DE3534780A1 - Chiral phenol esters of mesogenic carboxylic acids, a process for the preparation thereof and the use thereof as dopes in liquid-crystal phases - Google Patents
Chiral phenol esters of mesogenic carboxylic acids, a process for the preparation thereof and the use thereof as dopes in liquid-crystal phasesInfo
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- DE3534780A1 DE3534780A1 DE19853534780 DE3534780A DE3534780A1 DE 3534780 A1 DE3534780 A1 DE 3534780A1 DE 19853534780 DE19853534780 DE 19853534780 DE 3534780 A DE3534780 A DE 3534780A DE 3534780 A1 DE3534780 A1 DE 3534780A1
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- liquid crystal
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/58—Dopants or charge transfer agents
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- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Liquid Crystal Substances (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Die Kennlinien der in Flüssigkristall-Displays verwendeten elektro-optischen Effekte verändern sich im allgemeinen mit der Temperatur. Insbesondere bei einer Ansteuerung im Multiplexbetrieb ergeben sich daraus Schwierigkeiten, die zu einer unerwünschten Einschränkung des Arbeitstemperaturbereiches führen können. Bei verschiedenen elektrooptischen Effekten kann durch Zusatz chiraler Verbindungen zum nematischen Flüssigkristall über die Temperaturfunktion der Ganghöhe der dadurch induzierten cholesterischen Helixstruktur die Temperaturabhängigkeit der elektrooptischen Kennlinien vorteilhaft beeinflußt werden, so beim cholesterisch-nematischen Phasenumwandlungseffekt, der TN ("twisted nematic")-Zelle und dem kürzlich vorgestellten SBE ("supertwisted birefringence effect"). Die üblichen bekannten Dotierstoffe induzieren im allgemeinen eine mit zunehmender Temperatur ansteigende Ganghöhe; es sind in jüngster Zeit auch bereits Dotierstoffe beschrieben worden, die diesen oftmals unerwünschten Effekt nicht zeigen.The characteristics of those used in liquid crystal displays electro-optical effects generally change with the temperature. Especially when activated difficulties arise in multiplex operation, leading to an undesirable restriction of the working temperature range being able to lead. At different electro-optical effects can be achieved by adding chiral compounds to the nematic liquid crystal via the temperature function the pitch of the cholesteric induced thereby Helix structure the temperature dependence of the electro-optical characteristics are advantageously influenced, so with the cholesteric-nematic phase change effect, the TN ("twisted nematic") cell and the recently presented one SBE ("supertwisted birefringence effect"). The Commonly known dopants generally induce a pitch increasing with increasing temperature; dopants have also been described recently that have this often undesirable effect do not show.
Aus der DE-C 28 27 471 (= US-A 42 64 148) ist der Zusatz von zwei unterschiedlichen chiralen Dotierstoffen zu nematischen Trägersubstanzen bekannt; dabei erzeugt der eine chirale Dotierstoff in der nematischen Trägersubstanz eine rechtshändige Verdrillung, der andere eine linkshändige Verdrillung. Mit einer solchen Dotierung wird eine Abnahme der Ganghöhe erreicht, aber es sich zur Erreichung dieses Effekts relativ hohe Gesamtkonzentrationen erforderlich, die zu einer negativen Beeinflussung der anderen Materialparameter führen können. The addition is from DE-C 28 27 471 (= US-A 42 64 148) of two different chiral dopants known nematic carrier substances; the a chiral dopant in the nematic carrier a right-handed twist, the other a left-handed Twist. With such a doping a decrease in the pitch, but it becomes Achieving this effect relatively high total concentrations required leading to a negative influence which can lead to other material parameters.
In der DE-A 33 33 677 werden u. a. Umsetzungsprodukte (Ester) von chiralem Butandiol-(2,3) mit mesogenen Carbonsäuren beschrieben, die bereits in Einzeldosierung in Flüssigkristall-Phasen die Optimierung der Temperaturkompensation vereinfachen können. Diese bekannten Ester weisen aber oftmals ein für bestimmte Anwendungen noch zu niedriges Verdrillungsvermögen auf, dieses beträgt - ausgedrückt durch das "pc-Produkt" - nach den Angaben in dieser DE-A 9,2 bis 116 µm·Gew.-%.DE-A 33 33 677 describes, inter alia, reaction products (esters) of chiral butanediol- (2,3) with mesogenic carboxylic acids, which can simplify the optimization of the temperature compensation even in single doses in liquid crystal phases. However, these known esters often have a twisting capacity that is still too low for certain applications, and this is - expressed by the “ pc product” - according to the information in this DE-A 9.2 to 116 μm.% By weight.
