WO1995024455A1 - Novel polymerizable liquid-crystalline compounds - Google Patents

Novel polymerizable liquid-crystalline compounds Download PDF

Info

Publication number
WO1995024455A1
WO1995024455A1 PCT/EP1995/000693 EP9500693W WO9524455A1 WO 1995024455 A1 WO1995024455 A1 WO 1995024455A1 EP 9500693 W EP9500693 W EP 9500693W WO 9524455 A1 WO9524455 A1 WO 9524455A1
Authority
WO
WIPO (PCT)
Prior art keywords
independently
liquid
crystalline
another
polymerizable
Prior art date
Application number
PCT/EP1995/000693
Other languages
German (de)
French (fr)
Inventor
Paul Delavier
Karl-Heinz Etzbach
Frank Meyer
Karl Siemensmeyer
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO1995024455A1 publication Critical patent/WO1995024455A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
    • C07C69/92—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with etherified hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • 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
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • 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
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • 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
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate

Definitions

  • liquid-crystalline phases so-called mesophases
  • mesophases can occur during heating.
  • the individual phases differ in the spatial arrangement of the molecular centers on the one hand and in the molecular arrangement with regard to the longitudinal axes on the other hand (G.W. Gray,
  • the nematic liquid-crystalline phase is characterized in that there is only one long-range orientation by parallel storage of the longitudinal axes of the molecules.
  • a so-called cholesteric phase is formed, in which the longitudinal axes of the molecules form a helical superstructure that is perpendicular to them (H. Baessler, Solid Body Problems ⁇ I, 1971).
  • the chiral part of the molecule can either be present in the liquid-crystalline molecule itself or be added to the nematic phase as a dopant, the cholesteric phase being induced.
  • the cholesteric phase has remarkable optical properties: high optical rotation and a pronounced circular dichroism which arises from the selective reflection of circularly polarized light within the cholesteric layer.
  • the colors which appear different depending on the viewing angle, are dependent on the pitch of the helical superstructure, which in turn depends on the twisting capacity of the chiral component.
  • the pitch and thus the wavelength range of the selectively reflected light of a cholesteric layer can be varied by changing the concentration of a chiral dopant.
  • Such cholesteric systems offer interesting possibilities for practical use.
  • a cholesteric network can be obtained in which the chiral component can have a share of up to 50% of the material used; however, these polymers still contain significant amounts of soluble components (FH Kreuzer, R. Maurer, Ch. Müller-Rees, J. Stohrer, Lecture No. 7, 22nd Freiburg Working Conference on Liquid Crystals, Freiburg, 1993).
  • the application DE-OS-35 35 547 describes a method in which a mixture of cholesterol-containing monoacrylates can be processed into cholesteric layers by means of photo-crosslinking.
  • the total proportion of the chiral component in the mixture is approximately 94%.
  • a pure side chain polymer such a material is not mechanically very stable, but an increase in stability can be achieved by highly crosslinking diluents.
  • smectic networks are also known which are produced in particular by photopolymerization / photocrosslinking of smectically liquid-crystalline materials in the smectically liquid-crystalline phase.
  • the materials used for this are generally symmetrical, liquid-crystalline bisacrylates such as those used by DJ Broer and RAM Hikmet, Makromol. Chem., 190. 3201-3215 (1989). However, these materials have very high clarification temperatures of> 120 ° C., so that there is a risk of thermal polymerization.
  • piezoelectric properties can be achieved in the presence of an S c phase (RAM Hikmet, Macromolecules ZU, p. 5759, 1992).
  • the object of the present invention was to produce new polymerizable nematic liquid-crystalline materials which, alone or in mixtures with other polymerizable nematic liquid crystals, have or induce broad nematic phase ranges and clarification temperatures below 120 ° C. and which can be processed below 120 ° C.
  • the invention therefore relates to polymerizable, liquid-crystalline compounds of the general formula I.
  • Y is independently a direct bond, -0-
  • A is independently a spacer with 5 to
  • R ! , R 2 and R 3 independently of one another hydrogen, C ⁇ ⁇ bis
  • C 2 o _ alkyl C ⁇ ⁇ to C 2 o ⁇ alkoxy, C ⁇ ⁇ to C 2 o ⁇ alkoxycarbonyl, Ci to C 2 o * -monoalkylaminocarbonyl, formyl, Ci to C 2 o ⁇ alkylcarbonyl, fluorine, chlorine , Bromine, cyano, C 1 ⁇ to C 2 o * -alkylcarbonyloxy, C 1 ⁇ to C 2 o-alkylcarbonylamino, hydroxyl or nitro.
  • the polymerization of groups Z is preferably initiated photochemically.
  • spacer A All groups known for this purpose can be used as spacer A.
  • the spacers are usually linked to Z via ester or ether groups or a direct bond.
  • the spacers generally contain 5 to 30, preferably 5 to 12, carbon atoms and can be interrupted in the chain, for example by 0, S, NH or NCH 3 . Fluorine, chlorine, bromine, cyano, methyl or ethyl can also be used as substituents for the spacer chain.
  • Representative spacers are, for example, (CH 2 ) p , (CH ? CH ? 0) q CH 2 CH, (CH 2 CH 2 S) q CH 2 CH 2 , (CH 2 CH 2 NH) q CH 2 CH 2 , CH 3 CH 3 CH 3 CH 3 CI
  • the substituents R 1 , R 2 and R 3 can be hydrogen or the stated radicals. Preferred residues are those which suppress the formation of smectic phases and which promote nematic phases. Preferably one of the R groups is hydrogen. Of the substituents mentioned, chlorine, bromine, cyano, fluorine, hydroxy, methyl, ethyl, methoxy, ethoxy, methoxycarbonyl, formyl, acetyl and acetoxy and longer-chain ones with> .8 C atoms are preferred.
  • the compounds of the formula I are prepared by methods known per se. Details of the manufacture can be found in the examples, in which information on parts and percentages, unless stated otherwise, relate to the weight.
  • the compounds of the formula I are liquid-crystalline and, depending on the structure, can form smectic or nematic phases. They are suitable for all purposes in which liquid-crystalline compounds are usually used.
  • the compounds according to the invention alone, in mixtures with one another or mixed with other liquid-crystalline compounds, have phase structures such as low-molecular liquid crystals, but can be frozen into highly crosslinked polymers with highly freeze-dried polymers by free-radical or ionic polymerization processes which can be started by a photochemical reaction transfer liquid crystalline order structure.
  • the compounds according to the invention are particularly suitable as orientation layers for liquid-crystalline materials, as photocrosslinkable adhesives, as monomers for the production of liquid-crystalline networks, as base material for the production of chirally doped polymerizable liquid-crystal systems, as polymerizable matrix monomers for polymer-dispersed displays or as base material for polymerizable, liquid-crystalline materials for optical components, such as polarizers, delay plates or lenses. You are still starting materials for the production of liquid-crystalline ordered colorants.
  • the melting temperatures were recorded using polarization microscopy. The temperature was checked in a Mettler microscope heating table FP80 / 82.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Liquid Crystal Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention concerns polymerisable, liquid-crystalline compounds of general formula (I) in which the Z radicals, independently of one another, mean a polymerisable group having the structure CH2=CCl-, CH2=C(CH3)- or styryl; the Y radicals, independently of one another, mean a direct bond, -O-, -COO-, -OCO- or -S-; the A radicals, independently of one another, mean a spacer having 5 to 30 carbon atoms in which every third carbon atom can be replaced by 0, S, NH, N(CH3) or COO; R?1, R2 and R3¿, independently of one another, mean conventional substituents. The compounds of the invention are suitable, inter alia, for preparing colouring agents ordered as cholesteric liquid crystals.

