WO1997036847A1 - Composes de cristaux liquides, compositions de cristaux liquides contenant ces composes et dispositifs d'affichage a cristaux liquides fabriques au moyen de ces compositions - Google Patents
Composes de cristaux liquides, compositions de cristaux liquides contenant ces composes et dispositifs d'affichage a cristaux liquides fabriques au moyen de ces compositions Download PDFInfo
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- WO1997036847A1 WO1997036847A1 PCT/JP1997/001048 JP9701048W WO9736847A1 WO 1997036847 A1 WO1997036847 A1 WO 1997036847A1 JP 9701048 W JP9701048 W JP 9701048W WO 9736847 A1 WO9736847 A1 WO 9736847A1
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- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- 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
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- C09K19/06—Non-steroidal liquid crystal compounds
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- 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
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- C09K19/3001—Cyclohexane rings
- C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
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- 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
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- 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
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- C09K2019/0451—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 CH3CH=CHCH2CH2- chain
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- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
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Definitions
- a liquid crystal compound a liquid crystal composition containing the liquid crystal compound
- Liquid crystal display device using liquid crystal composition and liquid crystal composition
- the present invention mainly relates to a novel liquid crystal compound capable of exhibiting various physical properties suitable for a liquid crystal composition for a twisted nematic (TN) display system, a super twisted nematic (STN) display system, and a thin film transistor (TFT) display system. And a liquid crystal composition having suitable physical properties using the same, and a liquid crystal display device using the liquid crystal composition.
- TN twisted nematic
- STN super twisted nematic
- TFT thin film transistor
- Liquid crystal display devices utilize the optical anisotropy and dielectric anisotropy of liquid crystal materials, and are widely used in watches, calculators, word processors, televisions, etc., and the demand for them is increasing year by year.
- the liquid crystal phase is located between the solid phase and the liquid phase, and is roughly classified into a nematic phase, a smectic phase, and a cholesteric phase.
- display elements utilizing a nematic phase are currently most widely used.
- TN twisted nematic
- STN super twisted nematic
- TFT thin film transistor
- liquid crystal compounds required for these various liquid crystal display elements vary depending on the intended use, but all liquid crystal substances are stable against external environmental factors such as moisture, air, heat, and light. Further, it is required that the liquid crystal phase be as wide as possible around room temperature, exhibit a liquid crystal phase in a temperature range, have low viscosity, and have a low driving voltage. However, no single liquid crystal material that satisfies these conditions at the same time has been found.
- the liquid crystal material used for a liquid crystal display device has an optimum S-index anisotropy value ( ⁇ £), refractive index anisotropy value ( ⁇ ), viscosity and elastic constant ratio required for each display device.
- liquid crystal compositions are prepared by mixing non-liquid crystal compounds and used for display devices. For this reason, compatibility with other liquid crystal compounds, especially in recent years, requirements for use in various environments require good low-temperature compatibility. Is done.
- the active matrix method in particular, the thin film transistor (TFT) method has been actively adopted as a display mode for televisions and viewfinders in view of display performance such as contrast, display capacity, and response time.
- TFT thin film transistor
- the STN method which has a large display capacity but can be manufactured relatively easily and at a lower cost than the active matrix type display element due to the structure of the display element, is also widely used as a display such as a personal computer. Has been adopted.
- V th the threshold voltage (V th) is represented by the following equation (H. J. Deuling et al., Mol. Cryst. Lig. Cryst., 27 (1975) 81).
- V th 7r ( ⁇ / ⁇ ⁇ ) 1 /
- ⁇ is the elastic constant, £. Is the dielectric constant of vacuum.
- ⁇ is the elastic constant of vacuum.
- R represents an alkyl group.
- R and R ′ represent an alkyl group.
- the compound (c) has a relatively low viscosity, its clearing point is low to compensate for the low clearing point of the liquid crystal composition comprising the liquid crystal compound for low voltage as described above, and the amount of addition is relatively large. Because of the necessity, the characteristics of the composition are lost, and it is not suitable as a material for solving the above-mentioned problems. Further, although the clearing point of compound (d) is sufficiently high, its viscosity is remarkably large due to its four-ring structure, so that when added to the composition, an increase in the sharpness is inevitable. In addition, since the compound (d) itself has a smectic phase, if the prepared composition is left at a low temperature, a smectic phase may appear in the composition. Appropriate.
- the dielectric anisotropy value is very small, and when added to a low-voltage liquid crystal composition having a large dielectric anisotropy value as described above, the dielectric anisotropy is significantly reduced. However, the resulting increase in threshold voltage is not a preferable compound for solving the problem.
- IPS In-Plane Switching
- the configuration of IPS-driven liquid crystal panels is different from the conventional LCD panel in which electrodes are provided on the upper and lower substrates, whereas the IPS-driven liquid crystal panels are provided with interdigital electrodes only on one substrate. And that the major axis direction of the liquid crystal molecules is always parallel to the substrate.
- the advantage of the IPS drive is that, besides the wide viewing angle,
- the cell can be made thinner than conventional products
- the liquid crystal compound used must have low viscosity and large negative dielectric anisotropy.