Aufgabe der vorliegenden Erfindung ist es deshalb, neue Verbindungen aufzufinden, die bei ihrem Einsatz als chirale Dotierstoffe in Flüssigkristall-Phasen bei verhältnismäßig geringen Zusatzmengen bereits eine Optimierung der Temperaturkompensation und gleichzeitig eine hohe Verdrillung der induzierten Helixstrukturen bewirken.The object of the present invention is therefore to create new ones Find compounds when used as chiral Dopants in liquid crystal phases at relative small additional quantities already optimize the Temperature compensation and high twisting at the same time of the induced helix structures.
Die Erfindung geht aus von einem bekannten Ester aus einer chiralen Verbindung mit zwei OH-Gruppen und einer mesogenen Carbonsäure. Die erfindungsgemäßen Verbindungen sind gekennzeichnet durch die allgemeine Formel (I) in der MC einen Molekülrest einer mesogenen Monocarbonsäure nach Abspaltung einer OH-Gruppe bedeutet.The invention is based on a known ester of a chiral compound with two OH groups and a mesogenic carboxylic acid. The compounds according to the invention are characterized by the general formula (I) in the MC means a molecular residue of a mesogenic monocarboxylic acid after splitting off an OH group.
Eine weitere Lösung der gestellten Aufgabe ist eine verdrillbare Flüssigkristall-Phase mit einem Gehalt an mindestens einer chiralen Verbindung, die dadurch gekennzeichnet ist, daß sie als chirale Verbindung mindestens eine Verbindung der allgemeinen Formel (I) oder eines im aromatischen Teil des Phenolteils substituierten Phenolesters (entsprechend dieser allgemeinen Formel (I) als unsubstituiertem Grundmolekül) enthält. Unter dem Begriff "verdrillbare Flüssigkristall-Phase" sind nematische, cholesterische, geneigte ("tilted")-smektische, insbesondere smektisch C (Sc oder SmC), Phasen zu verstehen.A further solution to the problem is a twistable liquid crystal phase containing at least one chiral compound, which is characterized in that it contains at least one compound of the general formula (I) or a phenol ester substituted in the aromatic part of the phenol part as a chiral compound. according to this general formula (I) as an unsubstituted basic molecule). The term "twistable liquid crystal phase" means nematic, cholesteric, tilted smectic, in particular smectic C (S c or SmC) phases.
Die erfindungsgemäßen verdrillbaren Flüssigkristallphasen bestehen aus 2 bis 20, vorzugsweise 2 bis 15 Komponenten, darunter mindestens einem der erfindungsgemäß beanspruchten chiralen Dotierstoffe. Die anderen Bestandteile werden vorzugsweise ausgewählt aus den bekannten Verbindungen mit nematischen, cholesterischen und/oder geneigt- smektischen Phasen, dazu gehören beispielsweise Schiffsche Basen, Biphenyle, Terphenyle, Phenylcyclohexane, Cyclohexylbiphenyle, Pyrimidine, Zimtsäureester, Cholesterinester, verschieden überbrückte, terminal-polare mehrkernige Ester von p-Alkylbenzoesäuren. Im allgemeinen liegen die im Handel erhältlichen Flüssigkristall-Phasen bereits vor der Zugabe des chiralen Dotierstoffes als Gemische verschiedenster Komponenten vor, von denen mindestens eine mesogen ist, d. h. als Verbindung, in derivatisierter Form oder im Gemisch mit bestimmten Cokomponenten eine Flüssigkristall- Phase zeigt [= mindestens eine enantiotrope (Klärtemperatur Schmelztemperatur) oder monotrope (Klärtemperatur Schmelztemperatur) Mesophasenbildung erwarten läßt].The twistable liquid crystal phases according to the invention consist of 2 to 20, preferably 2 to 15 components, including at least one of those claimed in the invention chiral dopants. The other ingredients are preferably selected from the known compounds with nematic, cholesteric and / or inclined smectic phases, such as Schiffsche Bases, biphenyls, terphenyls, phenylcyclohexanes, cyclohexylbiphenyls, Pyrimidines, cinnamic acid esters, cholesterol esters, terminal bridged terminal polar multinuclear esters of p-alkylbenzoic acids. In general, the Commercially available liquid crystal phases before the addition of the chiral dopant as mixtures various components, of which at least one is mesogenic, d. H. as a compound, in derivatized form or mixed with certain co-components a liquid crystal Phase shows [= at least one enantiotropic (Clarification temperature melting temperature) or monotropic (clarification temperature Melting temperature) Expect mesophase formation leaves].