Description

Neue polymerisierbare flüssigkristalline VerbindungenNew polymerizable liquid crystalline compounds
Beschreibungdescription
Wie für formanisotrope Medien bekannt, können beim Erwärmen flüssigkristalline Phasen, sogenannte Mesophasen, auftreten. Die einzelnen Phasen unterscheiden sich durch die räumliche Anordnung der Molekülschwerpunkte einerseits sowie durch die Molekülanord- nung hinsichtlich der Längsachsen andererseits (G.W. Gray,As is known for shape-anisotropic media, liquid-crystalline phases, so-called mesophases, can occur during heating. The individual phases differ in the spatial arrangement of the molecular centers on the one hand and in the molecular arrangement with regard to the longitudinal axes on the other hand (G.W. Gray,
P.A. Winsor, Liquid Crystals and Plastic Crystals, Ellis Horwood Limited, Chichester 1974). Die nematisch flüssigkristalline Phase zeichnet sich dadurch aus, daß lediglich eine Orientierungsfern¬ ordnung durch Parallellagerung der Moleküllängsachsen existiert. Unter der Voraussetzung, daß die die nematische Phase aufbauenden Moleküle chiral sind, entsteht eine sogenannte cholesterische Phase, bei der die Längsachsen der Moleküle eine zu ihnen senk¬ rechte, helixartige Überstruktur ausbilden (H. Baessler, Fest¬ körperprobleme ∑I , 1971) . Der chirale Molekülteil kann sowohl im flüssigkristallinen Molekül selbst vorhanden sein als auch als Dotierstoff zur nematischen Phase gegeben werden, wobei die cholesterische Phase induziert wird. Dieses Phänomen wurde zuerst an Cholesterolderivaten untersucht (z.B. H. Baessler, M.M. Labes, J. Chem. Phys., l, 631 (1970); H. Baessler, T.M. Laronge, M.M. Labes, J. Chem. Phys., 51 799 (1969); H. Finkelmann,P.A. Winsor, Liquid Crystals and Plastic Crystals, Ellis Horwood Limited, Chichester 1974). The nematic liquid-crystalline phase is characterized in that there is only one long-range orientation by parallel storage of the longitudinal axes of the molecules. Provided that the molecules that make up the nematic phase are chiral, a so-called cholesteric phase is formed, in which the longitudinal axes of the molecules form a helical superstructure that is perpendicular to them (H. Baessler, Solid Body Problems ∑I, 1971). The chiral part of the molecule can either be present in the liquid-crystalline molecule itself or be added to the nematic phase as a dopant, the cholesteric phase being induced. This phenomenon was first investigated on cholesterol derivatives (e.g. H. Baessler, MM Labes, J. Chem. Phys., L, 631 (1970); H. Baessler, TM Laronge, MM Labes, J. Chem. Phys., 51 799 ( 1969); H. Finkelmann,
H. Stegemeyer, Z. Naturforschg. 28a. 799 (1973); H. Stegemeyer, K.J. Mainusch, Naturwiss., , 599 (1971), H. Finkelmann, H. Stegemeyer, Ber. Bunsenges. Phys. Chem. 22., 869 (1974)).H. Stegemeyer, Z. Naturforschg. 28a. 799 (1973); H. Stegemeyer, K.J. Mainusch, Naturwiss.,, 599 (1971), H. Finkelmann, H. Stegemeyer, Ber. Bunsenges. Phys. Chem. 22, 869 (1974)).
Die cholesterische Phase hat bemerkenswerte optische Eigen¬ schaften: eine hohe optische Rotation sowie einen ausgeprägten Zirkulardichroismus, der durch Selektivreflexion von zirkulär polarisiertem Licht innerhalb der cholesterischen Schicht ent¬ steht. Die je nach Blickwinkel unterschiedlich erscheinenden Farben sind abhängig von der Ganghöhe der helixartigen Über¬ struktur, die ihrerseits vom Verdrillungsvermögen der chiralen Komponente abhängt . Dabei kann insbesondere durch Änderung der Konzentration eines chiralen Dotierstoffes die Ganghöhe und damit der Wellenlängenbereich des selektiv reflektierten Lichtes einer cholesterischen Schicht variiert werden. Solche cholesterischen Systeme bieten für eine praktische Anwendung interessante Möglichkeiten. So kann durch Einbau chiraler Molekülteile in mesogene Acrylsäureester und Orientierung in der cholesterischen Phase, z.B. nach der Photovernetzung, ein stabiles, farbiges Netzwerk hergestellt werden, dessen Konzentration an chiraler Komponente dann aber nicht mehr verändert werden kann (G. Galli, M. Laus, A. Angelon, Makromol. Chemie, 187f 289 (1986)) . Durch Zumischen von nichtvernetzbaren chiralen Verbindungen zu nemati- schen Acrylsäureestern kann durch Photovernetzung ein farbiges Polymer hergestellt werden, welches noch hohe Anteile löslicher Komponenten enthält (I. Heyndricks, D.J. Broer, Mol. Cryst. Liq. Cryst. 203. 113 (1991)) . Weiterhin kann durch statistische Hydro- silylierung von Gemischen aus Cholesterolderivaten und acrylat- haltigen Mesogenen mit definierten zyklischen Siloxanen und anschließende Photopolymerisation ein cholesterisches Netzwerk gewonnen werden, bei dem die chirale Komponente einen Anteil von bis zu 50 % an dem eingesetzten Material haben kann; diese Poly¬ merisate enthalten jedoch noch deutliche Mengen löslicher Anteile (F.H. Kreuzer, R. Maurer, Ch. Müller-Rees, J. Stohrer, Vortrag Nr. 7, 22. Freiburger Arbeitstagung Flüssigkristalle, Freiburg, 1993) .The cholesteric phase has remarkable optical properties: high optical rotation and a pronounced circular dichroism which arises from the selective reflection of circularly polarized light within the cholesteric layer. The colors, which appear different depending on the viewing angle, are dependent on the pitch of the helical superstructure, which in turn depends on the twisting capacity of the chiral component. In particular, the pitch and thus the wavelength range of the selectively reflected light of a cholesteric layer can be varied by changing the concentration of a chiral dopant. Such cholesteric systems offer interesting possibilities for practical use. By incorporating chiral parts of the molecule into mesogenic acrylic acid esters and orientation in the cholesteric phase, for example after photocrosslinking, a stable, colored network can be produced, the concentration of chiral components of which can then no longer be changed (G. Galli, M. Laus, A. Angelon, Makromol. Chemie, 187 f 289 (1986)). By Mixing non-crosslinkable chiral compounds into nematic acrylic acid esters can be produced by photocrosslinking, which still contains high proportions of soluble components (I. Heyndricks, DJ Broer, Mol. Cryst. Liq. Cryst. 203, 113 (1991)). Furthermore, by statistical hydrosilylation of mixtures of cholesterol derivatives and acrylate-containing mesogens with defined cyclic siloxanes and subsequent photopolymerization, a cholesteric network can be obtained in which the chiral component can have a share of up to 50% of the material used; however, these polymers still contain significant amounts of soluble components (FH Kreuzer, R. Maurer, Ch. Müller-Rees, J. Stohrer, Lecture No. 7, 22nd Freiburg Working Conference on Liquid Crystals, Freiburg, 1993).
In der Anmeldung DE-OS-35 35 547 wird ein Verfahren beschrieben, bei dem eine Mischung cholesterolhaltiger Monoacrylate über eine Photovernetzung zu cholesterischen Schichten verarbeitet werden kann. Allerdings beträgt der Gesamtanteil der chiralen Komponente in der Mischung ca. 94 %. Als reines Seitenkettenpolymer ist ein solches Material zwar mechanisch nicht sehr stabil, eine Erhöhung der Stabilität kann aber durch hochvernetzende Verdünnungsmittel erreicht werden.The application DE-OS-35 35 547 describes a method in which a mixture of cholesterol-containing monoacrylates can be processed into cholesteric layers by means of photo-crosslinking. However, the total proportion of the chiral component in the mixture is approximately 94%. As a pure side chain polymer, such a material is not mechanically very stable, but an increase in stability can be achieved by highly crosslinking diluents.
