[go: up one dir, main page]

WO1995013257A1 - 2,6-difluorobenzenes et leur utilisation dans des melanges a cristaux liquides - Google Patents

2,6-difluorobenzenes et leur utilisation dans des melanges a cristaux liquides Download PDF

Info

Publication number
WO1995013257A1
WO1995013257A1 PCT/EP1994/003534 EP9403534W WO9513257A1 WO 1995013257 A1 WO1995013257 A1 WO 1995013257A1 EP 9403534 W EP9403534 W EP 9403534W WO 9513257 A1 WO9513257 A1 WO 9513257A1
Authority
WO
WIPO (PCT)
Prior art keywords
diyl
trans
liquid crystal
atoms
replaced
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP1994/003534
Other languages
German (de)
English (en)
Inventor
Hubert Schlosser
Dietmar Jungbauer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
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
Priority claimed from DE4338540A external-priority patent/DE4338540A1/de
Priority claimed from DE4423898A external-priority patent/DE4423898C2/de
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of WO1995013257A1 publication Critical patent/WO1995013257A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C07C17/2635—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions involving a phosphorus compound, e.g. Wittig synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C07C17/354—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/24—Halogenated aromatic hydrocarbons with unsaturated side chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C35/21—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a non-condensed ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • 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
    • 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
    • C09K19/0403—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • 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
    • C09K19/0403—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems
    • C09K2019/0407—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems containing a carbocyclic ring, e.g. dicyano-benzene, chlorofluoro-benzene or cyclohexanone