Mit Hilfe der neu-entwickelten Verbindungen als Dotierstoff gelingt es bei geringer Menge an Dotierstoff in Flüssigkristall-Phasen eine hohe Verdrillung zu erzielen, wobei die Verbindungen außerdem eine bei Temperaturänderung im wesentlichen unabhängige Ganghöhe aufweisen, d. h. die im allgemeinen im Bereich von 1% bis 1‰ pro K liegende Zu- oder Abnahme der Ganghöhe liegt insbesondere bei weniger als 3‰. Das Verdrillungsvermögen - ausgedrückt durch das Produkt p·c (p= Ganghöhe der induzierten Helixstruktur in µm, c= Konzentration des chiralen Dotierstoffes in Gew.-%), normiert auf 1 Gew.-% des chiralen Dotierstoffes und eine bestimmte Meßtemperatur (z. B. bei 25°C) - ist kleiner als 5, insbesondere liegt es zwischen 0,5 und 4. Ein weiterer Einsatz kann bei der Thermotopographie oder zur Erzeugung von "blue phases" (=cholesterische Systeme mit relativ kleiner Ganghöhe von z. B. weniger als 800 nm) erfolgen.With the aid of the newly developed compounds as dopants, it is possible to achieve a high twist with a small amount of dopant in liquid crystal phases, the compounds also having a pitch which is essentially independent when the temperature changes, ie generally in the range from 1% to 1 ‰ per K increase or decrease in the pitch is in particular less than 3 ‰. The twisting capacity - expressed by the product p · c ( p = pitch of the induced helical structure in µm, c = concentration of the chiral dopant in% by weight), normalized to 1% by weight of the chiral dopant and a certain measuring temperature (e.g. B. at 25 ° C) - is less than 5, in particular it is between 0.5 and 4. A further use can be in thermotopography or for the production of "blue phases" (= cholesteric systems with a relatively small pitch of e.g. less than 800 nm).
Unter den Verbindungen der allgemeinen Formel (I) sind die bevorzugt, bei denen der Rest MC bedeutet:Among the compounds of general formula (I) are the preferred ones where the rest are MC:
in der die Symbole folgende Bedeutung haben:
R3 = ein geradkettiges oder verzweigtes (C1-C12)Alkyl, wobei
eine oder zwei CH2-Gruppen durch O-Atome ersetzt sein
können, oder falls n1= 1 auch F, Cl, Br oder CN,
A1, A2 = unabhängig voneinander 1,4-Phenylen, Pyrimidin-2,5-
diyl, 1,4-Cyclohexylen, 1,3-Dioxan-2,5-diyl, 1,3-Dithian-2,5-diyl
oder 1,4-Bicyclo(2,2,2)octylen, wobei
diese Gruppen auch mindestens einfach substituiert
sein können durch F, Cl, Br, CN und/oder (C1-C12)Alkyl
(gegebenenfalls sind ein oder zwei CH2-Gruppen durch O-Atome
ersetzt),
B = CO-O, O-CO, CH2-CH2, OCH2, CH2O, CH=N, N=CH, N=N,
N(O)=N,
n1, n2, n3 = unabhängig voneinander 0 oder 1.in which the symbols have the following meaning:
R 3 = a straight-chain or branched (C 1 -C 12 ) alkyl, it being possible for one or two CH 2 groups to be replaced by O atoms, or, if n 1 = 1, also F, Cl, Br or CN,
A 1 , A 2 = independently of one another 1,4-phenylene, pyrimidine-2,5-diyl, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,3-dithiane-2,5- diyl or 1,4-bicyclo (2,2,2) octylene, where these groups can also be at least monosubstituted by F, Cl, Br, CN and / or (C 1 -C 12 ) alkyl (optionally one or two CH 2 groups replaced by O atoms),
B = CO-O, O-CO, CH 2 -CH 2 , OCH 2 , CH 2 O, CH = N, N = CH, N = N, N (O) = N,
n 1, n 2, n 3 = independently of one another 0 or 1.