- Another example of an attempt to improve the narrow viewing angle is the liquid crystal molecule.
- There is a method utilizing vertical alignment Japanese Patent Laid-Open No. 2-176666.
- One of the features of this method is that a liquid crystal composition having a negative dielectric anisotropy is used.
- compounds conventionally known and having a large negative dielectric anisotropy the following compounds are disclosed in patent gazettes. (e) Tokiko Sho 61-26899
- R represents an alkyl group.
- the compound (e) Japanese Patent Publication No. 61-266899
- a compound having a well-balanced combination of characteristics for realizing high-speed response and low-voltage driving in the IPS drive has not been known so far.
- An object of the present invention is to have a high specific resistance value and a high voltage holding ratio that can be sufficiently used in the TFT display method, are stable against heat and ultraviolet irradiation, and have an effect as a narrowing agent.
- the present invention has the configurations of [1] to [29].
- R 1 and Y 1 represent an alkyl group having 1 to 20 carbon atoms, and one or more non-adjacent methylene groups in the alkyl group are substituted with an oxygen atom, a sulfur atom, or a vinylene group. And one or more hydrogen atoms in the alkyl group may be substituted with a fluorine atom or a chlorine atom;
- XX 2 , and X 3 each independently represent a single bond, and each represents a 2-ethylene group, a vinylene group, a COO—, a CF 2 2—, or an OCF 2 —, but X 1 , X 2 , and X At least one of the three is —COO—, one CF 20 — or one OCF 2 —, and ring A ring A 2 , ring A 3 , and ring A 4 are, independently of one another, CH 2 on the ring
- the group is oxygen Trans], 4-cyclohexylene group, or a 1,4-phenylene group in which one or more hydrogen atoms may be substituted with a fluorine atom or a chlorine atom, m and n represents 0 or 1.
- ring A 2 , ring A 3 and ring A 4 represents a 2,3-difluoro or 4-phenylene group
- X ' is a single bond or 1, 2-ethylene group, and in the case of X 2 or C 00-, 1 or more hydrogen atoms of the ring A 2 is the radical fluorine Represents a 1,4-phenylene group substituted with an atom,
- ring A 2 has one or more hydrogen atoms in the group. Represents a 4-phenylene group substituted by a fluorine atom,
- X 3 is -COO-and X 1 and X 2 are each independently a single bond or a 1,2-ethylene group, ring A 3 is one or more hydrogen atoms in the group Represents a 1,4-phenylene group substituted with a fluorine atom,
- ring A 1 or ring A 4 has at least one hydrogen atom in the group as a chlorine atom or a fluorine atom Represents a 1,4-phenylene group substituted by.
- X 1 is a 2-ethylene group
- X 2 is —C 00
- ring A 2 is 3-fluoro-1,4-phenylene.
- X 1 is a single bond
- X 2 is —CF 20 — or —0 CF 2 —
- both ring A and ring A 2 are 1,4-cyclohexylene
- R 1 and Y 1 are alkyl groups
- ring A ′ and ring A 4 are both 1,4-cyclohexylene group
- both ring A 2 and ring A 3 are one.
- the above _ hydrogen atom may be substituted with a fluorine atom or a chlorine atom, 1,4-monophenylene group
- X 2 is —CF 20 — or 1 OC F 2 —
- both X 1 and X 3 are a single bond
- Y 1 are an alkyl group, the ring Alpha' general formula (1), R and ring A 4 are both 1, cyclohexylene group 4-cyclopropyl both 1 are ring A 2 and ring A 3
- the above hydrogen atom may be replaced by a fluorine atom or a chlorine atom 1,4-phenylene group-2? 2 ⁇ - Aruiwa Rei_0 2 -? Deari, one of X 1 and X 3 are single bonds, the other is 1, 2 - liquid crystal according to an ethylene group [1 5]
- Compound c Compound c
- a liquid crystal composition comprising at least two components, comprising at least one compound represented by the general formula (1).
- At least one kind of the liquid crystal compound according to any one of [1] to [ ⁇ 8] is contained as the first component, and the general formulas (2), (3), and (4) are used as the second component.
- R 2 represents an alkyl group having 1 to 10 carbon atoms, and one or more non-adjacent methylene groups in the alkyl group may be substituted with an oxygen atom or one CH 2 CH—, Any hydrogen atom in this alkyl group may be replaced by a fluorine atom, and Y 2 is a fluorine atom, a chlorine atom, — ⁇ CF 3 , —OCF 2 H, one CF 3 , —CF 2 H, one CFH 2 ⁇ CF 2 CF 2 H or 1 0 CF 2 CFHCF 3
- L 1 and L 2 independently represent a hydrogen atom or a fluorine atom
- Z 1 and Z 2 independently represent 1,2-ethylene, vinylene, 1,4-butylene, one COO—, —CF 20 —, one OCF 2— , or a single bond;
- Ring B is trans-4-cyclohexylene, 1,3-dioxane-1,2,5-diyl, or a hydrogen atom which may be substituted with a fluorine atom or 4-phenylene;
- Ring C represents trans-1,4-cyclohexylene, or 1,4-phenylene in which a hydrogen atom may be replaced by a fluorine atom,
- each atom constituting these compounds may be substituted with its isotope c
- a compound comprising at least one liquid crystal compound according to any one of [1] to [18] as a first component, and a compound represented by general formulas (5) and (6) as a second component
- a liquid crystal composition comprising at least one compound selected from the group.