Definitions

  • Optical effects can be achieved, for example, with the help of birefringence, the incorporation of dichroic dye molecules (guest host mode) or light scattering.
  • thermodynamic and electro-optical variables such as phase sequence and electro-optical variables
  • Phase temperature range refractive index, birefringence and dielectric anisotropy, switching time, threshold voltage, steepness of the electro-optical
  • electromagnetic radiation as well as to the materials with which they are associated during and after the manufacturing process (e.g.
  • the invention therefore relates to new 2,6-difluorobenzenes of the formula (I)
  • a 1 , A 2 , A 3 are identical or different 1, 4-phenylene, pyrazine-2,5-diyl, pyridine 2,5-diyl, pyrimidine-2,5-diyl, in which one or two H atoms are represented by F may be replaced, trans-1,4-cyclohexylene, 1,4-cyclohexenylene, (1,3,4) thiadiazole-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2, 6-diyl, bicyclo [2.2.2] octane-1,4-diyl or 1,3-dioxaborinane-2,5-diyl;
  • k, I, m, n, o, p are zero or one, provided that the sum k + m + o is greater than zero; with the following requirements:
  • R 1 is a straight-chain alkyl having 1 to 15 carbon atoms
  • a 1 , A 2 , A 3 are identical or different 1, 4-phenylene, in which one or two H atoms can be replaced by F, trans-1, 4-cyclohexylene or 1, 4cyclohexenylene;
  • M 1 , M 2 , M 3 are identical or different -CH 2 CH 2 -, -C ⁇ C-, -CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 -O-, -O- CH 2 CH 2 CH 2 -, -CH 2 CH 2 CO-O-, -O-CO-CH 2 CH 2 -, -CH 2 -O-, -O-CH 2 -, -CO-O- or - O-CO-; k, I, m, n, o, p are zero or one, provided that the sum k + m + o is greater than zero.
  • Particularly preferred compounds of the formula (I) are the 2,6-difluorobenzenes of the formulas (I1) to (228) listed below:
  • R 1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl.
  • the compounds according to the invention can generally be prepared without problems by methods known per se from literature and to the person skilled in the art.
  • 2,6-difluorophenol can by esterification with carboxylic acids or carboxylic acid halides of Z 2 or by etherification with hydroxymethyl or. Convert halomethyl derivatives of Z 2 to 2,6-difluorobenzene derivatives (I) (see: Tetrahedron 1980, 36, 2409; Organic Synthesis, Coll. Vol. 5, 1973, 258; Journal of the American Chemical Society 1947, 69, 245;
  • bromo-2,6-difluorobenzene (IV) By cross-coupling bromo-2,6-difluorobenzene (IV) with organometallic derivatives of Z 2 , for example Grignard, lithium and zinc derivatives, and boronic acids of Z 2 using transition metal catalysts, for example dichloro [1, 3-bis (diphenylphosphino) propane] nickel (II), tetrakis (triphenylphosphine) palladium and [1, 1 'bis (diphenylphosphino) ferrocene] palladium (II) chloride
  • transition metal catalysts for example dichloro [1, 3-bis (diphenylphosphino) propane] nickel (II), tetrakis (triphenylphosphine) palladium and [1, 1 'bis (diphenylphosphino) ferrocene] palladium (II) chloride
  • Methylphosphonium salts of Z 2 and subsequent hydrogenation of the olefinic intermediate to species (I) according to the invention see: I. Gosney, AG Rowley in Organophosphorous Reagents in Organic Synthesis, Academic Press, New York, 1979, Chpt. 2).
  • the preparation takes place under reaction conditions which are known and suitable for the reactions mentioned. Use can also be made of variants which are known per se and are not mentioned here in detail.
  • disubstituted pyridines and disubstituted pyrimidines can also be found, for example, in the corresponding volumes of the series "The
  • Dioxane derivatives are useful by reacting an appropriate aldehyde (or one of its reactive derivatives) with one
  • Sulfuric acid, benzene or p-toluenesulfonic acid at temperatures between about 20 ° C and about 150 ° C, preferably between 80 ° C and 120 ° C.
  • Acetals are primarily suitable as reactive derivatives of the starting materials.
  • the aldehydes are through Oxidation of corresponding alcohols or by reduction of nitriles or corresponding carboxylic acids or their derivatives, the diols obtainable by reduction of corresponding diesters.
  • Esters of the formula (I) can also be correspondingly esterified
  • Carboxylic acids (or their reactive derivatives) with alcohols or
  • the acid halides especially the chlorides and bromides
  • the anhydrides for example also mixed anhydrides, azides or esters, in particular alkyl esters with 1-4 C atoms in the alkyl group.
  • Reactive derivatives of the alcohols or phenols mentioned include, in particular, the corresponding metal alcoholates or phenolates,
  • an alkali metal such as sodium or potassium.
  • esterification is advantageously carried out in the presence of an inert solvent.
  • an inert solvent particularly suitable are ethers, such as diethyl ether,
  • Hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as carbon tetrachloride, dichloromethane or tetrachlorethylene and sulfoxides such as dimethyl sulfoxide or sulfolane.
  • Ethers of the formula (I) are more appropriate by etherification
  • Hydroxy compounds preferably corresponding phenols, are available, the hydroxyl compound expediently first in a corresponding
  • Metal derivative for example by treatment with NaH, NaNH 2 , NaOH, KOH, Na 2 CO 3 or K 2 CO 3 is converted into the corresponding alkali metal alcoholate or alkali metal phenolate.
  • This can then be reacted with the corresponding alkyl halide, sulfonate or dialkyl sulfate, advantageously in an inert solvent such as acetone, 1, 2-dimethoxyethane, DMF or dimethyl sulfoxide, or with an excess of aqueous or aqueous-alcoholic NaOH or KOH at temperatures between about 20 and 100 ° C.
  • the compounds of the general formula (I) according to the invention are chemically and photochemically stable. They have low melting points and generally broad liquid-crystalline phases, in particular broad nematic ones. Compounds of the formula (I) can be used, for example, for the preparation of nematic or chiral nematic liquid-crystal mixtures
  • Light modulators elements for image processing, signal processing or generally in the field of nonlinear optics are suitable. This also applies to compounds that have no liquid-crystalline phases as the pure substance.