Unter den Verbindungen sind die bevorzugt, bei denen die Symbole folgende Bedeutung haben: R3 = geradkettiges (C4-C10)Alkyl, wobei eine CH2-Gruppe durch ein O-Atom ersetzt sein kann, A1, A2= unabhängig voneinander unsubstituiertes 1,4-Phenylen oder 1,4-Cyclohexylen, B= CO-O, O-CO, n1= 1, n2= 1, und n3= 0 oder 1.Preferred among the compounds are those in which the symbols have the following meaning: R 3 = straight-chain (C 4 -C 10 ) alkyl, where a CH 2 group can be replaced by an O atom, A 1 , A 2 = independently 1,4-phenylene or 1,4-cyclohexylene unsubstituted from one another, B = CO-O, O-CO, n 1 = 1, n 2 = 1, and n 3 = 0 or 1.
Von der oder den erfindungsgemäßen Dotierstoffen enthalten die Flüssigkristall-Phasen im allgemeinen 0,01 bis 70 Gew.-%, insbesondere 0,05 bis 50 Gew.-%. Contained by the dopant (s) according to the invention the liquid crystal phases generally 0.01 to 70% by weight, in particular 0.05 to 50% by weight.
1,1′-Bi-2-naphtholdiester der p-(4-trans-Heptyl-cyclohexyl)- benzoesäure1,1′-Bi-2-naphthol diesters of p- (4-trans-heptyl-cyclohexyl) - benzoic acid
Zu 10 mmol der mesogenen p(4-trans-Heptyl-cyclohexyl)-benzoesäure werden 100 mmol SOCl2 zugesetzt. Es werden 5 Tropfen Pyridin zugegeben und das Reaktionsgemisch wird wärend 2 h unter Rückfluß erhitzt. Das überschüssige SOCl2 wird abgezogen (abdestilliert). Das entstehende Säurechlorid wird in Pyridin gelöst. Das optisch aktive 1,1′-Bi-2-naphthol wird in äquimolarer Menge langsam der Lösung zugesetzt und das Reaktionsgemisch unter Zusatz einer Spatelspitze Dimethylaminopyridin wird danach während 20 h unter Rückfluß erhitzt. Das Gemisch wird filtriert, die Lösung eingedampft und über eine Kieselgelsäure gereinigt. Das umkristallisierte Produkt entspricht nach den analytischen Daten (Elementaranalyse, NMR-Spektrum, IR-Spektrum) der angegebenen Formel (I).100 mmol SOCl 2 are added to 10 mmol of the mesogenic p (4-trans-heptyl-cyclohexyl) benzoic acid. 5 drops of pyridine are added and the reaction mixture is heated under reflux for 2 h. The excess SOCl 2 is drawn off (distilled off). The resulting acid chloride is dissolved in pyridine. The optically active 1,1'-bi-2-naphthol is slowly added to the solution in an equimolar amount and the reaction mixture with the addition of a spatula tip of dimethylaminopyridine is then heated under reflux for 20 h. The mixture is filtered, the solution is evaporated and purified over a silica gel. According to the analytical data (elemental analysis, NMR spectrum, IR spectrum), the recrystallized product corresponds to the formula (I) given.
Entsprechend wird die nachstehende Verbindung (2) synthetisiert. 1,1′-Bi-2-naphtholdiester der (p′-Pentyl-phenyl)-p- benzoesäure Accordingly, the following compound (2) is synthesized. 1,1'-Bi-2-naphthol diester of (p'-pentyl-phenyl) -p-benzoic acid
In einer handelsüblichen nematischen Weitbereichsmischung - "RO-TN 404" der Hoffmann-La Roche Aktiengesellschaft (Basel/Schweiz) - mit einem Klärpunkt von 104°C wird je eine der Verbindungen (1) und (2) und zum Vergleich je eine der Verbindungen (X) und (Y) zugesetzt; die Vergleichsverbindungen sind die handelsüblichen chiralen Dotierstoffe "CB 15" von BDH (British Drug House), Poole (GB) und "S 811" von E. Merck, Darmstadt (DE). In dieser Flüssigkristall-Phase werden dann die Verdrillung in µm·Gew.-% (=p·c) - angegeben bei einer Temperatur von 25°C - und die Temperaturabhängigkeit der Ganghöhe in ‰ pro K bestimmt.In a commercial nematic wide-range mixture - "RO-TN 404" from Hoffmann-La Roche Aktiengesellschaft (Basel / Switzerland) - with a clearing point of 104 ° C, one of the compounds (1) and (2) and for comparison each one of the compounds (X) and (Y) added; the comparison compounds are the commercial chiral dopants "CB 15" from BDH (British Drug House), Poole (GB) and "S 811" from E. Merck, Darmstadt (DE). In this liquid crystal phase, the twist in µm ·% by weight (= p · c ) - specified at a temperature of 25 ° C - and the temperature dependence of the pitch in ‰ per K are determined.