Neben oben beschriebenen nematischen und cholesterischen Netz¬ werken sind auch smektische Netzwerke bekannt, welche ins¬ besondere durch Photopolymerisation/Photovernetzung von smektisch flüssigkristallinen Materialien in der smektisch flüssig¬ kristallinen Phase hergestellt werden. Die hierfür verwendeten Materialien sind in der Regel symmetrische, flüssigkristalline Bisacrylate, wie sie z.B. D.J. Broer und R.A.M. Hikmet, Makromol. Chem., 190. 3201-3215 (1989) beschrieben haben. Diese Materialien weisen aber sehr hohe Klärtemperaturen von > 120°C auf, so daß die Gefahr einer thermischen Polymerisation gegeben ist. Durch Zumischen chiraler Materialien können beim Vorliegen einer Sc-Phase piezoelektrische Eigenschaften erzielt werden (R.A.M. Hikmet, Macromolecules ZU, S. 5759, 1992).In addition to the nematic and cholesteric networks described above, smectic networks are also known which are produced in particular by photopolymerization / photocrosslinking of smectically liquid-crystalline materials in the smectically liquid-crystalline phase. The materials used for this are generally symmetrical, liquid-crystalline bisacrylates such as those used by DJ Broer and RAM Hikmet, Makromol. Chem., 190. 3201-3215 (1989). However, these materials have very high clarification temperatures of> 120 ° C., so that there is a risk of thermal polymerization. By adding chiral materials, piezoelectric properties can be achieved in the presence of an S c phase (RAM Hikmet, Macromolecules ZU, p. 5759, 1992).
Aufgabe der vorliegenden Erfindung war die Herstellung neuer polymerisierbarer nematisch flüssigkristalliner Materialien, die allein oder in Mischungen mit anderen polymerisierbaren nematischen Flüssigkristallen breite nematische Phasenbereiche und Klärtemperaturen unterhalb 120°C aufweisen oder induzieren und die unterhalb von 120°C verarbeitet werden können. Die Erfindung betrifft daher polymerisierbare, flüssigkristalline Verbindungen der allgemeinen Formel IThe object of the present invention was to produce new polymerizable nematic liquid-crystalline materials which, alone or in mixtures with other polymerizable nematic liquid crystals, have or induce broad nematic phase ranges and clarification temperatures below 120 ° C. and which can be processed below 120 ° C. The invention therefore relates to polymerizable, liquid-crystalline compounds of the general formula I.
S-ϊ-Λ-ϊ Ϊ-A- Y-Z
Figure imgf000005_0001
 S -ϊ-Λ-ϊ Ϊ-A- YZ
Figure imgf000005_0001
in der die Restein which the leftovers
Z unabhängig voneinander eine polymerisierbare Gruppe der Struktur CH2=CC1-, CH2=C(CH3)- oder Styryl,Z independently of one another is a polymerizable group of the structure CH 2 = CC1-, CH 2 = C (CH 3 ) - or styryl,
Y unabhängig voneinander eine direkte Bindung, -0-,Y is independently a direct bond, -0-,
-COO-, -OCO- oder -S-,-COO-, -OCO- or -S-,
A unabhängig voneinander einen Spacer mit 5 bisA is independently a spacer with 5 to
30 C-Atomen, in denen jedes dritte C-Atom durch 0, S, NH, N(CH3) oder COO ersetzt sein kann und30 carbon atoms in which every third carbon atom can be replaced by 0, S, NH, N (CH 3 ) or COO and
R!,R2 und R3 unabhängig voneinander Wasserstoff, Cχ~ bisR ! , R 2 and R 3 independently of one another hydrogen, Cχ ~ bis
C2o_Alkyl, Cχ~ bis C2o~Alkoxy, Cχ~ bis C2o~Alkoxy- carbonyl, Ci- bis C2o*-Monoalkylaminocarbonyl, Formyl, Ci- bis C2o~Alkylcarbonyl, Fluor, Chlor, Brom, Cyan, Cι~ bis C2o*-Alkylcarbonyloxy, Cι~ bis C2o-Alkylcarbo- nylamino, Hydroxy oder Nitro bedeuten.C 2 o _ alkyl, Cχ ~ to C 2 o ~ alkoxy, Cχ ~ to C 2 o ~ alkoxycarbonyl, Ci to C 2 o * -monoalkylaminocarbonyl, formyl, Ci to C 2 o ~ alkylcarbonyl, fluorine, chlorine , Bromine, cyano, C 1 ~ to C 2 o * -alkylcarbonyloxy, C 1 ~ to C 2 o-alkylcarbonylamino, hydroxyl or nitro.
Die Polymerisation der Gruppen Z wird vorzugsweise photochemisch initiiert. Bevorzugt sind für Z CH =CC1- und CH2=C(CH3)-.The polymerization of groups Z is preferably initiated photochemically. For Z, CH = CC1- and CH 2 = C (CH 3 ) - are preferred.
Für Y sind neben einer direkten Bindung insbesondere Ether- und Estergruppen zu nennen.For Y, in addition to a direct bond, ether and ester groups in particular should be mentioned.
Als Spacer A können alle für diesen Zweck bekannten Gruppen verwendet werden. Üblicherweise sind die Spacer über Ester- oder Ethergruppen oder eine direkte Bindung mit Z verknüpft. Die Spacer enthalten in der Regel 5 bis 30, vorzugsweise 5 bis 12 C-Atome und können in der Kette z.B. durch 0, S, NH oder NCH3 unterbrochen unterbrochen sein. Als Substituenten für die Spacer- kette kommen dabei noch Fluor, Chlor, Brom, Cyan, Methyl oder Ethyl in Betracht. Repräsentative Spacer sind beispielsweise (CH2)p, (CH?CH?0)qCH2CH , (CH2CH2S)qCH2CH2, (CH2CH2NH)qCH2CH2, CH3 CH3 CH3 CH3 CIAll groups known for this purpose can be used as spacer A. The spacers are usually linked to Z via ester or ether groups or a direct bond. The spacers generally contain 5 to 30, preferably 5 to 12, carbon atoms and can be interrupted in the chain, for example by 0, S, NH or NCH 3 . Fluorine, chlorine, bromine, cyano, methyl or ethyl can also be used as substituents for the spacer chain. Representative spacers are, for example, (CH 2 ) p , (CH ? CH ? 0) q CH 2 CH, (CH 2 CH 2 S) q CH 2 CH 2 , (CH 2 CH 2 NH) q CH 2 CH 2 , CH 3 CH 3 CH 3 CH 3 CI
(CH?CH2N ) q CH2CH2 , ( CHCH20 ) qCHCH2 , (CH2 ) 6CH oder CH2CH2CH ,(CH ? CH 2 N) q CH 2 CH 2 , (CHCH 2 0) q CHCH 2 , (CH 2 ) 6 CH or CH 2 CH 2 CH,
wobei q 1 bis 3 und und p 5 bis 20, vorzugsweise 5 bis 12, sind.where q is 1 to 3 and and p are 5 to 20, preferably 5 to 12.
Die Substituenten R1 , R2 und R3 können Wasserstoff oder die ange¬ gebenen Reste sein. Bevorzugt sind solche Reste, die die Ausbil- düng von smektischen Phasen unterdrücken und die von nematischen Phasen fördern. Vorzugsweise ist einer der R-Reste Wasserstoff. Von den genannten Substituenten sind Chlor, Brom, Cyan, Fluor, Hydroxy, Methyl, Ethyl, Methoxy, Ethoxy, Methoxycarbonyl, Formyl, Acetyl und Acetoxy sowie längerkettige mit >.8 C-Atomen bevor- zugt.The substituents R 1 , R 2 and R 3 can be hydrogen or the stated radicals. Preferred residues are those which suppress the formation of smectic phases and which promote nematic phases. Preferably one of the R groups is hydrogen. Of the substituents mentioned, chlorine, bromine, cyano, fluorine, hydroxy, methyl, ethyl, methoxy, ethoxy, methoxycarbonyl, formyl, acetyl and acetoxy and longer-chain ones with> .8 C atoms are preferred.
Die Herstellung der Verbindungen der Formel I erfolgt nach an sich bekannten Methoden. Einzelheiten zur Herstellung können den Beispielen entnommen werden, in denen sich Angaben über Teile und Prozente, sofern nicht anders vermerkt, auf das Gewicht beziehen. Die Verbindungen der Formel I sind flüssigkristallin und können in Abhängigkeit von der Struktur smektische oder nematische Phasen ausbilden. Sie sind für alle Zwecke geeignet, bei denen man üblicherweise flüssigkristalline Verbindungen verwendet.The compounds of the formula I are prepared by methods known per se. Details of the manufacture can be found in the examples, in which information on parts and percentages, unless stated otherwise, relate to the weight. The compounds of the formula I are liquid-crystalline and, depending on the structure, can form smectic or nematic phases. They are suitable for all purposes in which liquid-crystalline compounds are usually used.
Die erfindungsgemäßen Verbindungen weisen allein, in Mischungen untereinander oder gemischt mit anderen flüssigkristallinen Verbindungen Phasenstrukturen wie niedermolekulare Flüssigkri¬ stalle auf, lassen sich jedoch durch radikalische oder ionische Polymerisationsverfahren, welche durch eine photochemische Reak¬ tion gestartet werden können, in hochvernetzte Polymere mit ein¬ gefrorener flüssigkristalliner Ordnungsstruktur überführen.The compounds according to the invention, alone, in mixtures with one another or mixed with other liquid-crystalline compounds, have phase structures such as low-molecular liquid crystals, but can be frozen into highly crosslinked polymers with highly freeze-dried polymers by free-radical or ionic polymerization processes which can be started by a photochemical reaction transfer liquid crystalline order structure.
