 nm caused by the dyes of the present invention.

This is accomplished by adjusting the concentration of each individual dye so that the absorb9nce at the wavelength of maximum absorption (Amax) for each dye is approximately equal.

Exemplary well-known dichroic dyes which are useful when combined in the proper ratio with the dyes of the present invention are:

Dye Xmax (nm) S H9C4 z N=N t N=CB z OC4H9 440 0.78 H9C4 ON=N H3NN N=N X N=N < B3 CH3 CH3 N\ CH3 CH H 3 H CH3 CH3 0S0C4H9 K 4H9 420 0.73 H9C4SO H N N < OH 590 0.65 Figure 2 shows the transmission spectra of a "phase-change" liquid crystal display employing four dichroic dyes, one of which is a dye of the present invention, in "ROTN--404" liquid crystal material a eutectic mixture of biphenyl pyrimidine liquid crystals commercially available from Hoffman LaRoche, and 4% by weight cholesteric additive +442methylbutyl)-4'-cyano biphenyl commercially available as "CB-1 5" from B. D. H. Ltd.The four dyes are:

Dye A max H9C4N=N X N=CH > OC4E9 440 nm H3 C 3 /3 H9C4 - N-N HgCq N=N X N=N N N=N zN 505 CH3 CH3 CH3 CH H H 3N- CH3 CH3 CH3 OCH3 CH /-7 H CB X CB W t N=N- N\CZCH: 610 CH3 CH CH3O 2 3 Curve C is the spectra for the device when an RMS voltage of 15 volts, kHz, is impressed across the electrode surfaces of the cell.The area between the electrodes appears clear and transmits about 70% of light having wave lengths between about 430 and 700 nm. Curve D is the spectra for the device in the absence of an electric field. The device appears black and uniformly absorbs about 85 percent of incident light throughout the region between about 400 and 700 nm.

The following examples illustrate compositions and devices in accordance with the invention.

EXAMPLE 1 The dye

was prepared by the following procedure. Sodium nitrite (1.5 g) was added portionwise to 10 ml of concentrated sulfuric acid. The resulting solution was cooled to 0--50C and 20 ml of 6:1 acetic acid/propionic acid was added dropwise keeping the temperature at less than 1 50C.

One half of this mixture was slowly added to 0.01 mole 5,6-dimethyl-2-aminobenzothiazole which was previously dissolved in 50 ml of a solution of 50% cold sulfuric acid in water, and kept at OOC.

When diazotization was complete, a coupling solution was added and the solution was stirred for 1 5 min. The coupling solution was prepared by dissolving 1.21 grams 2,5-dimethylaniline in 50 ml glacial acetic acid, and cooling this solution to OOC.

After coupling had occurred the mixture was buffered with the addition of saturated sodium acetate solution and stirred for two hours. Adjusting the pH to neutral with sodium hydroxide, recovery by vacuum filtration, and purification from the reaction components affordad the dye intermediate.

Verification by time of flight mass spectroscopy (TFMS), showed that the structure of the intermediate was:

3.1 G of the intermediate was dissolved in 25 ml sulfuric acid and diluted with 50 ml water. After cooling to 0--5 OC, 0.7 grams of sodium nitrite, as nitrosyl-sulfuric acid, was slowly added to form the clear diazonium solution. After one hour the diazonium solution was stirred into 1.71 grams of N-ethyl-1 naphthylamine in 50 ml of glacial acetic acid at OOC. Addition of sodium acetate afforded to the dichroic dye as green irridescent crystals. Filtration, column chromatography and recovery from heptane, yielded the subject dichroic dye:

The structure of this was confirmed by Nuclear Magnetic Resonance Spectroscopy (NMR).

