LIQUID CRYSTALLINE MATERIALS INCORPORATING DICHROIC DYE AND OPTICAL DISPLAYS UTILIZING SAME

Abstract: Disclosed are nematic liquid crystalline compositions and optical display devices utilizing a new family of optically active azo type dichroic dyes represented by the formulas: The dyes are imparted with both liquid crystalline and dichroic characteristics and are able to be mixed with one or more other types of organic dyes to provide the liquid crystalline materials improved color-to-color contrast and hue variation.

Description: LIQUID CRYSTALLINE MATERIALS INCORPORATiNG DICHROIC DYE AND OPTICAL DISPLAYS UTILIZING. SAML INTRODUCTION This invention relates generally to nematic liquid crystalline compositions incorporating a dichroic (pleochroic) dye for improving color contrast between electrically activated and de-activated states of the nematic liquid crystalline material and more particularly to nematic liquid crystalline compositions incorporating a new family of optically active azo type dichroic dyes that are imparted with both dichroic and liquid crystalline characteristics and that singularly and in combination with other members of the family and with other conventional dyes are able to provide improved contrast in color and color hues between the electrically activated and de-activated state of the liquid crystalline material. BACKGROUND OF THE INVENTION Electro-optical displays useful for utilizing the light transmission characteristics of nematic liquid crystalline materials are generally provided by hermetically sealing a several micron to about 100 micron thick layer of the nematic liquid crystalline material between a pair of plates of which at least one of the plates is transparent and which have transparent electrically conductive coatings in the form of discrete images on their inner facing surfaces adjacent the liquid crystalline material. Means is provided for attaching the conductive coating of one of the plates to a source of controlled electrical power and for transmitting a portion of the power across to the opposite conductive coating to provide a potential gradient across the liquid crystal layer that is able to rotate the liquid crystalline molecule when electrical power is applied. It is also known¯ that nematic liquid crystalline materials having positive dielectric anistrophy are provided by liquid crystal molecules having high polarity such as provided for example by appending a cyano group at the extreme end of one of the phenyl groups along the long molecular axis of a biphenyl type liquid crystal molecule. In addition, it is common practice to deposit an organic surfactant material such as polyvinyl alcohol over the conductive coatings--on the facing surfaces of the display plates that can be rubbed to providesufficienthomogeneous (parallel) alignment of a nematic liquid crystal having positive dielectric anistrophy. In contrast, nematic liquid crystalline materials having negative dielectric anistrophy are materials that change from homotropic alignment in the unenergized state to homogeneous (parallel) alignment in the electrically energized state. Generally, it has been the practice to use nematic liquid crystalline materials having positive dielectric anistrophy or blends of nematic liquid crystalline materials having both negative and positive dielectric anistrophy with sufficient amount of material having positive dielectric anistrophy to cause the blend to behave as having positive dielectric anistrophy. Although it has been the practice in the past to add selected organic dyes,separately or in conjunction with dichroic dyes for'coloring nemate liquid crystalline materials, such dies in the absence of a dichroic die have been unable to provide an effective contrast in the color that might otherwiseoccur when the nematic liquid crystalline molecules are rotated in the presence of an electrical field as previously described. It is believed that the improved contrast is provided by the fact that long axis of the dichroic dye molecule tends to align with the long axis of the nematic liquid crystal molecule and is caused to rotate with the liquid crystal molecules when an electrical potential gradient is imposed across the liquid crystalline material. Since most dichroic dyes have been found to absorb a greater amount of light when incident light's electric vector is directed along their long molecular axis than when it is directed along their short molecular axis, a greater contrast is provided in the appearance of the liquid crystalline material when its long molecules are rotated in a direction parallel to the incident light. An early example of thermometric liquid crystalline compositions that are able to change colors at different temperatures by using soluble diazo, indulene and nigrosine dyes is disclosed in United States Patent 3,576,761. Although such compositions may be suitable for the