Zur Einstellung gewünschter Eigenschaften kann es zweckmäßig sein, Mischungen von Verbindungen der Formel I oder Mischungen mit anderen Flüssigkristallen oder auch nicht flüssigkristallinen Verbindungen zu verwenden.To set the desired properties, it may be expedient to use mixtures of compounds of the formula I or mixtures with other liquid crystals or else non-liquid-crystalline compounds.
Die erfindungsgemäßen Verbindungen eignen sich insbesondere als Orientierungsschichten für flüssigkristalline Materialien, als photovernetzbare Kleber, als Monomere zur Herstellung flüssig¬ kristalliner Netzwerke, als Basismaterial zur Herstellung von chiral dotierbaren polymerisierbaren Flüssigkristallsystemen, als polymerisierbare Matrixmonomere für polymer dispergierte Displays oder als Basismaterial für polymerisierbare, flüssigkristalline Materialien für optische Bauelemente, wie Polarisatoren, Ver¬ zögerungsplatten oder Linsen. Sie sind weiterhin Ausgangs- materialien zur Herstellung flüssigkristallin geordneter Farb¬ mittel.The compounds according to the invention are particularly suitable as orientation layers for liquid-crystalline materials, as photocrosslinkable adhesives, as monomers for the production of liquid-crystalline networks, as base material for the production of chirally doped polymerizable liquid-crystal systems, as polymerizable matrix monomers for polymer-dispersed displays or as base material for polymerizable, liquid-crystalline materials for optical components, such as polarizers, delay plates or lenses. You are still starting materials for the production of liquid-crystalline ordered colorants.
BeispieleExamples
Die Schmelztemperaturen wurden polarisationsmikroskopisch aufge¬ nommen. Die Temperaturkontrolle erfolgte in einem Mettler Mikro¬ skopheiztisch FP80/82.The melting temperatures were recorded using polarization microscopy. The temperature was checked in a Mettler microscope heating table FP80 / 82.
Im folgenden bedeuten die AbkürzungenIn the following, the abbreviations mean
k kristalline Phase n nematische Phase i isotrope Phasek crystalline phase n nematic phase i isotropic phase
Beispiel 1example 1
Herstellung vonProduction of
Figure imgf000007_0001
Figure imgf000007_0001
a) Herstellung von 4-(ω-Hydroxyhexyloxy)-benzoesäureethylestera) Preparation of ethyl 4- (ω-hydroxyhexyloxy) benzoate
166 g (1 mol) 4-Hydroxybenzoesäureethylester werden in 400 ml DMF gelöst. Zu dieser Lösung werden 150 g Kaliumcarbonat, 6 g Kaliumjodid und 150 g l-Chlor-6-hydroxyhexan gegeben, danach wird 5 h bei 80 bis 90°C gerührt. Der Fortgang der Reaktion wird dünnschichtchromatografisch verfolgt. Nach vollständigem Umsatz wird das Reaktionsgemisch in 2 1 Wasser eingerührt, das ausgefallene Produkt abgesaugt und mit Wasser gewaschen. Zur Reinigung wird aus ca. 2,5 1 Cyclohexan umkristallisiert. Ausbeute: 201 g (75,5 % d.Th.)166 g (1 mol) of 4-hydroxybenzoic acid ethyl ester are dissolved in 400 ml of DMF. 150 g of potassium carbonate, 6 g of potassium iodide and 150 g of 1-chloro-6-hydroxyhexane are added to this solution, after which the mixture is stirred at 80 to 90 ° C. for 5 h. The progress of the reaction is monitored by thin layer chromatography. After conversion is complete, the reaction mixture is stirred into 2 l of water, the precipitated product is filtered off with suction and washed with water. For cleaning, it is recrystallized from approx. 2.5 l of cyclohexane. Yield: 201 g (75.5% of theory)
b) Herstellung von 4-(ω-Hydroxyhexyloxy)-benzoesäureb) Preparation of 4- (ω-hydroxyhexyloxy) benzoic acid
199 g (0,75 mol) 4-(ω-Hydroxyhexyloxy)-benzoesäureethylester und 56 g (1 mol) Kaliumhydroxid werden in 1 1 Ethanol gelöst und 4 Stunden unter Rückfluß erhitzt. Zur Aufarbeitung wird das Reaktionsgemisch mit konzentrierter Salzsäure angesäuert und der ausgefallene Feststoff abfiltriert, mit Wasser gewa- sehen und getrocknet. Anschließend wird aus Toluol/Ethanol (4/1) umkristallisiert. Ausbeute: 165 g ( = 92 % d.Th.).199 g (0.75 mol) of ethyl 4- (ω-hydroxyhexyloxy) benzoate and 56 g (1 mol) of potassium hydroxide are dissolved in 1 liter of ethanol and heated under reflux for 4 hours. For working up, the reaction mixture is acidified with concentrated hydrochloric acid and the precipitated solid is filtered off and washed with water. see and dried. The mixture is then recrystallized from toluene / ethanol (4/1). Yield: 165 g (= 92% of theory).
c) Herstellung von 4-(ω-Chloracryloxyhexyloxy) -benzoesäurec) Preparation of 4- (ω-chloroacryloxyhexyloxy) benzoic acid
160 g (0,67 mol) 4-(ω-Hydroxyhexyloxy)-benzoesäure, 108 g (1,5 mol) Acrylsäure und 5 g Paratoluolsulfonsäure werden in 900 ml Toluol gelöst und bis zur Beendigung der Wasser- abscheidung zum Rückfluß erhitzt. Zur Aufarbeitung wird das Reaktionsgemisch auf Wasser gegeben, der ausgefallene Fest¬ stoff abfiltriert und mit Wasser von Acrylsäure frei gewa¬ schen, anschließend getrocknet, und aus Ethanol um¬ kristallisiert. Ausbeute: 182 g (- 92 % d.Th.).160 g (0.67 mol) of 4- (ω-hydroxyhexyloxy) benzoic acid, 108 g (1.5 mol) of acrylic acid and 5 g of paratoluenesulfonic acid are dissolved in 900 ml of toluene and heated to reflux until the water separation has ended. For working up, the reaction mixture is poured onto water, the precipitated solid is filtered off and washed free of acrylic acid with water, then dried and recrystallized from ethanol. Yield: 182 g (- 92% of theory).
d) Herstellung von 4-(ω-Chloracryloxyhexyloxy) -benzoesäure- chloridd) Preparation of 4- (ω-chloroacryloxyhexyloxy) benzoic acid chloride
180 g 4-(ω-Acryloxyhexyloxy)-benzoesäure werden in 700 ml Oxalylchlorid gelöst und mit 1 ml Dimethylformamid versetzt. Die Reaktionsmischung wird dann über Nacht bei Raumtemperatur gerührt und danach zunächst unter Wasserstrahlvakuum und an¬ schließend unter Ölpumpenvakuum bei Raumtemperatur eingeengt. Ausbeute: 189 g.180 g of 4- (ω-acryloxyhexyloxy) benzoic acid are dissolved in 700 ml of oxalyl chloride and 1 ml of dimethylformamide is added. The reaction mixture is then stirred overnight at room temperature and then concentrated first under a water jet vacuum and then under an oil pump vacuum at room temperature. Yield: 189 g.
e) Herstellung von Bis-1,4-[4'-(4"-Chloracryloxyhexoy) -benzoyl- oxy] -benzole) Preparation of bis-1,4- [4 '- (4 "chloroacryloxyhexoy) benzoyl oxy] benzene
In 100 ml Pyridin werden 11,4 g (0,1 mol) Hydrochinon gelöst. Bei Raumtempertur wird langsam eine Lösung von 72,2 g (0,21 mol) 4-(ω-Chloracryloxyhexoxy)-benzoesäurechlorid in11.4 g (0.1 mol) of hydroquinone are dissolved in 100 ml of pyridine. At room temperature, a solution of 72.2 g (0.21 mol) of 4- (ω-chloroacryloxyhexoxy) benzoic acid chloride is slowly added
100 ml Toluol zugetropft. Nach vollständiger Zugabe wird die Reaktionsmischung auf 60°C erhitzt und bei dieser Temperatur 4 h gerührt. Der Fortgang der Reaktion wird dünnschichtchro- matografisch verfolgt. Nach Beendigung der Reaktion wird wie üblich aufgearbeitet. Ausbeute: 54,1 g (= 82 % d.Th.) Phasenverhalten: k 86 n 104 i Analog Beispiel 1 wurden die Verbindungen der folgenden Beispiele hergestellt:100 ml of toluene were added dropwise. After the addition is complete, the reaction mixture is heated to 60 ° C. and stirred at this temperature for 4 h. The progress of the reaction is monitored by thin-layer chromatography. After the reaction is worked up as usual. Yield: 54.1 g (= 82% of theory) phase behavior: k 86 n 104 i The compounds of the following examples were prepared analogously to Example 1:
Figure imgf000009_0001
Figure imgf000009_0001
Figure imgf000009_0003
Figure imgf000009_0003
Figure imgf000009_0002
Figure imgf000009_0002
Figure imgf000010_0001
Figure imgf000010_0001
Figure imgf000011_0001
Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000012_0001
Figure imgf000013_0002
Figure imgf000013_0001
Figure imgf000013_0002
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000014_0001
Figure imgf000014_0002
Figure imgf000014_0002
Figure imgf000015_0001
Figure imgf000015_0001