EXAMPLE 2 The dye

was prepared according to the following procedure. 5,6-Dimethyl-2-amino-benzothiazole (17.8 g, 0.1 mole) was dissolved in 200 ml of a solution of 50% sulfuric acid in water and the mixture was cooled in an ice bath to OOC with stirring. Sodium nitrite (6.9 g, 0.1 mole) was slowly added as a 20% solution in concentrated sulfuric acid. When the addition was complete the cold solution was allowed to form the diazonium (about two hours). 2,5-Dimethylaniline (12.1 g,0.1 mole) was dissolved in 100 ml glacial acetic acid and cooled in an Ice bath.When diazotization was complete, 200 g crushed ice was added to the acetic acid solution and the diazotized benzothiazole compound was stirred in, keeping the mass cold. Coupling occurred and anhydrous sodium acetate was stirred in to adjust the solution to a pH of about 5. After an hour the dyestuff product was collected by vacuum filtration, washed and dispersed in 500 ml water. The dyestuff dispersion was then treated with sodium carbonate to render the free base of the intermediate:

31 G (0.1 mole) of the above compound, I, was dissolved in a minimum quantity of 50 ml glacial acetic/propionic acid (8:2) and poured into a warmed (40 C) solution of 50% sulfuric acid in water (150 ml) and cooled to OOC in an ice bath.NaNO2 (6.9 g, 0.1 mole) as a 20% solution in concentrated sulfuric acid was slowly added and the diazonium was formed after two hours at OOC. 2,5- Dimethylaniline (12.1 g, O.1 mole) dissolved in 100 ml glacial acetic was cooled, 200 g ice was added and the diazonium solution was stirred in. Coupling occurred and the mixture was buffered and converted to the free base as above, yielding:

44 G (0.1 mole) of the compound immediately above, II, was dissolved in sulfuric acid solution and diazotized in the conventional manner. 1 7 G (0.1 M) N-ethyl-l -naphthylamine dissolved in glacial acetic acid was coupled to the diazonium.The dyestuff was neutralized with sodium hydroxide solution, collected on a filter, washed and recrystallized from pyridine/petroleum ether. Column chromatography of the dyestuff resulted in the dichroic dye III in 60% yield

The structure of the dye was confirmed by Time of Flight Mass Spectroscopy.

EXAMPLES 3-8 The following dichroic dyes were prepared according to the prodecure described hereinbeiow:

Ex. No. Dye Structure CH3 CH3 H 3 C2H50 X \ N=N X N=N- N=N 0N -N CH3 4 Cm30' N=NO N=N X N;;N t 0 CH3 H3OCH3 5 N 05N=ON=NO N=N XN N(C2H5)2 CH3 OCH3 FH3 6 C2 H5 NH3 i tNXc C2Hs\ N=N N=N N CH3 CH3 CH3 ONHCH3 CH3 N=N-( t t NX 9H3 CH3 6 Cs 1 \\N=N < N=N C511110 t N (C25s) CH3 0 0 )N=N OCHN=N N=N0 N N (C2H5) 2 3 CH3 CH3 An appropriate amount of a benzothiazole (iisted in the table hereinbelow) was dissolved in 100 ml concentrated sulfuric acid by portionwise addition with stirring at room temperature.This solution was cooled to -1 00C in an ice salt bath (500 gm ice/1 00 gm salt). To this cooled solution was added slowly through a dropping funnel a solution of 1.2 gm of nitrosylsulfuric acid dissolved in 20 gm concentrated sulfuric acid and 10 g of a 7:3 by volume acetic acid/propionic acid solution. The temperature of the mixture was maintained at about 0 C throughout the addition. The diazotization reaction was allowed to proceed for about 4 hours at about 0--1 O"C. The diazotization product was then slowly poured into a solution of an appropriate amount of a first aniline (listed in the table hereinbelow) in 100 ml glacial acetic acid. Coupling was allowed to proceed for 30 minutes at a temperature less than 50C.After coupling about 50 g of anhydrous sodium acetate was stirred into the solution, followed by the addition of 100 gm of ice. The mixture is allowed to warm to room temperature overnight (about 1 8 hours). The precipitated sulfate salt of the first dye intermediate was recovered by vacuum filtration and thoroughly washed with water and oven dried.