- R 3 and R 4 independently represent an alkyl group having 1 to 10 carbon atoms, and at least one non-adjacent methylene group in the alkyl group is substituted with an oxygen atom or a vinylene group. And any hydrogen atom in the alkyl group may be replaced by a fluorine atom;
- Y 3 represents a CN group or one C ⁇ C—CN
- Ring D represents trans-1,4-cyclohexylene; 4-phenylene, pyrimidin-2,5-diyl; or 1,3-dioxane-1,2,5-diyl;
- Ring E represents trans-1 1,4-cyclohexylene, 1,4-phenylene which may be substituted with a hydrogen atom for fluorine atom, or pyrimidine-1,2,5-diyl;
- ring F is trans-1,4-cyclohexylene Or 1, 4 —indicates phenylene.
- Z 3 represents a 1,2-ethylene group, —COO—, or a single bond;
- LL ⁇ and L 5 each independently represent a hydrogen atom or a fluorine atom, a, b, and c each independently represent 0 or 1,
- Each atom constituting these compounds may be substituted with its isotope.
- a liquid crystal composition comprising at least one compound selected from the group consisting of:
- Ring G, ring I and ring J are each independently of trans-1,4-cyclohexylene, pyrimidine-1,5-diyl, or one or more hydrogen atoms replaced by fluorine atoms. May indicate 1,4-phenylene,
- Z 4 and Z 5 independently represent one C ⁇ C—, one COO—, one CH 2 CH 2 —, —CH—CH—, or a single bond;
- each atom constituting the compound may be substituted with its isotope r
- liquid crystal compound according to any one of [1] to [18] as the first component is reduced.
- Ring K represents trans-1,4-cyclohexylene or 1,4-phenylene, and Z 6 and Z 7 independently of one another —CH 2 CH 2 —, —CH 2 0—, or Indicates a single bond,
- each atom constituting these compounds may be substituted with its isotope.
- a liquid crystal composition comprising at least one compound selected from the group consisting of compounds represented by general formulas (10), (11) and (12) as a third component. .
- liquid crystal compound As a first component, at least one kind of the liquid crystal compound according to any one of [1] to [; 18] is contained, and as a second component, general formulas (2), (3), And at least one compound selected from the group consisting of (4) and (3) A liquid crystal composition comprising at least one compound selected from the group consisting of compounds represented by formulas (7), (8) and (9).
- a compound group comprising at least one liquid crystal compound according to any one of [1] to [18] as a first component, and a compound consisting of general formulas (5) and (6) as a second component At least one compound selected from the group consisting of compounds represented by general formulas (7), (8), and (9) as the third component.
- Liquid crystal composition At least one compound selected from the group consisting of compounds represented by general formulas (7), (8), and (9) as the third component.
- the first component contains at least one kind of the liquid crystal compound according to any one of [1] to [18], and the second component has a general formula (2), (3), or (4) )) And at least one compound selected from the compound group consisting of general formulas (5) and (6) as a third component, and a fourth component as a third component.
- a liquid crystal composition comprising at least one compound selected from the compound group consisting of the general formulas (7), (8), and (9).
- a liquid crystal composition which further comprises one or more optically active compounds in addition to the liquid crystal composition according to any one of [19] to (: 27].
- a liquid non-element configured using the liquid crystal composition according to any one of [19] to [28].
- All the compounds of the formula (1) of the present invention have a high clearing point and low viscosity.
- the compounds in which 2,3-difluoro and 4-phenylene groups are selected exhibit large negative dielectric anisotropy values. All of these compounds have excellent compatibility with other liquid crystal compounds, have high specific resistance, high voltage holding ratio, and are physically and chemically stable.
- those in which an alkyl group is selected as the molecular terminal substituent show a very high voltage holding ratio, and are very effective as a viscosity reducing agent for TF ⁇ display devices.
- An alkenyl group or the like having a relatively large elastic constant ratio exhibits a relatively large elastic constant ratio, and is very effective as a viscosity reducing agent for STN display devices.
- 2,3-difluoro-1,4-phenylene was selected as the ring structure. Since the compound without the compound has a medium dielectric anisotropy value compared to the compound (c) or (d) shown in the section of the prior art, the liquid crystal group for low voltage with large dielectric anisotropy When added to a composition, it is possible to increase the clearing point and further maintain or decrease the viscosity while suppressing the decrease in dielectric anisotropy (increase in threshold voltage). In addition, the 2,3-difluoro-1,4-phenylene group selected as the ring structure has a low viscosity as described above and exhibits a large negative dielectric anisotropy value.
- a liquid crystal composition capable of low-voltage driving and capable of high-speed response is provided. And a liquid crystal display element can be provided.
- the compounds of the invention exhibit both suitable physical properties (1) of R ', Y', ring eight 1, proper selection of ⁇ ⁇ ⁇ X 1, X 2 , X 3, m and ⁇
- a liquid crystal composition suitable for the purpose can be prepared.
- an alkyl group or an alkoxy group is selected for the side chains R 1 and Y 1 , and a large elastic constant ratio such as for STN is required.
- a substituent having an unsaturated bond group such as an alkenyl group or an alkynyl group on the side chains R 1 and Y 1 may be selected.
- a compound having a partial structure in which two 1,4-phenylene groups are cross-linked with one CF 2 -1 is selected.
- one or two fluorine atoms may be substituted at the ortho position of the phenyl ring on the difluoromethylene side, and if a higher dielectric anisotropy value is required, the above-mentioned fluorine atom-substituted compound
- One or two fluorine atoms may be further substituted at the meta position on the phenyl ring on the oxygen atom side, and the objective can be achieved by introducing dipoles in the same direction.
- either —CF 20 — or —COO— is selected as one of the bonding groups XX 2 , X 3 , and the oxygen atom of those bonding groups is selected. If you choose 2,3-difluoro-1,4-monophenylene as the ring structure on the side good. Further, those in which a 2,3-difluoro-4-alkoxyphenyl group is selected in place of the above-mentioned 2,3-difluoro-1,4-phenylene group show a larger negative dielectric anisotropy.
- the refractive index anisotropy value can also be adjusted to an appropriate value by appropriately selecting the RY ⁇ ring ⁇ ′, ⁇ 2 , ⁇ X 1 , X 2 , X 3, m and ⁇ in the equation (1). That is, when a large refractive index anisotropy value is required, a compound containing a large number of 1,4-phenylene rings and having a single bond as the bonding group may be selected, and a small refractive index anisotropy value is required. In this case, a compound containing a large amount of trans-1,4-cyclohexylene may be selected.
- ⁇ alkyl group '' means a straight-chain or branched alkyl group having 1 to 15 carbon atoms, and particularly preferably a group having 1 to 5 carbon atoms from the viewpoint of low viscosity. .
- methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, isopropyl, isobutyl, isoamyl, isohexyl, 2- A methylbutyl group, a 2-methylpentyl group, a 3-methylpentyl group and the like are preferable, but they include racemic forms, S-forms, and R-forms.
- alkenyl group means a straight-chain alkenyl group having 2 to 15 carbon atoms, wherein 1E-alkenyl, 2'-alkenyl, 3'-alkenyl, and 4-alkenyl group are Preferred, more specifically, 1-ethenyl, 1 E-probenyl, 1 E-butenyl, 1 E-hexenyl, 2-propenyl, 2'-butenyl, 2'-pentenyl, 2'-hexenyl , 3-butenyl, 3'-pentenyl and 3'-hexenyl groups.
- Rings A 1 , ⁇ 2 , ⁇ 3 and ⁇ 4 include a benzene ring, a cyclohexane ring, a pyrimidine ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a dioxane ring, a dithane ring or a halogen-substituted ring thereof.
- a ring is mentioned, a cyclohexene ring, a benzene ring or a halogen-substituted ring thereof is particularly preferred.
- a preferred embodiment of the compound represented by the general formula (1) of the present invention is a compound represented by the following general formulas (111) to ⁇ (111).
- the compounds represented by the above general formulas (1-1) to (1-11), (1-21)-(1-64), (111-1)-(111-1) All have low viscosity and show moderate dielectric anisotropy.
- bicyclic and tricyclic compounds represented by the general formulas (111) to (111) and (1-21) to (1 to 42) have particularly low deadness and low Because of its excellent temperature compatibility, when the present compound is added as a component of the composition, only the viscosity can be significantly reduced without lowering the clearing point.
- the four-ring compounds represented by the general formulas (1 to 43) to (1 to 64) and (1 to 81) to (1 to 81) have a wide nematic phase temperature range. It has low viscosity with the compound, and when the compound is added as a component of the composition, only the clearing point can be increased without increasing the viscosity.
- the compounds represented by the general formulas (1-197) to (1-136) and (1-160) to (1-181) have the characteristics of the four-ring compound described above.
- the tranducer represented by the general formulas (1-160) to (1-181) has a low viscosity and a very large refractive index anisotropy. It has excellent properties as a liquid crystal material for STN.
- the liquid crystal composition according to the present invention contains at least one compound represented by the general formula (1) in a proportion of 0.1 to 99.9% by weight. It is necessary to include them together in order to bring out the elegance of life.
- the liquid crystal composition provided by the present invention comprises, in addition to the first component containing at least one compound represented by the general formula (1), It is completed by mixing compounds arbitrarily selected from the compound groups represented by (2) to (4).
- the compounds represented by the general formulas (2) to (4) preferably include the following compounds. (Wherein, R 2 and ⁇ 2 have the same meaning as described above.)
- the compounds represented by the general formulas (2) to (4) have a positive dielectric constant value, are very excellent in thermal stability and chemical stability, have a high voltage holding ratio, and This compound is particularly useful when preparing a liquid crystal composition for a TFT display system requiring high reliability represented by a large specific resistance value.
- the liquid crystal composition is represented by general formulas (2) to (4) in addition to the first component containing at least one compound represented by general formula (1).
- the compound can be optionally used in the range of 0.1 to 9.9% by weight, preferably 10 to 97% by weight, based on the total weight of the liquid crystal composition. More preferably, it is 40 to 95% by weight.
- the compound represented by any of the general formulas (2) to (4) can be used, but the use amount is preferably 50% by weight or less.
- liquid crystal composition comprising the compound represented by the general formula (1) and the compounds represented by the general formulas (2) to (4), this composition is described below.
- Compounds selected from the group of compounds represented by the general formulas (5) to (12) may be further added.
- the compounds represented by the general formulas (5) and (6) have a large positive dielectric anisotropy value, and are used particularly for the purpose of reducing the threshold voltage of the liquid crystal composition. It is also used for adjusting the refractive index anisotropy value and expanding the nematic range such as increasing the clearing point. Further, it is used for the purpose of improving the steepness of a voltage-transmittance curve of a liquid crystal composition for an STN display mode or a TN display mode.
- the amount of the compounds represented by the general formulas (5) to (6) may be in the range of 0.1 to 9.9% by weight when preparing a liquid crystal composition for STN display mode or TN display mode. Can be used arbitrarily, but is preferably 10 to 97% by weight, more preferably 40 to 95% by weight. It is.
- Preferred examples of the compounds represented by the general formulas (7) and (9) used in the present invention include the following compounds, wherein R 5 and R 6 have the same meanings as described above.
- the compounds represented by the general formulas (7) to (9) have a small absolute value of the dielectric anisotropy value and are almost neutral.
- the compound represented by the general formula (7) is mainly used for adjusting the viscosity of the liquid crystal composition or adjusting the refractive index anisotropy value.
- the compounds represented by the general formulas (8) and (9) are used for the purpose of expanding the nematic range such as increasing the clearing point of the liquid crystal composition, or for adjusting the refractive index anisotropy value. You. When the amount of the compound represented by any of the general formulas (7) to (9) is increased, the threshold voltage of the liquid crystal composition increases and the viscosity decreases.
- the amount of the compounds represented by the general formulas (7) to (9) is preferably 40% by weight, more preferably 35% by weight or less when a liquid crystal composition for a TFT display system is prepared. .
- the content is 70% by weight or less, more preferably 60% by weight or less.
- Preferred examples of the compounds represented by formulas (10) to (12) used in the present invention include the following compounds. (Wherein, R 7 and R 8 have the same meanings as described above)
- the compounds represented by the general formulas (10) to (12) have a negative dielectric anisotropy value and can be mixed with a compound having a positive dielectric anisotropy value to obtain a dielectric anisotropy value.
- the elastic constant of the liquid crystal composition which is a function of the value, can be controlled, whereby the steepness of the voltage-transmittance curve of the liquid crystal composition can be controlled. Therefore, it can be used for various driving methods.
- the amount of the compound represented by any of the general formulas (10) to (12) may be 0.1 to 0.1 when a liquid crystal composition for a TFT display system, an STN display system, or a TN display system is prepared.
- liquid crystal compositions are usually used to induce the helical structure of the liquid crystal composition, adjust the required twist angle, and prevent reverse twist.
- An optically active compound may be added to the liquid crystal composition, and the optically active compound can be similarly added to the liquid crystal composition of the present invention.
- known optically active compounds can be used for such purpose, preferred optically active compounds are listed below.
- the twist pitch is preferably adjusted in the range of 10 to 200 ⁇ m for a liquid crystal composition for a TFT display system and a TN display system.
- a liquid crystal composition for STN display mode it is preferable to adjust the liquid crystal composition in the range of 6 to 20 m.
- the bistable (Bistable II) mode it is preferable to adjust it to the $ fi range of 1.5 to 4 m.
- two or more optically active compounds may be added.
- the liquid crystal composition of the present invention is prepared by a conventional method. Generally, a method is used in which various components are dissolved at a high temperature.
- the liquid crystal composition of the present invention is prepared by adding a dichroic dye such as a merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone, or tetrazine compound to form a guest host (GH) mode.
- a dichroic dye such as a merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone, or tetrazine compound
- GH guest host
- the nematic liquid crystal composition containing the liquid crystal compound of the present invention As the nematic liquid crystal composition containing the liquid crystal compound of the present invention, the following composition examples can be shown. However, the compounds in the composition examples are abbreviated according to the rules shown in Table 1.
- Example 1 3—H2B (F, F) B (F) —F
- Example 3 1V2-BEB (F, F) -C
- V-HB-C 1 1.0%
- V 2 -HHB-1 1 1.0% 3 -HHB-1 5.0% 1 V2 -HBB- 2 10.0% 3 -HHE BH- 3 5.0% Composition example
- 6-Py B-05 3 0% 6-P y B - ⁇ 63 0% 6-P y B -07 3, 0% 6-P y B-08 3.0%
- J ⁇ 3 Si- 8 is / ufcl -ic /.
- V-HHB-1 5.0% V-HB B- 2 4.0% 3 -H2 BTB 4.0% Composition 5 8
- the liquid crystalline compound of the present invention represented by the general formula (1) can be easily produced by a general organic synthetic chemistry technique. For example, it can be easily synthesized by appropriately selecting and combining the methods described in Organic 'Synthesis, Organic' Reactions, Experimental Chemistry Course, etc.
- a dehydrating agent such as dicyclohexylcarboimide (DCC) and 4-dimethylaminopyridine (DMAP).
- a halogenated compound (15) is used as a Grignard reagent or a lithiated product using magnesium / gold / lithium, and is reacted with carbon disulfide to produce a dithiocarboxylic acid derivative (16). Then, thionyl chloride is allowed to act on (16) to give thione carboxylic acid chloride,
- DAST getylaminosulfur trifluoride
- NB N-promosquenimide
- S getylaminosulfur trifluoride
- DBH 1,3-jibu-mouth 5,5-dimethylhydantoin
- the above thione 10-ester derivative (17) can be produced by derivatizing a dithiocarboxylic acid derivative (16) into an alkali metal salt and then reacting it with an alcoholate or phenolate in the presence of iodine. Obtained by the above manufacturing method Of 2,4-bis (4-methoxyphenyl)-13-dithia-2,4-diphosphethane-1,2,4-disulphide (hereinafter abbreviated as Rohtz reagent) to the ester derivative (11-A) Can also be manufactured.
- Rohtz reagent 2,4-bis (4-methoxyphenyl)-13-dithia-2,4-diphosphethane-1,2,4-disulphide
- the compound (1-1C) in which X 2 is —CF 20 — and the compound (1—D) in which X 2 is —COO— can be suitably produced by the following method.
- a Wittig reagent (19) that can be prepared from a promomethane derivative (18) and triphenylphosphine is used.
- E, Z reactive compounds obtained by reacting an aldehyde derivative (21) with an iridium prepared by reacting a base such as sodium alkoxide or alkyllithium in tetrahydrofuran (hereinafter abbreviated as THF).
- THF tetrahydrofuran
- Benzenesulfonate or p-toluenesulfonate is applied to the isocyanate mixture (22) in accordance with the method described in JP-B No. 4-330382, or According to the method described in No.
- the carboxylic acid derivative (26) can be produced by subjecting the compound (25) obtained by the above operation to lithiation with butyllithium or the like and then reacting with carbon dioxide. (26) )
- the target compound (1-1D) can be produced by treating in the same manner as in the production.
- XX 2 or X 3 is Echinire down group
- m and n secondary 1
- X 1 Gar C ⁇ C is one
- X 2 A compound in which is —CF 2 ⁇ 1 (1 E) and a compound in which X 2 is —CO 0—
- (1-F) can be suitably produced by the following method. That is, according to the method described in J. ⁇ rg, Chem., 28, 2163, 33133 (1963), the acetylene derivative (27) was added to the compound (2 Acts on 8) to produce compound (29). By treating the compound (29) thus obtained in the same manner as in the case of the above (11-B), the target compound (11-E) can be produced.
- a carboxylic acid derivative (30) can be produced by subjecting the compound (29) obtained by the above operation to lithiation with butyllithium or the like and then reacting with carbon dioxide, and (30) is converted to the above (1—C )
- the target compound (1-F) can be produced by treating in the same manner as in the production.
- the acetylene derivative (27) can be easily prepared by adding bromine to the corresponding vinyl derivative to give a dibumid compound (31) according to J. Org. Chem., 38, 1367.
- 2,3-difluorophenol 100 g (0.77m0)), bromide chill 100g (0.92m01), potassium carbonate 127g (0.92mo) l), 1.0 g (6.0 mm 01) of potassium iodide, and 1.3 L of dimethylformamide (DMF) were mixed and heated to reflux for 7 hours. After the reaction, add 1.0 L of water to the reaction solution, Then it was extracted with 2.0 L of toluene. After washing the Xu Xinyi for 1 lei with water, it was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was distilled under reduced pressure to obtain 87.5 g of 2,3-difluoroethoxyquinbenzene (yield: 71.4%).
- reaction solution was poured into a saturated aqueous solution of sodium carbonate to terminate the reaction.
- methylene chloride phase was separated, washed successively with a 10% aqueous sodium hydrogen sulfite solution and water, and dried over anhydrous magnesium sulfate.
- the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (elution solvent: heptane) to obtain the title compound 0.72 ⁇ (yield 35.5%).
- the aqueous layer was further extracted with 200 ml of toluene, and the combined toluene layer was extracted with 200 ml of water, 800 ml of a 2N aqueous sodium hydroxide solution, and 300 ml of water. After washing sequentially, the extract was dried over anhydrous magnesium sulfate, and toluene was distilled off under reduced pressure to obtain 28.3 g of a deep reddish purple paste-like residue.
- 4-pentylphenyl 4- (trans-41-n-propylcyclohexyl) thiobenzoate obtained by the above operation 5.0 g (12. 3 mm 01) was dissolved in dichloromethane 60m], and 7.9 g (49. Ommol) of DAST was added at room temperature, followed by stirring for 25 hours.
- the reaction solution was added to 200 ml of ice water to terminate the reaction, the dichloromethane layer was separated, and the aqueous layer was extracted with 100 ml of dichloromethane.
- the combined dichloromethane layer was washed successively with 200 ml of water, 50 ml of a 2N aqueous sodium hydroxide solution and 200 m of water], and dried over anhydrous magnesium sulfate.
- the dichloromethane was distilled off and concentrated to obtain 3.8 g of pale yellow crystalline crude product.
- the crude product was purified by silica gel column chromatography (elution solvent: heptane), and then recrystallized from heptane to obtain colorless needle-shaped difluoro- (4-pentylphenyloxy) (4-1). Trans-4-Provircyclohexyl) phenyl) methane was added to obtain 7 g.
- the various spectrum data supported the structure of the compound.
- the production processes include 1) the synthesis of 4- (4-hydroxyphenyl) cyclohexanone, 2) the synthesis of a cyclohexanone intermediate (32), and 3) the difluoro- (4- (trans-14-ethenylcyclo) Hexyl) phenyloxy) (4-propylphenyl) Can be roughly divided into three stages of methane production. It is divided into each manufacturing stage and described in detail below.
- the toluene was distilled off under reduced pressure to obtain 73.6 g of a brown solid product.
- This product was dissolved in toluene (340 ml) in a 1 L eggplant-shaped flask equipped with a Dean-Stark dewatering tube, and 5.9 g of nonaqueous acidic ion exchange resin (Amberlyst) was used as an acid catalyst. Was added, and the mixture was refluxed for 3 hours while stirring. After removing the catalyst by filtration, toluene was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (elution solvent: toluene), and then recrystallized from toluene to give a colorless needle-like cyclo. Hexene derivatives (3 3) 1.8 g were obtained.
- the cyclohexene derivative (33) obtained in the first step was dissolved in 200 ml of 1Z1 mixed solvent of toluene / ethanol in a 1-L eggplant-shaped flask, and 5% palladium-carbon catalyst was used 2. 5 g was added, and a hydrogenation reaction was performed at room temperature under a hydrogen pressure of 1 to 2 kg / cm 2 for 6 hours. After removing the catalyst by filtration, the reaction solution was concentrated to give the reaction product 30.
- the toluene was distilled off under reduced pressure to obtain 33.2 g of a deep red-purple paste-like product.
- This product is subjected to silica gel column chromatography (elution solvent: mixed solvent of heptanol and toluene 1Z1). And recrystallized from heptane to obtain 18.4 g of pale yellow needle-like product.
- the solvent was distilled off under reduced pressure to obtain 18.5 g of a crude product.
- the crude product was purified by silica gel column chromatography (elution solvent: toluene) to obtain 7.6 g of a tan product.
- the obtained product was dissolved in 200 ml of toluene in 50 ml of eggplant type thrasco, and 99 g of formic acid (5.3 g, 11.0 mm 01) was added. The mixture was heated under reflux for 2 hours. did. 50 ml of water was added to the reaction solution, and extracted with 50 ml of toluene.
- the toluene layer was washed successively with 100 ml of water, 30 ml of a 2N aqueous solution of sodium hydroxide and 100 ml of water, and then dried over anhydrous magnesium sulfate.
- the solvent was distilled off under reduced pressure, and the obtained residue (7.3 g) was purified by silica gel column chromatography (eluent: toluene) to obtain a colorless crystalline cyclohexanecarbaldehyde derivative (3). 5.6 g of 5) was obtained.
- the combined toluene layer was washed successively with 100 mK water 2N aqueous sodium hydroxide solution (30 ml) and water (100 ml) and dried over anhydrous magnesium sulfate.
- the toluene was distilled off under reduced pressure, and 7.0 g of the obtained residue was purified by silica gel column chromatography (elution solvent: toluene), and 5.9 g of a yellow-brown crystalline aldehyde derivative (36) was obtained.
- the reaction was terminated by adding 5 Om 1 of water to the reaction solution, the THF layer was separated, and the aqueous layer was extracted with 100 ml of toluene.
- the combined THF layer and toluene layer were washed with 200 ml of water, and dried over anhydrous magnesium sulfate.
- 5.6 g of the product obtained by evaporating the solvent under reduced pressure was purified by silica gel column chromatography (elution solvent: heptane), and further recrystallized from heptane to obtain colorless needle-like crystals 2 4 g were obtained. This is the target difluoro
- reaction solution was heated to 60 ° C on a warm bath, stirred for 3 hours and aged. After cooling to room temperature, water (20 Om 1) and 6N hydrochloric acid (80 m 1) were added to the reaction solution, the toluene layer was separated, and the aqueous layer was further extracted with toluene (300 ml). The combined toluene layer was washed successively with 80 ml of a 40,0 m2 aqueous sodium hydroxide solution and 400 ml of water, and then dried over anhydrous magnesium sulfate.
- the combined dichloromethane layer was washed successively with 50Om1 of water, 80m1 of a 2N aqueous sodium hydroxide solution and 500m1 of water, and dried over anhydrous magnesium sulfate.
- the pale yellow crystalline mixture (14.1 g) obtained by distilling off dichloromethane was purified by silica gel column chromatography (elution solvent: toluene), and then recrystallized from heptane to give colorless needles. 7.1 g of crystals were obtained. This is the cyclohexanone derivative (39).
- this reaction product was dissolved in toluene (40 ml) in a 200 ml eggplant type slasco, and added with 99% -formic acid (4.1 g, 88.2 mmol) for 2 hours. after adding water 5 Om 1 to heat refluxing c reaction solution was extracted with toluene 5 Om l, extracted layer water 1
- 2,3-difluo--4-ethoxyethoxy trans-14- (trans-14-propylcyclohexyl) benzoate obtained by the above procedure 20.
- Dissolve 8 g (50.9 mmo 1) in toluene 150 m 1 add 24.7 g (61 .1 mmo 1) of Lawson Reagent, and put it on an oil bath at 140 ° C. For 8 hours. After adding 200 ml of water to the reaction solution, the toluene layer was separated. The toluene layer was washed three times with water (150 ml) and dried over anhydrous magnesium sulfate. Dried.
- the reaction solution was poured into a saturated aqueous solution of sodium carbonate to terminate the reaction, and then a methylene chloride layer was separated.
- the methylene chloride layer was washed successively with a 10% aqueous solution of sodium hydrogen sulfite and water, and then dried over anhydrous magnesium sulfate.
- the solvent was distilled off under reduced pressure, and the obtained residue was subjected to silica gel column chromatography.
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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US09/155,595 US6190576B1 (en) | 1996-04-02 | 1997-03-27 | Liquid crystal compounds, liquid crystal compostions containing the compounds, and liquid crystal display devices made by using the compositions |
JP53512097A JP3231333B2 (ja) | 1996-04-02 | 1997-03-27 | 液晶性化合物、この液晶性化合物を含有する液晶組成物、及び液晶組成物を用いた液晶表示素子 |
EP97908523A EP0916639B1 (en) | 1996-04-02 | 1997-03-27 | Liquid crystal compounds, liquid crystal compositions containing the compounds, and liquid crystal display devices made by using the compositions |
DE69713339T DE69713339T2 (de) | 1996-04-02 | 1997-03-27 | Flüssigkristallverbindungen, flüssigkristalle enthaltende zubereitungen, und aus diesen verbindungen hergestellte flüssigkristallanzeigen |
KR1019980707900A KR100333020B1 (ko) | 1996-04-02 | 1997-03-27 | 액정화합물,이러한화합물을함유하는액정조성물및이러한조성물을사용하여제조된액정표시소자 |
AU20434/97A AU2043497A (en) | 1996-04-02 | 1997-03-27 | Liquid crystal compounds, liquid crystal compositions containing the compounds, and liquid crystal display devices made by using the compositions |
AT97908523T ATE219041T1 (de) | 1996-04-02 | 1997-03-27 | Flüssigkristallverbindungen, flüssigkristalle enthaltende zubereitungen, und aus diesen verbindungen hergestellte flüssigkristallanzeigen |
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US09/597,280 Continuation US6319570B1 (en) | 1996-04-02 | 2000-06-19 | Liquid crystalline compound, liquid crystal composition comprising the liquid crystal-line compound, and liquid crystal display device using the liquid crystal composition |
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US (2) | US6190576B1 (ja) |
EP (2) | EP1043299B1 (ja) |
JP (2) | JP3231333B2 (ja) |
KR (1) | KR100333020B1 (ja) |
CN (1) | CN1118449C (ja) |
AT (2) | ATE219041T1 (ja) |
AU (1) | AU2043497A (ja) |
DE (2) | DE69739049D1 (ja) |
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Also Published As
Publication number | Publication date |
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EP1043299A2 (en) | 2000-10-11 |
JP3231333B2 (ja) | 2001-11-19 |
TW416979B (en) | 2001-01-01 |
EP0916639A1 (en) | 1999-05-19 |
DE69713339D1 (de) | 2002-07-18 |
EP1043299A3 (en) | 2004-01-02 |
CN1118449C (zh) | 2003-08-20 |
KR100333020B1 (ko) | 2002-10-31 |
KR19990077385A (ko) | 1999-10-25 |
EP0916639B1 (en) | 2002-06-12 |
AU2043497A (en) | 1997-10-22 |
DE69739049D1 (de) | 2008-11-27 |
CN1218451A (zh) | 1999-06-02 |
EP0916639A4 (en) | 1999-07-07 |
US6319570B1 (en) | 2001-11-20 |
EP1043299B1 (en) | 2008-10-15 |
JP2002053529A (ja) | 2002-02-19 |
JP3646671B2 (ja) | 2005-05-11 |
ATE411371T1 (de) | 2008-10-15 |
ATE219041T1 (de) | 2002-06-15 |
DE69713339T2 (de) | 2002-12-05 |
US6190576B1 (en) | 2001-02-20 |
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