Claims

Patentansprüche claims
1. Polymerisierbare, flüssigkristalline Verbindungen der allge- meinen Formel I1. Polymerizable, liquid-crystalline compounds of the general formula I
Figure imgf000016_0001
Figure imgf000016_0001
in der die Restein which the leftovers
Z unabhängig voneinander eine polymerisierbareZ is independently polymerizable
Gruppe der Struktur CH2=CC1-, CH2=C(CH3)- oder Styryl,Group of the structure CH 2 = CC1-, CH 2 = C (CH 3 ) - or styryl,
Y unabhängig voneinander eine direkte Bindung,Y independently of one another a direct bond,
-0-, -COO-, -OCO- oder -S-,-0-, -COO-, -OCO- or -S-,
A unabhängig voneinander einen Spacer mit 5 bisA is independently a spacer with 5 to
30 C-Atomen, in denen jedes dritte C-Atom durch 0, S, NH, N(CH3) oder COO ersetzt sein kann und30 carbon atoms in which every third carbon atom can be replaced by 0, S, NH, N (CH 3 ) or COO and
R ,R2 und R3 unabhängig voneinander Wasserstoff, Ci- bis C20-Alkyl, Ci- bis C20-Alkoxy, Cx- bis C20-Alkoxy- carbonyl, C - bis C2o~Monoalkylaminocarbonyl, Formyl, Ci*- bis C2o~Alkylcarbonyl, Fluor, Chlor, Brom, Cyan, Cι~ bis C2o~Alkylcarbonyloxy, Cι~ bis C2o-Alkylcarbonylamino, Hydroxy oder Nitro bedeu- ten.R, R 2 and R 3 independently represent hydrogen, Ci- to C 20 alkyl, Ci to C 20 alkoxy, C x - C 20 alkoxy carbonyl, C - C 2 o ~ M onoalkylaminocarbonyl, formyl, Ci * - to C 2 o ~ alkylcarbonyl, fluorine, chlorine, bromine, cyano, Cι ~ to C 2 o ~ alkylcarbonyloxy, Cι ~ to C 2 o-alkylcarbonylamino, hydroxy or nitro mean.
2. Polymerisierbare flüssigkristalline Verbindungen gemäß An¬ spruch 1, bei denen die Reste Y unabhängig voneinander eine direkte Bindung, -0-, -COO- oder -OCO- sind.2. Polymerizable liquid-crystalline compounds according to claim 1, in which the radicals Y are, independently of one another, a direct bond, -0-, -COO- or -OCO-.
3. Polymerisierbare flüssigkristalline Verbindungen gemäß An¬ spruch 1, bei denen die Reste A unabhängig voneinander gege¬ benenfalls durch Ethersauerstoff oder Estergruppen unterbro¬ chenes C;,- bis C2o~Alkylen sind, wobei die Sauerstoffatome oder Estergruppen in der Kette dritte C-Atome ersetzen kön¬ nen. 3. Polymerisable liquid-crystalline compounds according to claim 1, in which the radicals A are, independently of one another, optionally interrupted by ether oxygen or ester groups, C 1 -C 2 -alkylene, the oxygen atoms or ester groups in the chain being third C. -Atoms can replace.
4. Polymerisierbare flüssigkristalline Verbindungen gemäß An¬ spruch 1, bei denen R1, R2 und R3 unabhängig voneinander Was¬ serstoff, Ci bis Ci5--Alkyl, Cj- bis Cis-Alkoxy, Cι~ bis Ci s-Alkoxycarbonyl, Ci- bis Cι*.-Monoalkylaminocarbonyl, Formyl, C]- bis Ci-.-Alkylcarbonyl, Fluor, Chlor, Brom, Cyan, C*- bis Ci ',-Alkylcarbonyloxy, Ci- bis Cis-Alkylcarbonylamino, Hydroxy oder Nitro bedeuten.4. Polymerizable liquid-crystalline compounds according to claim 1, in which R 1 , R 2 and R 3 independently of one another are hydrogen, Ci to Ci5-alkyl, Cj- to Cis-alkoxy, Cι ~ to Ci s-alkoxycarbonyl, Ci - to Cι * .- monoalkylaminocarbonyl, formyl, C] - to Ci -.- alkylcarbonyl, fluorine, chlorine, bromine, cyano, C * - to Ci ' , -alkylcarbonyloxy, Ci- to Cis-alkylcarbonylamino, hydroxy or nitro.
5. Polymerisierbare flüssigkristalline Verbindungen gemäß An- spruch 4, bei denen R1, R2 und R3 unabhängig voneinander Was¬ serstoff, Methyl, Ethyl, Ce bis Cis-Alkyl, Methoxy, Ethoxy, Cβ- bis Cis-Alkoxy, Methoxycarbonyl, Ethoxycarbonyl, C8- bis Ci5-Alkoxycarbonyl, Formyl, Acetyl, Cβ- bis Cis-Alkylcarbonyl, Fluor, Chlor, Brom, Cyan, Acetoxy, Hydroxy oder Nitro sind.5. Polymerizable liquid-crystalline compounds according to claim 4, in which R 1 , R 2 and R 3 independently of one another are hydrogen, methyl, ethyl, Ce to cis-alkyl, methoxy, ethoxy, Cβ- to cis-alkoxy, methoxycarbonyl, Ethoxycarbonyl, C 8 - to Ci 5 -alkoxycarbonyl, formyl, acetyl, Cβ- to cis-alkylcarbonyl, fluorine, chlorine, bromine, cyan, acetoxy, hydroxy or nitro.
6. Polymerisierbare flüssigkristalline Verbindungen gemäß An¬ spruch 5, bei denen R^, R? und R3 unabhängig voneinander Was¬ serstoff, Methyl, Ethyl, Methoxy, Ethoxy, Methoxycarbonyl, Formyl, Acetyl, Fluor, Chlor, Brom, Cyan, Acetoxy, Hydroxy oder Nitro sind.6. Polymerizable liquid-crystalline compounds according to claim 5, in which R ^, R ? and R 3 are, independently of one another, hydrogen, methyl, ethyl, methoxy, ethoxy, methoxycarbonyl, formyl, acetyl, fluorine, chlorine, bromine, cyano, acetoxy, hydroxy or nitro.
7. Verwendung der Verbindungen gemäß Anspruch 1 bis 6 als Orien¬ tierungsschichten für flüssigkristalline Materialien, als photovernetzbare Kleber, als Monomere zur Herstellung flüssigkristalliner Polymere, als Basismaterial zur Herstel¬ lung von chiral dotierbaren polymerisierbaren Flüssig¬ kristallsystemen, als polymerisierbare Matrixmonomere für polymer dispergierte Displays oder als Basismaterial für po¬ lymerisierbare, flüssigkristalline Materialien für optische Bauelemente.7. Use of the compounds according to claims 1 to 6 as orientation layers for liquid-crystalline materials, as photocrosslinkable adhesives, as monomers for the production of liquid-crystalline polymers, as base material for the production of chirally doped polymerizable liquid-crystal systems, as polymerizable matrix monomers for polymer-dispersed displays or as a base material for polymerizable, liquid-crystalline materials for optical components.
8. Verwendung der Verbindungen gemäß Anspruch 1 bis 6 zur Her¬ stellung cholesterisch flüssigkristallin geordneter Farb¬ mittel. 8. Use of the compounds according to claims 1 to 6 for the production of cholesteric liquid-crystalline ordered colorants.
PCT/EP1995/000693 1994-03-11 1995-02-25 Novel polymerizable liquid-crystalline compounds WO1995024455A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19944408170 DE4408170A1 (en) 1994-03-11 1994-03-11 New polymerizable liquid crystalline compounds
DEP4408170.7 1994-03-11