purpose intended, they are generally unable to provide effective color contrast and variations in hue. United States Patent 3,960,750 discloses a more recent example of the use of two particular pleochroic dyes with at least one other type of a dye of different hue in a liquid crystal having positive dielectric anistrophy provided fby a mixture of liquid crystals having both positive- and negative dielectric anistrophy. Although the two pleochroic dyes disclosed are proported to provide good color-to-color contrast -by the previously described phenomenon of light absorbtion differences between their long and short molecular axis, they are not themselves optically active liquid crystalline materials and thus are unable to provide improved color contrast and hue variations,. Another example of a¯pair of pleochroic dyes proported to be useful in improving color contrast in nematic liquid crystalline materials is disclosed in United States Patent 3,960,751. But here also, the dyes are not imparted with both liquid crystalline characteristics and dichroic characteristics and thus are unable to achieve a high order of contrast and hue variation. An example of an optically active diazo compound having branched carbon chains appended to the phenyl groups is disclosed in United States Patent 3,977,769. Although such compounds are proported to be useful in adjusting the threshold voltage level of. liquid crystalline materials, they are not imparted with both the optically active liquid crystalline and dichroic characteristics and generally would not provide high order of color contrast and hue variation. An example of the use of azo type and/or azoxy type compounds for broadening the nematic operating temperature range of nematic liquid crystalline materials is disclosed in United States Patent 3,989,639 Generally, the broadening is provided by halide groups appended to one of the phenyl groups and none of the compounds disclosed provide a high order of color contrast and hue variation* SUMSiARY OE THE INVENTION Accordingly, it is an object of this invention to provide a nematic liquid crystalline composition that has a high order of color-to-color contrast and hue variation between the electrically activated and de-activated states of the composition. It is another object to this invention to provide a nematic liquid crystalline composition having improved color-to-color contrast provided by a new family of optically active dichroic dye components that are imparted with both liquid crystalline and dichroic characteristics. It is yet a further object of this invention to provide a nematic liquid crystalline composition having improved color-to-color contrast and hue variation between the electrically activated and de-activate states of the composition by the incorporation of one or more of the members of a new family of optically active dichroic dye'components that are imparted with both liquid crystalline and dichroic characteristics either alone or- in conjunction with one or more other typesof organic dyes. It is another object of this invention to provide a liquid crystal display utilizing a nematic liquid crystalline composition provided with improved color-to-color contrast and hue variation by the incorporation of a new'family of optically active dichroic dye components that are imparted with both liquid crystal and dichroic characteristics either alone or in conjunction with other types of organic dyes. DETAILED DESCRIPTION OF THE INVENTION The above objects and others have been achieved by providing a new family of dichroic dyes represented by the formulas: EMI7.1 and EMI7.2 Where for Formula I: EMI8.1 is an ester of the formula EMI8.2 -or a ketone of the formula EMI8.3 where n is an integer from 1 through 22; and where for both Formulas I and II: EMI8.4 is a substituted phenyl of the formula EMI8.5 or is a biphenyl of the formula EMI9.1 or is a disubstituted cyclohexane of the formula EMI9.2 or is a bicyclo (2,2,2) octane ring of the formula EMI9.3 or is an ester of the formula EMI9.4 0 II CH -O-C- n 2n where n is an integer from 1 through 22 or is a hydrogen group wherein R1 is a cyano group or an alkyl of the formula -CnH2n + 1 or an alkoxy of the formula CnH2n + 1 - O - or is an ester of the formula EMI10.1 or a ketone of the formula EMI11.1 EMI11.2 where n is an integer from 1 through 22. is a phenyl of the formula EMI11.3 or'is a substituted cyclohexane of the formula EMI11.4 or is a bicyclo (2,2,2) octane ring of the formula EMI11.5 or is a substituted cyclohexane of the formula EMI12.1 or is a biphenyl of the formula EMI12.2 or is a substituted biphenyl of the formula EMI12.3 or is a phenyl-cyclohexane derivative of the formula EMI12.4 or is an alkyl of the formula Cn 2n + 1 where n is an integer from 1 through 22 where R2 is a cyano group or an alkyl of the formula - CnH H2 1 or an alkoxy of the formula CnH2n + 1- O - or is an ester of the formula EMI13.1 or a ketone of the formula EMI13.2 where n is an integer from 1 through 22. Preferred subgroups of the above described family of optically active dichroic dyes are provided where R1 EMI14.1 is an hydrogen group and R2 EMI14.2 is a substituted phenyl or cyclohexane ring or alkyl group as respectively illustrated in following formulas III, IV and V: EMI14.3 where n is an integer from 1 through 22. Particularly preferred embodiments of the opitcally active dichroic dyes are shown in tollowing formulas VI through X: EMI15.1 EMI16.1 Following Table I illustrates the nematic and esotropic temperature characteristics determined for Formulas VI through X. ,Table I Formula Temperature Temperature at which at which nematic esotropic ( C) ( C) VI - 84 C VII 1000 s 114.90 VIII 1030 113.40 IX 1030 113.70 X 95.5 -96.7 145.60 Generally, the optically actiye dichroic dye components represented by formulas VI through X have a yellowish orange color and, as previously described, other types of suitably selected organic dyes can be added to the compositions of the invention to impart the various color contrast and hue variations desired for a particular application. The dichroic dye components of formulas VI through X do not have polar groups appended to either of the phenyl groups and thus exhibit negative dielectric anistrophy. Although it has been common practice in the past to use polarizer plates on either one or both of the outer surfaces of the previously described plates between which nematic liquid crystalline materials are contained, it has been found that because of the highly effective light absorbtion characteristics of the dichroic dyes of the invention, polarizer plates are not required in many instances. It has also been found that the dichroic dye components of the invention exhibit excellent light stability and in many instances are able to raise the isotropic temperature.of the liquid crystalline materials to which they are added. An example of one method of making a typical dichroic dye component of the invention is where a gasoline colorant commercially available from Abridge Chemical Company having the formula: EMI17.1 is reacted with: EMI18.1 to provide: EMI18.2 The dichroic dye components of the invention are able to be mixed amongst themselves and with other types of organic dyes or previously described. Often it is also advantageous to add an optically active twisting agent to formulations imparting the dichroic dye components of the invention such as C15 or CB15 biphenyls -sold by Merck Chemical Company. A typical mixture for providing a white image on a dark- background when,the-liquid crystalline material is electr,ically energized-in a transmission type optical display where both pla,tes are tra,nsparent and a single polarizer is used on the back plate such that it is 900 out of phase with the rubbing direction on the back plate is to add the following components by percent weight to the total weight of a typical host nematic liquid crystalline material such as E-7 sold by Merck Chemical Company: : Component % (by Weight) Formula X 5 Formula VIII 5 Blue organic dye such 1.7 as anthroquinone PDH-I3-D16 sold by Merck Chemical Company Suitable Red organic dye .3 Merck C-15 Twisting agent .1 An example of a formulation for use in providing a white image on a dark background in a reflective type optical display that has a white reflector on the inside of the back plate and does not require polarizers is where, to a typical nematic liquid crystalline material having positive dielectric anistrophy, the following components are added in the indicated percentages by weight to the total weight of the liquid crystalline material: : Component % (by eight) Formula X 5 Formula VIII 5 Suitable blue organic dye .6 Suitable red organic dye .2 Merck C-15 Twisting Agent 4 -- 50 An example of providing a transmissive type optical display device with a dark image on a light background when the liquid crystalline material is electrically energized and there are no rubbing lines on the inner surface of the plates is to add to a nematic liquid crystalline material having negative dielectric anistrophy the following components in the indicated percentages by weight to the total weight of the liquid crystalline material: : Component % (by Weight) Formula X- 5 Formula VII-I 5 Suitable blue organic dye- .6 Suitable rd organic dye .2 Nematic liquid crystalline compositions of the invention that incorporate one or more of the members of the optically active dichroic dye components of the invention are able to provide both transmissive and reflective type electro optical displays having improved color-to-color contrast and hue variation and are readily adaptable to combine with one or more other types of suitable organic dye colorants and twisting agents when desired to provide a broad spectrum of hue variation and color-to-color contrast.

Claims: WHAT IS CLAIMED IS: 1. A nematic liquid crystalline composition comprising a mixture of at least one nematic liquid crystalline material and at least one optically active dichroic dye component represented by the formula EMI21.1 where for formula I: EMI21.2 is an ester of the formula EMI21.3 EMI22.1 or a ketone of the formula EMI22.2 where n is an integer from 1 through 22; and and where for both Formulas I and II: EMI22.3 is a substituted phenyl of the -formula EMI22.4 or is a byphenyl of the formula EMI22.5 or is a disubstituted cyclohexane of the formula EMI23.1 or is a bicyclo (2,2,2) octane ring of the formula EMI23.2 or is an ester of the formula: : EMI23.3 where n is an integer from 1 through 22 or is a hydrogen group wherein R1 is a cyano group or an alkyl of the formula Cnh2n + 1 or an alkoxy of the formula CnH 2n + 1 or is an ester of the formula EMI24.1 or a ketone of the formula EMI24.2 where n is an integer from 1 through 22 EMI24.3 R2 is a phenyl of the formula EMI24.4 or is a substituted cyclohexane of the formula EMI25.1 or is a bicyclo (2,2,2) octane ring of the formula EMI25.2 or is a biphenyl of the formula EMI25.3 or is a substituted biphenyl of the formula EMI25.4 or is a substituted cyclohexane of the formula EMI25.5 or is a phenyl-cyclohexane derivative of the formula EMI26.1 or is an alkyl of the formula - CnH2n + 1 where n is an integer of from 1 through 22 where R2 is a cyano group or an alkyl ot the formula - CnH2n + 1 or an alkoxy of the formula nN2n + 1 or is an ester of the formula EMI27.1 or is a ketone of the formula EMI27.2 where n is an integer from 1 through 22. 2* The liquid crystalline composition of Claim 1 wherein the dichroic dye component has the formula EMI27.3 where n is an integer from 1 through 22. 3. The liquid crystalline composition of Claim 1 wherein the dichroic dye component has the formula EMI28.1 where n is an integer from 1 through 22. 4. The liquid crystalline composition of Claim I wherein the dichroic dye component has the formula EMI28.2 where n is an integer from 1. through 22. 5. The liquid. crystalline composition of Claim 1 wherein the dichroic dye component comprises a. mixture of at least one component having the formula EMI28.3 with at least one other component having the formula EMI29.1 where n is an integer from 1 through 22. 6. The liquid crystalline composition of Claim 1 wherein the dichroic dye component comprises a mixture of at least two components having the formula EMI29.2 where n is an integer from 1 through 22 and the integer is different for each of the two components. 7. The liquid crystalline composition of Claims 1, 2, 3, 4, 5 or 6 having an effective amount of at least one twisting agent included therein. 8. The liquid crystalline composition of Claim 7 wherein the twisting agent is an optically active biphenyl type twisting agent. 9. The, liquid crystalline composition of Claims 1, 2, 3, 4, 5 or 6 having an effective amount of coloring matter included therein that is soluble in said composition. 10. The liquid crystalline composition of Claim 9 wherein the coloring matter comprises at least one organic dye selected from the class consisting of azo, diazo, anthraquinone, azine, indulene, xanthene and nigrosine dyes and mixtures thereof. 11.- A liquid crystal display device incorporating the liquid crystalline composition of Claim 1.

Inventors: FERRATO, JOSEPH PATRICK
Applicants: CRYSTALOID ELECTRONICS COMPANY
Application year: 1982
Main classification: C09K3
IPC codes: C09K19, C09B29, G02F1