In dieser Meßreihe werden vom jeweiligen Dotierstoff 10 mol% zugesetzt. In this series of measurements 10 mol% of the respective dopant are added.
Claims (8)
R3 = ein geradkettiges oder verzweigtes (C1-C12)Alkyl, wobei eine oder zwei CH2-Gruppen durch O-Atome ersetzt sein können, oder falls n1 = 1 auch F, Cl, Br oder CN,
A1, A2 = unabhängig voneinander 1,4-Phenylen, Pyrimidin- 2,5-diyl, 1,4-Cyclohexylen, 1,3-Dioxan-2,5-diyl, 1,3- Dithian-2,5-diyl oder 1,4-Bicyclo(2,2,2)octylen, wobei diese Gruppen auch mindestens einfach substituiert sein können durch F, Cl, Br, CN und/oder (C1-C12)Alkyl (gegebenenfalls sind ein oder zwei CH2-Gruppen durch O- Atome ersetzt),
B = CO-O, O-CO, CH2-CH2, OCH2, CH2O, CH=N, N=CH, N=N, N(O)=N,
n1, n2, n3 = unabhängig voneinander 0 oder 1. 2. Ester according to claim 1, characterized in that the residue MC of the mesogenic carboxylic acid in the general formula (I) is expressed by the general formula (II) in which the symbols have the following meaning:
R 3 = a straight-chain or branched (C 1 -C 12 ) alkyl, it being possible for one or two CH 2 groups to be replaced by O atoms, or, if n 1 = 1, also F, Cl, Br or CN,
A 1 , A 2 = independently of one another 1,4-phenylene, pyrimidine-2,5-diyl, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,3-dithiane-2,5- diyl or 1,4-bicyclo (2,2,2) octylene, where these groups can also be at least monosubstituted by F, Cl, Br, CN and / or (C 1 -C 12 ) alkyl (optionally one or two CH 2 groups replaced by O atoms),
B = CO-O, O-CO, CH 2 -CH 2 , OCH 2 , CH 2 O, CH = N, N = CH, N = N, N (O) = N,
n 1, n 2, n 3 = independently of one another 0 or 1.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19853534780 DE3534780A1 (en) | 1985-09-30 | 1985-09-30 | Chiral phenol esters of mesogenic carboxylic acids, a process for the preparation thereof and the use thereof as dopes in liquid-crystal phases |
EP86112903A EP0217239B1 (en) | 1985-09-30 | 1986-09-18 | Chiral phenol esters of mesogenic carboxylic acids and their use as doping agents in liquid crystalline phases |
DE8686112903T DE3675136D1 (en) | 1985-09-30 | 1986-09-18 | CHIRAL PHENOLESTER OF MESOGENIC CARBONIC ACIDS AND THEIR USE AS DOPE IN LIQUID CRYSTAL PHASES. |
JP22851786A JPS6281354A (en) | 1985-09-30 | 1986-09-29 | Antipodal phenol ester of mesogenic carboxylic acid and use as doping agent in liquid crystal phase |
US07/144,789 US4826620A (en) | 1985-09-30 | 1988-01-21 | Chiral phenolic esters of mesogenic carboxylic acids and their use as admixture in liquid crystal phases |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19853534780 DE3534780A1 (en) | 1985-09-30 | 1985-09-30 | Chiral phenol esters of mesogenic carboxylic acids, a process for the preparation thereof and the use thereof as dopes in liquid-crystal phases |
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DE3534780A1 true DE3534780A1 (en) | 1987-04-02 |
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DE19853534780 Withdrawn DE3534780A1 (en) | 1985-09-30 | 1985-09-30 | Chiral phenol esters of mesogenic carboxylic acids, a process for the preparation thereof and the use thereof as dopes in liquid-crystal phases |
Country Status (2)
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JP (1) | JPS6281354A (en) |
DE (1) | DE3534780A1 (en) |
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-
1985
- 1985-09-30 DE DE19853534780 patent/DE3534780A1/en not_active Withdrawn
-
1986
- 1986-09-29 JP JP22851786A patent/JPS6281354A/en active Pending
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