Publications (1)

Publication Number Publication Date
WO1995024455A1 true WO1995024455A1 (en) 1995-09-14

Family

ID=6512462

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/000693 WO1995024455A1 (en) 1994-03-11 1995-02-25 Novel polymerizable liquid-crystalline compounds

Country Status (2)

Country Link
DE (1) DE4408170A1 (en)
WO (1) WO1995024455A1 (en)

Cited By (55)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996024647A1 (en) * 1995-02-06 1996-08-15 Merck Patent Gmbh Direactive mesogenic compounds and intermediates
EP0755918A3 (en) * 1995-07-28 1998-08-05 Rolic AG Photocrosslinkable liquid crystalline 1,2-phenylene derivatives
WO2000005189A1 (en) * 1998-07-24 2000-02-03 Rolic Ag Crosslinkable liquid crystalline compounds
US6616990B2 (en) 2000-03-20 2003-09-09 Basf Aktiengesellschaft Chiral 1, 3-dioxane compounds
US6632909B2 (en) 1997-02-24 2003-10-14 Rolic Ag Photocrosslinkable polymers
US6660344B2 (en) 2000-10-04 2003-12-09 Koninklijke Philips Electronics N.V. Polymerizable liquid crystalline dioxetanes, their preparation and use
US6695977B2 (en) 2000-12-11 2004-02-24 Basf Aktiengesellschaft Use of chiral, uncharged metal compounds as dopants for liquid-crystalline materials
US7258902B2 (en) 2002-07-01 2007-08-21 Basf Aktiengesellschaft Chiral 3,4-dihydro-2H-pyran compounds
US7264749B2 (en) 2002-04-29 2007-09-04 Basf Aktiengesellschaft Alkyne compounds
WO2008081631A1 (en) 2006-12-29 2008-07-10 Adeka Corporation Polymerizable compound and polymerizable composition
WO2009023762A1 (en) * 2007-08-15 2009-02-19 E. I. Du Pont De Nemours And Company Alkaloid monomers, liquid crystal compositions and polymer networks derived therefrom
US7736532B2 (en) 2005-12-29 2010-06-15 E.I. Du Pont De Nemours And Company Composition for reducing the transmission of infrared radiation
US7744970B2 (en) 2005-05-26 2010-06-29 E. I. Du Pont De Nemours And Company Multilayer laminates comprising twisted nematic liquid crystals
WO2010143684A1 (en) 2009-06-11 2010-12-16 富士フイルム株式会社 Infrared light reflector, infrared light reflecting laminated glass, and laminated glass and laminate having cholesteric liquid crystal layers
WO2010143683A1 (en) 2009-06-11 2010-12-16 富士フイルム株式会社 Infrared reflecting plate and infrared reflective bonded glass sheet
WO2010143682A1 (en) 2009-06-11 2010-12-16 富士フイルム株式会社 Process for production of light reflection film
EP2362248A2 (en) 2010-01-27 2011-08-31 Fujifilm Corporation Infrared light reflecting plate, laminated interlayer film sheet for laminated glass and its production method, and laminated glass
WO2012111715A1 (en) 2011-02-18 2012-08-23 富士フイルム株式会社 Infrared reflection plate, interlayer sheet for laminated glass, and laminated glass, and production method therefor
WO2012124719A1 (en) 2011-03-16 2012-09-20 富士フイルム株式会社 Polymerizable compound, polymerizable liquid crystal composition, polymeric compound, and film
WO2013035733A1 (en) 2011-09-08 2013-03-14 富士フイルム株式会社 Polymerizable liquid crystal compound, polymerizable composition, polymer material, and film
US8608977B2 (en) 2008-06-17 2013-12-17 Basf Se Polymerizable chiral compounds comprising 2,6-naphthyl and isomannitol units, and use thereof as chiral dopants
WO2014045878A1 (en) 2012-09-18 2014-03-27 富士フイルム株式会社 Heat ray cutting film and method for producing same, and laminated glass and heat ray cutting member
WO2014061279A1 (en) 2012-10-19 2014-04-24 日本化薬株式会社 Heat-ray-shielding sheet
WO2014185518A1 (en) 2013-05-16 2014-11-20 日本化薬株式会社 Infrared-shielding sheet, method for manufacturing same, and application for same
US8951616B2 (en) 2009-07-09 2015-02-10 Rolic Ag Ester group containing liquid crystals for optical or electro optical devices
WO2015050203A1 (en) 2013-10-03 2015-04-09 富士フイルム株式会社 Half mirror for displaying projected image, method for producing same, and projected image display system
WO2015050256A1 (en) 2013-10-04 2015-04-09 富士フイルム株式会社 Film for thermal compression bonding, which contains cholesteric liquid crystal layer, and application thereof
WO2017130683A1 (en) 2016-01-29 2017-08-03 富士フイルム株式会社 Half mirror and mirror with image display function
WO2017183428A1 (en) 2016-04-21 2017-10-26 富士フイルム株式会社 Mirror with image display function and half mirror
WO2018084076A1 (en) 2016-11-04 2018-05-11 富士フイルム株式会社 Windshield glass, head-up display system, and half-mirror film
WO2018146958A1 (en) 2017-02-09 2018-08-16 富士フイルム株式会社 Half mirror, method for producing half mirror, and mirror provided with image display function
WO2018198559A1 (en) 2017-04-28 2018-11-01 富士フイルム株式会社 Image display function-equipped anti-glare mirror
WO2019009252A1 (en) 2017-07-04 2019-01-10 富士フイルム株式会社 Half mirror
WO2019050019A1 (en) 2017-09-07 2019-03-14 富士フイルム株式会社 One-way mirror film for displaying projected images, laminated glass for displaying projected images, and image display system
US10386569B2 (en) 2015-02-10 2019-08-20 Fujifilm Corporation Optical member, optical element, liquid crystal display device, and near-to-eye optical member
WO2019163969A1 (en) 2018-02-23 2019-08-29 富士フイルム株式会社 Method for manufacturing laminated glass for displaying image, laminated glass for displaying image, and image display system
WO2019188846A1 (en) 2018-03-29 2019-10-03 富士フイルム株式会社 Image-forming method
WO2020008961A1 (en) 2018-07-02 2020-01-09 富士フイルム株式会社 Decorative film, decoration method, decorative molded body production method, and decorative molded film
WO2020080355A1 (en) 2018-10-17 2020-04-23 富士フイルム株式会社 Projection image display member, windshield glass, and head-up display system
WO2020122023A1 (en) 2018-12-10 2020-06-18 富士フイルム株式会社 Projection image displaying member, windshield glass, and head-up display system
WO2020179787A1 (en) 2019-03-06 2020-09-10 富士フイルム株式会社 Laminated film for displaying projection image, laminated glass for displaying projection image, and image display system
WO2020194831A1 (en) 2019-03-28 2020-10-01 富士フイルム株式会社 Ink set for inkjet recording, and image recording method
US10816709B2 (en) 2014-12-19 2020-10-27 Nippon Kayaku Kabushiki Kaisha Light reflection film and laminate having the light reflection film
WO2020262474A1 (en) 2019-06-27 2020-12-30 富士フイルム株式会社 Decorative film for molding, molded article, and display
WO2021059879A1 (en) 2019-09-27 2021-04-01 富士フイルム株式会社 Image recording method
WO2021060402A1 (en) 2019-09-27 2021-04-01 富士フイルム株式会社 Projector for head-up display
WO2021200655A1 (en) 2020-03-30 2021-10-07 富士フイルム株式会社 Reflective film, windshield glass, and head-up display system
WO2021220794A1 (en) 2020-04-28 2021-11-04 富士フイルム株式会社 Compound, liquid crystal composition, cured product and film
WO2021246402A1 (en) 2020-06-03 2021-12-09 富士フイルム株式会社 Reflective film, laminated glass production method, and laminated glass
WO2022075184A1 (en) 2020-10-09 2022-04-14 富士フイルム株式会社 Reflective film, windshield glass, and head-up display system
WO2022123946A1 (en) 2020-12-09 2022-06-16 富士フイルム株式会社 Reflection film, windshield glass, and head-up display system
WO2022138142A1 (en) 2020-12-25 2022-06-30 富士フイルム株式会社 Image recording method and ink jet recorded matter
WO2023054324A1 (en) 2021-09-30 2023-04-06 富士フイルム株式会社 Head-up display system and transport
WO2023080115A1 (en) 2021-11-05 2023-05-11 富士フイルム株式会社 Virtual image display device, head-up display system, and transport machine
WO2023085370A1 (en) 2021-11-12 2023-05-19 富士フイルム株式会社 Image recorded object and image recording method