(0.01 M) of the first intermediate sulfate salt was dissolved in 50 ml concentrated sulfuric acid and this solution was cooled to 00C using an ice-salt bath. Diazotization of this dye intermediate was accomplished using 1.20 g nitrosylsulfuric acid in 20 mls of sulfuric acid and 20 mls of a 8:2 by volume solution of acetic acid/propionic acid. The diazotization reaction was allowed to proceed for four hours at about 0--1 OOC. The diazotized amine was then slowly poured into a solution of an appropriate amount of a second aniline (listed in the table hereinbelow) in 50 ml glacial acetic acid containing 100 g of ice.While the mixture was kept cold and stirred it is brought to pH 5 with anhydrous sodium acetate and allowed to couple overnight at room temperature (18--200C). Filtration yielded the sulfuric acid salt of the second dichroic dye intermediate.

In the case of dye number 8 the second dye intermediate was again diazotized as above using nitrosylsulfuric acid, and coupled again to the second aniline to yield the sulfuric acid salt of the third dichroic dye intermediate, having three dimethyl phenylazo linkages.

0.01 moles of the sulfuric acid salt of the second dichroic dye intermediate, for Examples 3-7, and the third dichroic dye intermediate, for Example 8, was dissolved in 100 ml of concentrated sulfuric acid by making a paste of the intermediate in water (5-1 0 ml) and crushing any lumps. This thick paste was stirred portionwise into the sulfuric acid, allowing each quantity, i.e., 1.0 g to go into solution prior to the addition of the next portion.When all the dye intermediate had been added, the stirring solution was cooled to -1 00C in an ice bath.0.01 moles of nitrosylsulfuric acid was added and the mixture was stirred for 6 hours at-I 00C. The diazotization product was coupled with an appropriate amount of a coupler (listed in the table hereinbelow) dissolved in 100 ml glacial acetic acid. The cold diazonium was slowly added to the coupler solution with stirring and the resultant mixture was kept cold. Coupling was allowed to proceed overnight (at room temperature). The mixture was then brought to a pH of 5 using anhydrous sodium acetate and the crude dye was filtered. The crude dye was dispersed in a rapidly stirring solution of 50 gm sodium carbonate in 1 of water.The neutralized dye precipitated and was recovered by vacuum filtration. The solid material was washed with water until the wash was colorless.

The crude dye was dissolved in toluene (50 ml) and chromatographed on a silica column using toluene followed by a 9:1 by volume solution of toluene/methanol, as elutants. The eluted dye was concentrated to half volume on a rotary evaporator and recrystallized by using a iarge volume (20:1) of n-heptane.

The dye product was recovered as a microcrystalline powder by filtration and vacuum drying.

The structure of each dye was confirmed by Time of Flight Mass Spectroscopy and NMR.

When utilized in traditional "guest-host" type liquid crystal display cells the dyes prepared by Examples 3-8 exhibited absorbances with Amax in the region above 600 nm, with the voltage off. In addition the dyes had optical order parameters in "E-7", "ROTN 404" and "PCH 11 32" liquid crystal materials of greater than 0.7.

Exampel Benzothiazole First Aniline Second Aniline Coupler No. (Amount) (Amount) (Amount) (Amount) 3 2-amino-5-ethoxy benzo- 2,5-dimethylaniline 2,5-dimethylaniline N-(n)-butyl-1-aminothiazole (1.8 g) (1.21 g) (1.21 g) naphthalenen (1.97 g) 4 2-amino-5-methyoxybenzo- &alpha;-naphthyiamine 2,5-dimethylaniline N,N'-methylethyl-1-aminothiazole (1.81 g) (1.43 g) (1.21 g) naphthalene (1.85 g) 5 2-amino-[5,6]-cyclopropyl- 3,5-dimethylaniline 2,5-dimethoxyaniline N,N'-dithyl-aminobenzothiazole (1.9 g) (1.21 g) (1.52 g) naphthalene (1.99 g) 6 2-amino-5.6-diethyibenzo- 2.5-dimethylaniline 2,5-dimethylaniline 2,3-dihydro-2,2'-dimethylthizole (1.82 g) (1.21 g) (1.21 g) permidene (1.98 g) 7 2-amino-5-methyl-benzo- 2.5-dimethylaniline &alpha;;-naphthylamine N-methyl-1-amino-naphthalene (1.57 g) 8 2-amino-5-pentoxybenzo- 2,5-dimethylaniline 2.5-dimethylaniline N-pentyl-1-aminothiazole (2.33 g) (1.21 g) (1.21 g) naphthalene EXAMPLE 9 A "phase-change" type liquid crystal display which is black in the absence of an electric field and is clear in the presence of an electric field, was constructed as follows.

A display cell was assembled comprising two opposing glass plates coated on their interior surfaces with tin/indium oxides to form a conductive electrode pattern. Overlaying the electrode pattern, a homeotropic orientation layer was created by the vapor deposition of a dielectric silicone monoxide layer about 100 A thick, at an angle of less than 300. The cell was provided with a reflectorized backing, and had a 18 m cell spacing.

A mixture of the following four dyes was prepared, in the concentrations indicated.

Dye Amax (nm) % by weight H9C400 N=N- N=N 0C4H9 440 0.93 CH3 CH3 ;CH3 HgC4 N=N =N CH3N=NN=N N=N CH3 N 505 0.74 CH3 C,H3 H s3 585 N=N---( N=N- 585 0.60 N N=NON=NO CH3 t N=N z OCH3 t CH3 0 0 OCH3 CH3 H CH3 ,"" \ N X N=N 4 N ; 1.10 CH3 CH3 (o\ CH2CH3 CH3 2 Percent by weight of the above dye mixture was dissolved in "ROTN--404" liquid crystal material and 4 percent by weight of the cholesteric additive "CB-1 5", whIch is a +4-(2-methylbutyl)- 4'-cyano biphenyl commercially available from Hoffman LaRoche. This mixture was used to fill the display cell.

Figure 2 illustrates the transmission spectra for the above "phase-change" device using a Beckman Model 5230 ultraviolet-visible spectrometer with a tungsten source. Curve C is the spectra for the device when an RMS voltage of 1 5 volts, 1 kHz, was impressed across the electrode surfaces of the cell. The cell transmitted more than about 70 percent of the incident light between about 430 and 700 nm, in the area between the electrodes, when in the "on" state. Curve D is the spectra for the device when the voltage is reduced to zero. Very little light is absorbed between about 400 and 650 nm when the cell is in the "off" state.

The contrast ratio of the cell in the "on" and "off" state was determined by the following method.

The filled cell was mounted on an optical bench and a collimated tungsten light source located at an angle of 450 with respect to the cell surface, was focused on the display. An intermittent RMS voltage of 5 volts at 1 kHz was impressed across the electrode surfaces of the cell. The electro-optic modulation of the cell was observed via light reflected from the cell to a photometer, available from Spectra Physics cho., Princeton, N.J., fitted with a photopic filter and connected to a time base oscilloscope. The contrast ratio was determined by measuring the reflectance (or "Brightness") in foot lamberts in the "voltage on" and "voltage off" states, and using the following equation: Brightness cell on (v > O) Transmission cell on Contrast Ratio =~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ - 1= - 1 Brightness cell off (v = O) Transmission cell off The contrast ratio over the range of wave lengths between about 400 and 700 nm was about 10:1.

Claims (22)

1. A dichroic dyestuff characterized in that it has the general formula Q-A-Z wherein: A is a polyazo group; Q is a 5,6-di-substituted benzothiazyl group; and Z is selected from the group consisting of substituted naphthalene, permidene or jujolidene groups.

2. The dichroic dyestuff of Claim 1 further characterized in that the polyazo group A has the general formula:

wherein m is 0, or an integer from 1 to 6, R is independently selected from alkyl or alkoxy groups having from 1 to 8 carbon atoms, and x is independently 0, 2 or 4, provided that when x is 2, the two R groups are not substituted or adjacent ring carbon atoms.

3. The dichroic dyestuff of Claim 1 further characterized n that the polyazo group A has the general formula:

wherein m is O or an integer from 1 to 6, and wherein in from 0 to m aromatic rings, x is 2 and the two R groups are combined in the group -C=CH-CH=CH-- are substituted on two adjacent ring carbon atoms, such that the aromatic nucleus is a naphthalene group.

4. The dichroic dyestuff of Claim 1 further characterized in that the 5,6-di-substituted benzothiazyl group Q has the general formula:

wherein B and B' are independently selected from the group consisting of H, CnH2n+,, OCnH2n,1, phenyl or phenoxy, wherein n is an integer frorn 1 to 8.

5. The dichroic dyestuff of Claim 1 further characterized in that the 5,6-di-substituted benzothiazyl group 0 has the general formula:

6. The dichroic dyestuff of Claim 1 further characterized in that Z is a substituted naphthalene having the formula:

wherein R, is selected from the group consisting of H and CnH2n+, and wherein R2 is CnH2n+" wherein n is an integer from 1 to 6.

7. The dichroic dyestuff of Claim 1 further characterized in that Z is a permidene group having the general formula:

wherein R3 and R4 are independently selected from the group consisting of lower alkyls having 1-6 carbon atoms.

8. The pelochroic dyestuff of Claim 1 further characterized in that Z is a permidene group containing a cyclopentyl group and has the general formula:

wherein said cyclopentyl group is substituted in available positions by groups independently selected from the group consisting of H and lower alkyls having 1-8 carbon atoms.

9. The dichroic dyestuff of Claim 1 further characterized in that Z is a permidene group containing a cyclohexyl group arid has the general tormula:

wherein said cyclohexyl group is substituted in available positions by groups independently selected from the group consisting of H and lower alkyls having 1-8 carbon atoms.

10. The dichroic dyestuff of Claim 1 further characterized in that Z is a jujolidene group having the formula:

11. The dichroic dyestuff of Claim 1 further characterized in that the dichroic dyestuff is selected from the group consisting of:

1 2. A composition of matter comprising a nematic liquid crystal material in admixture with a dichroic dyestuff characterized in that said dichroic dyestuff is the dichroic dyestuff of Claim 1.

1 3. The composition of Claim 1 2 further characterized in that said composition additionally comprises at least one dichroic dye having maximum absorption at wavelengths between 400 and 600 nm.

14. The composition of Claim 12 further characterized in that said dichroic dyestuff is present in an amount of 0.5 to 5 percent by weight.

1 5. The composition of Claim 12 further characterized in that there is additionally present an optically active compound in an amount sufficient to provide a cholesteric phase.

1 6. A "guest-host" type liquid crystal display device which is responsive to the absence or presence of an electric field, said device comprising a layer of a nematic liquid crystal composition in admixture with a dichroic dyestuff, and two conductive electrodes positioned, respectively, adjacent opposing surfaces of said layer, characterized in that said dichroic dyestuff is the dichroic dyestuff according to Claim 1.

1 7. A "guest-host" type liquid crystal display which is responsive to the absence or presence of an electric field, and which appears neutral black in the absence of said electric field and clear in the presence of said electric field, said device comprising: a) a "guest-host" layer comprising a nematic liquid crystal material and a plurality of dichroic dyes which together strongly absorb throughout the region between 400 and 600 nm; and b) two conductive electrodes positioned, respectively, adjacent opposing surfaces of said layer; characterized in that said "guest-host" layer additionally comprises the dichroic dyestuff of Claim 1 in admixture with said "guest-host", liquid crystal-dichroic dye mixture.

1 8. A "phase change" type liquid crystal display device which is responsive to the absence or presence of an electric field, said device comprising a layer of a nematic liquid crystal material in admixture with an optically active compound and a dichroic dyestuff, and two conductive electrodes positioned, respectively, adjacent opposing surfaces of said layer, characterized in that said dichroic dyestuff is the dichroic dyestuff of Claim 1.

19. A "phase-change" type liquid crystal display device which is responsive to the absence or presence of an electric field, and which appears neutral black in the absence of said electric field and clear in the presence of said electric field, said device comprising: a) a layer of a nematic liquid crystal material in admixture with a plurality of dichroic dyes which together absorb strongly throughout the region between about 400 and 600 nm, and an optically active compound; and b) two conductive electrodes positioned, respectively, adjacent opposing surfaces of said layer; characterized in that said layer additionally comprises the dichroic dyestuff of Claim 1 in admixture with said liquid crystal material.

20. A dyestuff as claimed in Claim 1 substantially as herein described with reference to any one of the Examples.

21. A composition as claimed in Claim 1 2 substantially as herein described with reference to any one of the Examples.

22. A liquid crystal display substantially as herein described with reference to any one of the Examples.