  • the compounds of formula (I) are for introduction or
  • the invention therefore also relates to the use of compounds of the formula (I) in liquid-crystal mixtures.
  • the invention further relates to liquid crystal mixtures which contain one or more compounds of the formula (I).
  • the liquid crystal mixtures according to the invention generally consist of 2 to 20, preferably 2 to 15 components, including at least one, preferably 1 to 5, particularly preferably 1 to 3, compounds of the formula (I).
  • the LC mixtures according to the invention can be nematic or chiral nematic, for example.
  • the liquid crystal mixtures generally contain 0.1 to 70 mol%, preferably 0.5 to 50 mol%, in particular 1 to 25 mol%, of the compound (s) of the formula (I) according to the invention.
  • constituents of the mixtures according to the invention are preferably selected from the known compounds with nematic or
  • cholesteric phases include, for example, biphenyls, terphenyls, phenylcyclohexanes, bicyclohexanes, cyclohexylbiphenyls, mono-, di- and
  • Trifluorophenyls Generally, there are those available commercially
  • nematic or chiral nematic liquid crystal mixtures are, for example, 4-fluorobenzenes, as for example in EP-A 494 368, WO 92/06 148, EP-A 460 436, DE-A 4 1 1 1 766, DE-A 4 1 12 024, DE-A 4 1 12 001, DE-A 4 100 288, DE-A 4 101 468, EP-A 423 520, DE-A 392 3064, EP-A 406 468, EP-A 393 577 , EP-A 393 490, - 3,4-difluorobenzenes, as described for example in DE-A 4 108 448, EP-A 507 094 and EP-A 502 407, - 3,4,5-trifluorobenzenes, as for example in DE-A 4 108 448, EP-A
  • Liquid-crystalline mixtures which contain compounds of the general formula (I) are particularly suitable for use in electro-optical switching and display devices (displays). Such switching and
  • Display devices generally have, inter alia, the following
  • a liquid-crystalline medium e.g. made of glass or plastic
  • carrier plates e.g. made of glass or plastic
  • transparent electrodes at least one orientation layer
  • spacers spacers
  • adhesive frames at least one orientation layer
  • spacers spacers
  • adhesive frames at least one orientation layer
  • spacers spacers
  • adhesive frames at least one orientation layer
  • spacers spacers
  • adhesive frames at least one orientation layer
  • spacers spacers
  • polarizers polarizers
  • thin color filter layers for color displays.
  • Other possible components are antireflection, passivation, compensation and barrier layers as well as electrically non-linear elements, such as thin-film transistors (TFT) and metal-insulator-metal (MIM) elements.
  • TFT thin-film transistors
  • MIM metal-insulator-metal
  • phase transition temperatures are determined with the help of a polarizing microscope on the basis of the texture changes.
  • the melting point is determined with a DSC device
  • Glass transition (Tg) takes place in ° C and the values are between the phase names in the phase sequence.
  • Parentheses are set, or the phase sequence is given ascending and descending in temperature.
  • Electro-optical investigations are carried out using methods known from the literature (e.g. B. Bahadur: Liquid Crystals Application and Uses, Vol. I, World Scientific, Singapore, 1990).
  • nematic liquid crystals pure or in a mixture
  • the values for the optical and dielectric anisotropy and the electro-optical characteristic are recorded at a temperature of 20 ° C.
  • Liquid crystals which do not have a nematic phase at 20 ° C. are mixed to 10% by weight in ZLI-1565 and / or to 20% by weight in ZLI-4792 (commercial nematic liquid crystal mixtures from E. Merck, Darmstadt) the values are extrapolated from the results of the mixture.
  • Electro-optical characteristics are determined on the basis of the transmission of a measuring cell.
  • the cell is positioned between crossed polarizers in front of a light source.
  • There is a light detector behind the cell the sensitivity of which is optimized by filters for the visible area of the light. Analogous to the gradual increase in the voltage applied to the cell, the change in transmission is recorded. Values such as threshold voltage and slope are determined from this.
  • the optical anisotropy is determined using an Abb ⁇ refractometer (from Zeiss). To orient the liquid crystal, a
  • Orientation layer obtained from a 1% by weight lecithin-methanol solution.
  • the electrical variable HR (holding ratio) is in accordance with the
  • Measuring cell attached to the turntable of a polarizing microscope between crossed analyzer and polarizer. To determine the contrast, the measuring cell is positioned by turning so that a photodiode is minimal Indicates light passage (dark state). The microscope illumination is controlled so that the photodiode shows the same light intensity for all cells. After a switching operation, the light intensity (bright state) changes, and the contrast is calculated from the ratio of the light intensity of these states.
  • triphenylphosphine are at 0 ° C in 40 ml
  • Example 12 The following are prepared as in Example 1 1: Example 12:
  • the table shows examples of mixtures with substances according to the invention in comparison with the commercial mixture
  • the two trinuclear substances according to the invention suppress the recrystallization and melting of crystals in the basic mixture, which is very advantageous. A higher order smectic phase transition is also not observed, which leads to a clear broadening of the nematic phase range.
  • the electro-optical examinations show a reduction in the threshold voltage, which is also an advantage.
  • the 4-core substances according to the invention also significantly reduce the smectic phase transition in the mixture and in some cases also suppress recrystallization very well. They also advantageously increase the nematic-isotropic phase transition; especially the substance from Ex. 28 far more than expected after the pure substance phases.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Liquid Crystal Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