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4441651A1 (en) * 1994-11-23 1996-04-25 Basf Ag Polymerisable material for coating and printing substrates
DE19532408A1 (en) * 1995-09-01 1997-03-06 Basf Ag Polymerizable liquid crystalline compounds
US6107427A (en) * 1995-09-15 2000-08-22 Rolic Ag Cross-linkable, photoactive polymer materials
DE19612974A1 (en) * 1996-04-01 1997-10-02 Hoechst Ag Powder coatings with a color impression depending on the viewing angle
DE19714119A1 (en) 1997-04-05 1998-10-08 Daimler Benz Ag Compounds, processes for their preparation and processes for the production of liquid-crystalline polymers using these compounds
DE19745647A1 (en) 1997-10-15 1999-04-22 Basf Ag Heat insulation covering for e.g. insulation and in automobile sector
AU2006249382A1 (en) 2005-05-26 2006-11-30 Performance Materials Na, Inc. High strength multilayer laminates comprising twisted nematic liquid crystals
US7879256B2 (en) 2006-03-31 2011-02-01 E. I. Du Pont De Nemours And Company Liquid crystal compositions, polymer networks derived therefrom and process for making the same
US7914700B2 (en) 2006-03-31 2011-03-29 E. I. Du Pont De Nemours And Company Liquid crystal compositions and polymer networks derived therefrom
EP2176268A2 (en) 2007-08-15 2010-04-21 E. I. du Pont de Nemours and Company Chiral compounds, liquid crystal compositions and polymer networks derived therefrom
US7988881B2 (en) 2008-09-30 2011-08-02 E. I. Du Pont De Nemours And Company Multilayer laminates comprising chiral nematic liquid crystals
EP2272937A1 (en) * 2009-07-09 2011-01-12 Rolic AG Ester group containing compounds for optical or electro optical devices

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0261712A1 (en) * 1986-09-04 1988-03-30 Koninklijke Philips Electronics N.V. Picture display cell, method of forming an orientation layer on a substrate of the picture display cell and monomeric compounds for use in the orientation layer
EP0331233A2 (en) * 1988-02-29 1989-09-06 Koninklijke Philips Electronics N.V. Method of manufacturing a laminated element and the element thus obtained
EP0397263A1 (en) * 1989-05-10 1990-11-14 Koninklijke Philips Electronics N.V. Method of manufacturing a polarisation filter, a polarisation filter thus obtained and a display having such a polarisation filter
WO1993005436A1 (en) * 1991-08-29 1993-03-18 Merk Patent Gesellschaft Mit Beschränkter Haftung Electrooptical liquid crystal system
JPH0616616A (en) * 1992-07-03 1994-01-25 Canon Inc Reactive liquid crystal compound, polymeric liquid crystal compound, liquid crystal composition and liquid crystal element
DE4226994A1 (en) * 1992-08-14 1994-02-17 Siemens Ag Heat resistant, thermally conductive anisotropic polymers - obtd. by in-situ crosslinking of mesogenic monomers in the liq. crystalline state, used in (micro)electronics esp. for multilayer circuits

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0261712A1 (en) * 1986-09-04 1988-03-30 Koninklijke Philips Electronics N.V. Picture display cell, method of forming an orientation layer on a substrate of the picture display cell and monomeric compounds for use in the orientation layer
EP0331233A2 (en) * 1988-02-29 1989-09-06 Koninklijke Philips Electronics N.V. Method of manufacturing a laminated element and the element thus obtained
EP0397263A1 (en) * 1989-05-10 1990-11-14 Koninklijke Philips Electronics N.V. Method of manufacturing a polarisation filter, a polarisation filter thus obtained and a display having such a polarisation filter
WO1993005436A1 (en) * 1991-08-29 1993-03-18 Merk Patent Gesellschaft Mit Beschränkter Haftung Electrooptical liquid crystal system
JPH0616616A (en) * 1992-07-03 1994-01-25 Canon Inc Reactive liquid crystal compound, polymeric liquid crystal compound, liquid crystal composition and liquid crystal element
DE4226994A1 (en) * 1992-08-14 1994-02-17 Siemens Ag Heat resistant, thermally conductive anisotropic polymers - obtd. by in-situ crosslinking of mesogenic monomers in the liq. crystalline state, used in (micro)electronics esp. for multilayer circuits

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 0894, Derwent World Patents Index; AN 94-062029 *