2,6-difluorobenzènes de formule générale (I) dans laquelle les symboles et les indices ont les significations suivantes: R<1> est un H, un alkyle à chaîne droite ou ramifiée (avec, ou sans atome de C asymétrique) de 1 à 15 atomes de C, où un ou deux groupes CH2 non voisins peuvent être remplacés par -O-, -S-, -CO-, -CO-O-, -O-CO-, -CO-S-, -S-CO-, -O-CO-O-, -CH=CH-, -CC-, cyclopropane-1,2-diyle ou -Si(CH3)2- et où un ou plusieurs atomes H du reste alkyle peuvent être substitués par F, Cl ou CN; A<1>, A<2>, A<3>, qui peuvent être identiques ou différents, représentent les restes suivants: 1,4-phénylène, pyrazine-2,5-diyle, pyridine-2,5-diyle, pyrimidine-2,5-diyle, dans lesquels un ou deux atomes H peuvent être remplacés par F, trans-1,4-cyclohexylène, 1,4-cyclohexènylène, (1,3,4)-thiadiazole-2,5-diyle, 1,3-dioxanne-2,5-diyle, naphtaline-2,6-diyle, bicyclo[2.2.2]octane-1,4-diyle ou 1,3-dioxaborinane-2,5-diyle; M<1>, M<2>, M<3>, qui peuvent être identiques ou différents, représentent -CH2CH2-, -CH=CH-, -CC-, -CH2CH2CH2CH2-, -CH2CH2CH2-O-, -O-CH2CH2CH2-, -CH2CH2CO-O-, -O-CO-CH2CH2-, -CH2-O-, -O-CH2-, -CO-O- ou -O-CO-; k, l, m, n, o, p valent zéro ou un, pour autant que la somme k+m+o soit supérieure à zéro; avec les conditions suivantes: a) lorsque M<3> est -O-CO-, R<1>(-A<1>)k(-M<1>)l(-A<2>)m(-M<2>)n(-A<3>)o est remplacé par la formule (II) et par la formule (III); b) et lorsque M<3> est -CO-O-, R<1>(-A<1>)k(-M<1>)l(-A<2>)m(-M<2>)n(-A<3>)o est remplacé par la formule (IV) avec g=0 ou 1 et par la formule (V). Les composés de formule générale (I) sont stables chimiquement et photochimiquement. Ils présentent de bas points de fusion et présentent en général de larges phases à cristaux liquides, en particulier de larges phases nématiques.
PCT/EP1994/003534 1993-11-11 1994-10-27 2,6-difluorobenzenes et leur utilisation dans des melanges a cristaux liquides Ceased WO1995013257A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DEP4338540.0 1993-11-11
DE4338540A DE4338540A1 (de) 1993-11-11 1993-11-11 2,6-Difluorbenzole und ihre Verwendung in Flüssigkristallmischungen
DEP4423898.3 1994-07-08
DE4423898A DE4423898C2 (de) 1994-07-08 1994-07-08 2,6-Difluorbenzole und ihre Verwendung in Flüssigkristallmischungen

Publications (1)

Publication Number Publication Date
WO1995013257A1 true WO1995013257A1 (fr) 1995-05-18

Family

ID=25931142

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/003534 Ceased WO1995013257A1 (fr) 1993-11-11 1994-10-27 2,6-difluorobenzenes et leur utilisation dans des melanges a cristaux liquides

Country Status (1)

Country Link
WO (1) WO1995013257A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1352886A1 (fr) * 2002-04-09 2003-10-15 Chisso Corporation Composé crystal liquide ayant un atome d'hydrogène comme groupe terminal, composition contenant le composé et dispositif d'affichage à crystaux liquides contenant la composition
JP2013170246A (ja) * 2012-02-22 2013-09-02 Dic Corp ネマチック液晶組成物
JP2013170247A (ja) * 2012-02-22 2013-09-02 Dic Corp ネマチック液晶組成物
JP2013170248A (ja) * 2012-02-22 2013-09-02 Dic Corp ネマチック液晶組成物
JP2014031322A (ja) * 2012-08-01 2014-02-20 Dic Corp 化合物、液晶組成物および液晶表示素子
WO2015016093A1 (fr) * 2013-07-30 2015-02-05 Semiconductor Energy Laboratory Co., Ltd. Composé organique, composition de cristaux liquides, élément à cristaux liquides, et dispositif d'affichage à cristaux liquides

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0090183A1 (fr) * 1982-03-13 1983-10-05 MERCK PATENT GmbH Composés aromatiques polyhalogénés
GB2234979A (en) * 1989-08-15 1991-02-20 Merck Patent Gmbh 4-Alkyl-4'-(o-fluorophenethyl)bicyclohexanes as liquid crystal components
EP0580122A1 (fr) * 1992-07-20 1994-01-26 Citizen Watch Co., Ltd. Dérivé d'ester

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0090183A1 (fr) * 1982-03-13 1983-10-05 MERCK PATENT GmbH Composés aromatiques polyhalogénés
GB2234979A (en) * 1989-08-15 1991-02-20 Merck Patent Gmbh 4-Alkyl-4'-(o-fluorophenethyl)bicyclohexanes as liquid crystal components
EP0580122A1 (fr) * 1992-07-20 1994-01-26 Citizen Watch Co., Ltd. Dérivé d'ester

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1352886A1 (fr) * 2002-04-09 2003-10-15 Chisso Corporation Composé crystal liquide ayant un atome d'hydrogène comme groupe terminal, composition contenant le composé et dispositif d'affichage à crystaux liquides contenant la composition
US7125589B1 (en) 2002-04-09 2006-10-24 Chisso Corporation Liquid crystal compound having hydrogen as a terminal group, composition comprising the compound, and liquid crystal display element comprising the composition
JP2013170246A (ja) * 2012-02-22 2013-09-02 Dic Corp ネマチック液晶組成物
JP2013170247A (ja) * 2012-02-22 2013-09-02 Dic Corp ネマチック液晶組成物
JP2013170248A (ja) * 2012-02-22 2013-09-02 Dic Corp ネマチック液晶組成物
JP2014031322A (ja) * 2012-08-01 2014-02-20 Dic Corp 化合物、液晶組成物および液晶表示素子
WO2015016093A1 (fr) * 2013-07-30 2015-02-05 Semiconductor Energy Laboratory Co., Ltd. Composé organique, composition de cristaux liquides, élément à cristaux liquides, et dispositif d'affichage à cristaux liquides
JP2015044797A (ja) * 2013-07-30 2015-03-12 株式会社半導体エネルギー研究所 有機化合物、液晶組成物、液晶素子及び液晶表示装置
KR20160040249A (ko) * 2013-07-30 2016-04-12 가부시키가이샤 한도오따이 에네루기 켄큐쇼 유기 화합물, 액정 조성물, 액정 소자, 및 액정 표시 장치
US9580651B2 (en) 2013-07-30 2017-02-28 Semiconductor Energy Laboratory Co., Ltd. Organic compound, liquid crystal composition, liquid crystal element, and liquid crystal display device
KR102274669B1 (ko) * 2013-07-30 2021-07-09 가부시키가이샤 한도오따이 에네루기 켄큐쇼 유기 화합물, 액정 조성물, 액정 소자, 및 액정 표시 장치

Similar Documents

Publication Publication Date Title
EP0306505B1 (fr) Derives d&#39;acetylene comme composants de phases de cristaux liquides
EP0837851B1 (fr) Derives de phenanthrene fluores et leur utilisation dans des melanges a cristaux liquides
EP0308438A1 (fr) Phase liquide cristalline contenant des tolanes.
DE19500768A1 (de) Phenanthren-Derivate und ihre Verwendung in flüssigkristallinen Mischungen
DE4423044A1 (de) 1-(3-Alkyloxiran-2-yl)alkylester mesogener Carbonsäuren und ihre Verwendung in flüssigkristallinen Mischungen
EP1028935A1 (fr) Derives fluores de phenanthrene et leur utilisation dans des melanges a cristaux liquides
EP0824520A1 (fr) Derives de 1-fluoro-5,6,7,8-tetrahydroisoquinoleine et leur utilisation dans des melanges a cristaux liquides
DE4417441A1 (de) Fluormethylethinyl- und Difluormethylethinylbenzole und ihre Verwendung in Flüssigkristallmischungen
WO1995013257A1 (fr) 2,6-difluorobenzenes et leur utilisation dans des melanges a cristaux liquides
DE4331679C2 (de) Spiro[5,5]undecane, diese enthaltende Flüssigkristallmischung und diese enthaltende Schalt- und/oder Anzeigevorrichtung
WO1995010498A1 (fr) 3,4-trifluorobenzene et leur utilisation dans des melanges a cristaux liquides
DE4336265A1 (de) 3-Trifluormethylbenzole und ihre Verwendung in Flüssigkristallmischungen
WO1995009827A1 (fr) 3,4 difluorobenzenes et leur utilisation dans des melanges de cristaux liquides
DE4336391A1 (de) 3,5-Bis(trifluormethyl)benzole und ihre Verwendung in Flüssigkristallmischungen
EP0743971B1 (fr) Derives de phenanthridine et leur utilisation dans des melanges de cristaux liquides
WO1995009829A1 (fr) 2,4-difluorobenzenes et leur utilisation dans des melanges a cristaux liquides
DE4423898C2 (de) 2,6-Difluorbenzole und ihre Verwendung in Flüssigkristallmischungen
WO1995009828A1 (fr) 2,4,5-trifluorobenzenes et leur utilisation dans des melanges de cristaux liquides
WO1995011890A1 (fr) 6-fluorobenzothiazoles et leur utilisation dans des melanges a cristaux liquides
WO1995013999A1 (fr) 3,5-difluorobenzenes et leur utilisation dans des melanges de cristaux liquides
DE4333862A1 (de) 4-Fluor-3-trifluormethylbenzole und ihre Verwendung in Flüssigkristallmischungen
DE4409724B4 (de) 2,3,4-Trifluorbenzole zur Verwendung in Flüssigkristallmischungen
DE4430668B4 (de) Derivate des 4,4-Difluorcyclohexans und 4,4-Difluor-1-cyclohexens und ihre Verwendung in Flüssigkristallmischungen
DE4338267A1 (de) 3-Fluorbenzole und ihre Verwendung in Flüssigkristallmischungen
DE19627899A1 (de) Verbindungen mit mehrfach methylverzweigten Seitenketten und deren Verwendung in Flüssigkristallmischungen

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): 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