Cited By (59)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996024647A1 (en) * 1995-02-06 1996-08-15 Merck Patent Gmbh Direactive mesogenic compounds and intermediates
EP0755918A3 (en) * 1995-07-28 1998-08-05 Rolic AG Photocrosslinkable liquid crystalline 1,2-phenylene derivatives
US6632909B2 (en) 1997-02-24 2003-10-14 Rolic Ag Photocrosslinkable polymers
WO2000005189A1 (en) * 1998-07-24 2000-02-03 Rolic Ag Crosslinkable liquid crystalline compounds
US6613245B1 (en) 1998-07-24 2003-09-02 Rolic Ag Crosslinkable liquid crystalline compounds
US6616990B2 (en) 2000-03-20 2003-09-09 Basf Aktiengesellschaft Chiral 1, 3-dioxane compounds
US6660344B2 (en) 2000-10-04 2003-12-09 Koninklijke Philips Electronics N.V. Polymerizable liquid crystalline dioxetanes, their preparation and use
US6695977B2 (en) 2000-12-11 2004-02-24 Basf Aktiengesellschaft Use of chiral, uncharged metal compounds as dopants for liquid-crystalline materials
US7264749B2 (en) 2002-04-29 2007-09-04 Basf Aktiengesellschaft Alkyne compounds
US7258902B2 (en) 2002-07-01 2007-08-21 Basf Aktiengesellschaft Chiral 3,4-dihydro-2H-pyran compounds
US7744970B2 (en) 2005-05-26 2010-06-29 E. I. Du Pont De Nemours And Company Multilayer laminates comprising twisted nematic liquid crystals
US7736532B2 (en) 2005-12-29 2010-06-15 E.I. Du Pont De Nemours And Company Composition for reducing the transmission of infrared radiation
WO2008081631A1 (en) 2006-12-29 2008-07-10 Adeka Corporation Polymerizable compound and polymerizable composition
US8197710B2 (en) 2006-12-29 2012-06-12 Adeka Corporation Polymerizable compound and polymerizable composition
US8137582B2 (en) 2007-08-15 2012-03-20 E. I. Du Pont De Nemours And Company Alkaloid monomers, liquid crystal compositions and polymer networks derived therefrom
WO2009023762A1 (en) * 2007-08-15 2009-02-19 E. I. Du Pont De Nemours And Company Alkaloid monomers, liquid crystal compositions and polymer networks derived therefrom
US8608977B2 (en) 2008-06-17 2013-12-17 Basf Se Polymerizable chiral compounds comprising 2,6-naphthyl and isomannitol units, and use thereof as chiral dopants
WO2010143683A1 (en) 2009-06-11 2010-12-16 富士フイルム株式会社 Infrared reflecting plate and infrared reflective bonded glass sheet
WO2010143682A1 (en) 2009-06-11 2010-12-16 富士フイルム株式会社 Process for production of light reflection film
WO2010143684A1 (en) 2009-06-11 2010-12-16 富士フイルム株式会社 Infrared light reflector, infrared light reflecting laminated glass, and laminated glass and laminate having cholesteric liquid crystal layers
US8951616B2 (en) 2009-07-09 2015-02-10 Rolic Ag Ester group containing liquid crystals for optical or electro optical devices
EP2362248A2 (en) 2010-01-27 2011-08-31 Fujifilm Corporation Infrared light reflecting plate, laminated interlayer film sheet for laminated glass and its production method, and laminated glass
WO2012111715A1 (en) 2011-02-18 2012-08-23 富士フイルム株式会社 Infrared reflection plate, interlayer sheet for laminated glass, and laminated glass, and production method therefor
WO2012124719A1 (en) 2011-03-16 2012-09-20 富士フイルム株式会社 Polymerizable compound, polymerizable liquid crystal composition, polymeric compound, and film
WO2013035733A1 (en) 2011-09-08 2013-03-14 富士フイルム株式会社 Polymerizable liquid crystal compound, polymerizable composition, polymer material, and film
WO2014045878A1 (en) 2012-09-18 2014-03-27 富士フイルム株式会社 Heat ray cutting film and method for producing same, and laminated glass and heat ray cutting member
WO2014061279A1 (en) 2012-10-19 2014-04-24 日本化薬株式会社 Heat-ray-shielding sheet
WO2014185518A1 (en) 2013-05-16 2014-11-20 日本化薬株式会社 Infrared-shielding sheet, method for manufacturing same, and application for same
WO2015050203A1 (en) 2013-10-03 2015-04-09 富士フイルム株式会社 Half mirror for displaying projected image, method for producing same, and projected image display system
WO2015050256A1 (en) 2013-10-04 2015-04-09 富士フイルム株式会社 Film for thermal compression bonding, which contains cholesteric liquid crystal layer, and application thereof
US10816709B2 (en) 2014-12-19 2020-10-27 Nippon Kayaku Kabushiki Kaisha Light reflection film and laminate having the light reflection film
US10386569B2 (en) 2015-02-10 2019-08-20 Fujifilm Corporation Optical member, optical element, liquid crystal display device, and near-to-eye optical member
WO2017130683A1 (en) 2016-01-29 2017-08-03 富士フイルム株式会社 Half mirror and mirror with image display function
WO2017183428A1 (en) 2016-04-21 2017-10-26 富士フイルム株式会社 Mirror with image display function and half mirror
WO2018084076A1 (en) 2016-11-04 2018-05-11 富士フイルム株式会社 Windshield glass, head-up display system, and half-mirror film
WO2018146958A1 (en) 2017-02-09 2018-08-16 富士フイルム株式会社 Half mirror, method for producing half mirror, and mirror provided with image display function
WO2018198559A1 (en) 2017-04-28 2018-11-01 富士フイルム株式会社 Image display function-equipped anti-glare mirror
WO2019009252A1 (en) 2017-07-04 2019-01-10 富士フイルム株式会社 Half mirror
WO2019050019A1 (en) 2017-09-07 2019-03-14 富士フイルム株式会社 One-way mirror film for displaying projected images, laminated glass for displaying projected images, and image display system
EP4312066A2 (en) 2017-09-07 2024-01-31 FUJIFILM Corporation One-way mirror film for displaying projected images, laminated glass for displaying projected images, and image display system
WO2019163969A1 (en) 2018-02-23 2019-08-29 富士フイルム株式会社 Method for manufacturing laminated glass for displaying image, laminated glass for displaying image, and image display system
WO2019188846A1 (en) 2018-03-29 2019-10-03 富士フイルム株式会社 Image-forming method
WO2020008961A1 (en) 2018-07-02 2020-01-09 富士フイルム株式会社 Decorative film, decoration method, decorative molded body production method, and decorative molded film
WO2020080355A1 (en) 2018-10-17 2020-04-23 富士フイルム株式会社 Projection image display member, windshield glass, and head-up display system
WO2020122023A1 (en) 2018-12-10 2020-06-18 富士フイルム株式会社 Projection image displaying member, windshield glass, and head-up display system
WO2020179787A1 (en) 2019-03-06 2020-09-10 富士フイルム株式会社 Laminated film for displaying projection image, laminated glass for displaying projection image, and image display system
WO2020194831A1 (en) 2019-03-28 2020-10-01 富士フイルム株式会社 Ink set for inkjet recording, and image recording method
WO2020262474A1 (en) 2019-06-27 2020-12-30 富士フイルム株式会社 Decorative film for molding, molded article, and display
WO2021059879A1 (en) 2019-09-27 2021-04-01 富士フイルム株式会社 Image recording method
WO2021060402A1 (en) 2019-09-27 2021-04-01 富士フイルム株式会社 Projector for head-up display
WO2021200655A1 (en) 2020-03-30 2021-10-07 富士フイルム株式会社 Reflective film, windshield glass, and head-up display system
WO2021220794A1 (en) 2020-04-28 2021-11-04 富士フイルム株式会社 Compound, liquid crystal composition, cured product and film
WO2021246402A1 (en) 2020-06-03 2021-12-09 富士フイルム株式会社 Reflective film, laminated glass production method, and laminated glass
WO2022075184A1 (en) 2020-10-09 2022-04-14 富士フイルム株式会社 Reflective film, windshield glass, and head-up display system
WO2022123946A1 (en) 2020-12-09 2022-06-16 富士フイルム株式会社 Reflection film, windshield glass, and head-up display system
WO2022138142A1 (en) 2020-12-25 2022-06-30 富士フイルム株式会社 Image recording method and ink jet recorded matter
WO2023054324A1 (en) 2021-09-30 2023-04-06 富士フイルム株式会社 Head-up display system and transport
WO2023080115A1 (en) 2021-11-05 2023-05-11 富士フイルム株式会社 Virtual image display device, head-up display system, and transport machine
WO2023085370A1 (en) 2021-11-12 2023-05-19 富士フイルム株式会社 Image recorded object and image recording method

Also Published As

Publication number Publication date
DE4408170A1 (en) 1995-09-14

Similar Documents

Publication Publication Date Title
WO1995024455A1 (en) Novel polymerizable liquid-crystalline compounds
EP0749466B1 (en) Novel polymerisable liquid-crystalline compounds
WO1995022586A1 (en) New polymerisable liquid crystal compounds
WO1998023580A1 (en) Polymerizable oligomesogenes
EP0675186B1 (en) Photo-curable liquid crystals
DE60118776T2 (en) POLYMERIZABLE LIQUID CRYSTALLINE DIOXETANESES, THEIR PREPARATION AND USE
US5886242A (en) Polymerizable, chiral compounds and their use
DE60037659T2 (en) LIQUID CRYSTAL COMPOUNDS
EP1142863B1 (en) Polymerisable liquid crystals
EP0700981B1 (en) Photopolymerisable liquid crystals
DE19520704A1 (en) Polymerizable chiral compounds and their use
EP0748852B1 (en) Photocrosslinkable liquid crystalline dyestuffs
DE69915454T2 (en) LIQUID CRYSTALLINE, PHOTOVERNETIC MIXTURE
EP0731084B1 (en) Photocrosslinkable naphthyl derivatives
DE10064291A1 (en) New phenylacetylene (meth)acrylate esters are used in liquid crystal composition and preparing polymer and birefringent product, e.g. optical display and recording material, optical compensator, polarizer, reflector or scattering plate
WO1998004544A1 (en) New liquid crystal compounds and their precursors
DE2722589A1 (en) Enantiomorphic liquid-crystalline polymers - prepd. from substd. phenyl(oxy)alkylene (meth)acrylates
DE68902443T2 (en) FLUORINATED OLIGOPHENYL DERIVATIVES.
EP0951520A1 (en) Flat element with a cholesteric liquid crystal structure
DE69010147T2 (en) Ester compounds and liquid crystalline compositions containing them.
WO1997049694A1 (en) Chiral doping agents for liquid crystalline media
DE102004038131B4 (en) Polymerisable or crosslinkable dopants, liquid crystalline composition containing them and their use
EP0583605A1 (en) Defined oligomeric liquid crystalline compounds with smectic liquid crystalline phases
DE68913156T2 (en) Optically active compound and liquid-crystalline ferroelectric composition containing it.
EP0815094A1 (en) Liquid crystal compounds

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): BR CA CN JP KR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA