WO1998020006A1 - Derives de dioxane fluoroalkyle, compositions de cristaux liquides et elements d'ecran a cristaux liquides - Google Patents

Derives de dioxane fluoroalkyle, compositions de cristaux liquides et elements d'ecran a cristaux liquides Download PDF

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Publication number
WO1998020006A1
WO1998020006A1 PCT/JP1997/004069 JP9704069W WO9820006A1 WO 1998020006 A1 WO1998020006 A1 WO 1998020006A1 JP 9704069 W JP9704069 W JP 9704069W WO 9820006 A1 WO9820006 A1 WO 9820006A1
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liquid crystal
formula
atom
independently
crystal composition
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PCT/JP1997/004069
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English (en)
Japanese (ja)
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Yasuhiro Haseba
Shuichi Matsui
Kazutoshi Miyazawa
Hiroyuki Takeuchi
Yasuhiro Kubo
Fusayuki Takeshita
Etsuo Nakagawa
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Chisso Corporation
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Priority to AU48861/97A priority Critical patent/AU4886197A/en
Publication of WO1998020006A1 publication Critical patent/WO1998020006A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/40—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
    • 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
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • 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
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring

Definitions

  • Dioxane derivative having fluoroalkyl group liquid crystal composition and liquid crystal display device
  • the present invention relates to a liquid crystal compound and a liquid crystal composition, and more particularly, to a liquid crystal composition, particularly a dioxane derivative having a fluoroalkyl group, which is a liquid crystal compound suitable as a component of a liquid crystal composition for TFT, and a liquid crystal composition containing the same. And a liquid crystal display device formed using the liquid crystal composition.
  • Liquid crystal display devices utilize the optical anisotropy and dielectric anisotropy of liquid crystal materials.
  • TN type twisted nematic type
  • DS type dynamic scattering type
  • GH liquid crystal materials
  • guest-host type liquid crystal type
  • DAP type alignment phase change type
  • STN type super twisted nematic type
  • the liquid crystal material used in any display element must be stable to moisture, air, heat, light, etc., exhibit a liquid crystal phase over as wide a temperature range as possible around room temperature, have low viscosity, Good compatibility with liquid crystal compounds (hereinafter referred to as compounds having a liquid crystal phase and compounds that do not impair the liquid crystal phase even when mixed with other liquid crystals) and liquid crystal compositions, and have a large dielectric anisotropy value It must have ( ⁇ ⁇ ), optimal optical (refractive index) anisotropy value ( ⁇ ⁇ ) and high resistivity. However, at present, no single compound satisfies all of these conditions, and at present the liquid crystal composition obtained by mixing several liquid crystal compounds is used.
  • the compound (10) is used mainly as a component of a liquid crystal composition for TFTs because it has a higher specific resistance value than a liquid crystal compound having a cyano group, but its external ⁇ is 8. 7 and cannot be used as a liquid crystal material for low-voltage driving represented by the currently required 2.5 V driving.
  • the above-mentioned extrapolation ⁇ is determined by dissolving compound (10) in a mother liquid crystal having a nematic phase, ⁇ p of the composition thus obtained, ⁇ p of the mother liquid crystal, and mixing of the compound in the composition. Although it is a calculated value obtained from the ratio, it substantially reflects the value of the compound (10) (in the following description, the value of ⁇ e for the compound is used in the same meaning as described above).
  • a trifluorophenyl derivative represented by the following formula (11) is known as a compound having a ⁇ £ larger than that of the compound (10) (Japanese Patent Application Laid-Open No. H02-233366).
  • the compound (1 1) has a value of 11.7, which is larger than that of the compound (10). However, for the same reason as described above, a material that can meet the demand for a lower voltage in the market is used. Absent.
  • This compound (14) has a ⁇ £ of 13.0, which is 4.3 larger than that of the above compound (13). However, for the same reason as above, it is necessary to reduce the market voltage. It is not a material that can meet the demands.
  • a dioxane derivative represented by the following formula (15) is also known as a compound exhibiting a larger ⁇ £. (Japanese Unexamined Patent Publication (Kokai) No. 02-2333626).
  • this compound exhibits a large value of about 15 as a result, but by using this compound, the driving voltage of the TFT-type liquid crystal display element can be brought to a required level. However, it is still insufficient to reduce the amount to a lower value, and the appearance of a compound having a larger ⁇ is expected.
  • a dioxane derivative similar to the above compound (15) a dioxane derivative having a fluoroalkyl group as shown in the formula (1) (6) is also known (US Pat. No. 5494946). 06), but the ⁇ of this compound does not exceed that of the compound (15). Disclosure of the invention
  • An object of the present invention is to solve the above-mentioned drawbacks of the prior art, to obtain a significantly large ⁇ , a high specific resistance value, electrical and chemical stability, and compatibility with existing liquid crystal compounds.
  • Another object of the present invention is to provide a liquid crystal compound which is suitable for driving a TFT type liquid crystal display element at a low voltage, a liquid crystal composition containing the same, and a liquid crystal display element using the same.
  • the present inventors have conducted intensive studies in order to achieve the above object. As a result, the present inventors have found that the molecule has a combination of a fluor ⁇ alkyl group and a 1,3-dioxane-1,2,5-diyl group, Benzene, cyclohexane or silinane ring which may be substituted by a fluorine or chlorine atom via a covalent bond, — CH 2 CH 2 — or CH 2 CH 2 CH 2 CH 2 —
  • the dioxane derivative has a large structure, has good compatibility with existing liquid crystal compounds, and shows high specific resistance. They found it to be the best material and completed the invention.
  • the configuration of the present invention is as follows.
  • ⁇ 0 is an integer of 2 to 10
  • ⁇ 1 and ⁇ 2 are each independently an integer of 0 to 2
  • ⁇ 3 and ⁇ 4 are each independently 0 or 1.
  • Q and Q 2 each independently represent a hydrogen atom, a fluorine atom or a chlorine atom
  • Za, Zb and Z c each independently represent a single atom A bond, — CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 —, —COO— or one CF 20 —
  • ring A 1 and ring A 2 are each independently a group represented by formulas (a) to ( i)
  • the methylene group may be replaced by an oxygen atom or a sulfur atom.
  • Each element constituting the compound may include those selected from their isotopes.
  • a liquid crystal composition comprising at least one kind of the dioxane derivative according to any one of (7).
  • R 3 Yi, L]
  • L 2 , and Z 2 may be the same or different from each other in each formula
  • R 3 is an alkyl group having 1 to 10 carbon atoms
  • one or more non-adjacent methylene groups may be substituted with an oxygen atom or one CH 2 CH—, and an arbitrary hydrogen atom may be substituted with a fluorine atom.
  • L, and L 2 hydrogen atoms each independently may Is a fluorine atom
  • Z 2 is each independently — CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 —, —COO—, —CF 2 0—, — OCF 2 —, — CH-CH— Or simple -O 98/20006 is indicated.
  • Ring B is trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or 1,4-phenylene in which a hydrogen atom may be substituted by a fluorine atom
  • ring C is trans-1,1, 4-cyclohexylene or 1,4-phenylene in which a hydrogen atom may be replaced by a fluorine atom.
  • each element constituting them may include those selected from their isotopes.
  • a liquid crystal composition comprising at least one compound selected from the group consisting of:
  • R 4 and R 5 each independently represent an alkyl group having 1 to 10 carbon atoms.
  • non-adjacent ⁇ or more methylene groups are an oxygen atom or one CH 2 CH
  • any hydrogen atom may be replaced by a fluorine atom
  • Y 2 is one CN group or one C ⁇ C—CN
  • ring E is trans-1,4-cyclohexyl.
  • Methoxyhexylene, 1,4-phenylene, 1,3-dioxane-1,2,5-diyl or pyrimidine-1,2,5-diyl, ring G is trans-1,4-cyclohexylene, hydrogen atom 1,4-Phenylene or pyrimidine-2,5-diyl which may be substituted by a fluorine atom, ring H is trans and 4-cyclohexylene or 1,4-phenylene, Z 3 is CH 2 CH 2 - one COO- or a single bond, L 3, L 4 and L 5 represents a hydrogen atom or a fluorine atom each independently, b, c Oyo d is each independently 0 or ⁇ .
  • each element constituting them may include those selected from their isotopes.
  • a liquid crystal composition comprising at least one of the following. (11) As the first component, at least one dioxane derivative according to any of (1) to (7) is contained, and as the second component, the general formulas (2), (3) and (4) )
  • L 2 , and Z 2 may be the same or different from each other in each formula, and R 3 is an alkyl group having 1 to 10 carbon atoms, In the alkyl group, one or more non-adjacent methylene groups may be substituted with an oxygen atom or one CH 2 CH—, and an arbitrary hydrogen atom may be substituted with a fluorine atom.
  • L, and L 2 are each independently hydrogen atom Is a fluorine atom
  • Ring B is trans-1,4-cyclohexylene, 1,3-dioxane-1,2,5-diyl or a hydrogen atom in which a hydrogen atom may be substituted by a fluorine atom 1,4-phenylene
  • Ring C is trans-1 1,4-cyclohexylene or 1,4-phenylene in which a hydrogen atom may be replaced by a fluorine atom.
  • each element constituting them may include those selected from their isotopes.
  • R 6 , RTI, J and K may be the same or different from each other in each formula, and R 6 and R 7 are each independently an alkyl group having 1 to 10 carbon atoms.
  • R 6 and R 7 are each independently an alkyl group having 1 to 10 carbon atoms.
  • a liquid crystal composition comprising:
  • At least one dioxane derivative according to any one of (1) to (7) is contained, and as a part of the second component, the general formulas (2) and (3) And at least one compound selected from the group consisting of (4), and as the other part of the second component, selected from the above general formulas (5) and Z or (6).
  • a liquid crystal composition comprising at least one compound selected from the group consisting of the general formulas (7), (8) and (9) as a third component. object.
  • liquid crystal composition according to any one of (8) to (13), further comprising an optically active compound.
  • the liquid crystal compound represented by the general formula (1) of the present invention that is, the dioxane derivative having a fluoroalkyl group, has a combination of a fluoroalkyl group and a 1,3-dioxane-2,5-diyl group in a molecule, and A fluorine or chlorine atom is substituted through a covalent bond at the 2-position of the ring, i. (: ⁇ 1 2 (?
  • liquid crystal compound of the present invention when used as a component of a liquid crystal composition, a liquid crystal composition particularly useful for lowering the voltage of a TFT type liquid crystal display device can be provided.
  • n 0 is an integer related to the determination of the chain length (the number of carbon atoms) of the fluoroalkyl group, and the value is 2 to 10 from the viewpoint of the balance between the viscosity required for the compound and the clearing point. Suitable, preferably 2-7, more preferably 2-5.
  • Z a, Zb and Z c of the linking group are as described above, and each is independently a single bond, one CH 2 CH 2 —, — CH 2 CH 2 CH 2 CH 2 —, one C ⁇ 0— or one Indicates CF 2 -1.
  • n2 is an integer for determining the chain length (the number of carbon atoms) of the linking group provided between the 2-position of the dioxane ring and the other ring, and 0 to 2 is suitable.
  • Ru 1 or 2 der each linking group is a single bond, - CH 2 CH 2 - or a CH 2 CH 2 CH 2 C h 2 - become.
  • a single bond has a relatively high clearing point, a relatively low viscosity, And electrically stable compounds — CH 2 CH 2 — and — CH 2 C'H 2 CH 2 C
  • H 2- is a chemically and electrically stable compound having excellent compatibility with other liquid crystal compounds or liquid crystal compositions
  • -C 00- is a compound having a high clearing point and showing a large ⁇ ⁇ .
  • the compound, —CF 20 — has a low viscosity, a relatively large hardness, and can provide a chemically and electrically stable compound, respectively.
  • Nl is an integer of 0 to 2; n3 and n4 are each independently 0 or 1; n3 ⁇ n4 and n1 + n3 + n4 ⁇ 2.
  • nl, 113 and 114 are all 0, 111 and 114 are both 0, 113 is 1, n1 is 1, and n3 and n4 are both 0 and n 1 + n 3 + n 4 is 2 (11 1 and 11 3 are both 1 and n 4 is 0, n 1 is 2 and n 3 and n 4 are both 0).
  • those represented by the formula (1-1a) are low in viscosity, have excellent compatibility with other liquid crystal compounds or liquid crystal compositions, and have a large ⁇ .
  • the compound represented by b) has a large ⁇ and a large ⁇ , and n 2 n 0 in the compounds represented by the formulas (1 c), (1 ⁇ d) and (1—e).
  • the four-ring compounds represented by the formulas (1 to f) to (1 to h) have a high clearing point and a large ⁇ .
  • ⁇ in the terminal substituent represents a hydrogen atom, a halogen atom or a halogenated alkyl group having 1 to 5 carbon atoms as described above, and the halogenated alkyl group is one or more methylene groups which are not adjacent to each other in the group. May be replaced by an oxygen atom or a sulfur atom.
  • compounds in which the halogen atom is a fluorine atom have a relatively large ⁇ , have low viscosity, and have excellent compatibility with other liquid crystal compounds or liquid crystal compositions.
  • the compound halogenated alkyl group is CF 3 are those having a very large delta epsilon, is also a compound which is ⁇ _CF 3 is a low viscosity.
  • the above-mentioned halogen atom is a chlorine atom, and the halogenated alkyl group in which one or more non-adjacent methylene groups in the group are replaced with an oxygen atom.
  • the compound represented by 3 has a large ⁇ and a high transparent point, and the compound replaced by the same oxygen atom is OCH 2 CF 2 H ⁇ OCH 2 CF 3 has a high clear point. Very low viscosity.
  • Preferred examples of the alkyl group or halogenated alkyl group in which one or more non-adjacent methylene groups in the group are replaced by an oxygen atom further include a difluoromethyl group and a difluorochloro group.
  • Methyl group, 2,2,2-Trifluoroethyl group, 1,2,2,2-Tetrafluoroethoxy group, 2-Fluoroethyl group, 3-Fluoropropyl group, 4-Fluorobutyl group, Difluoromethoxy group, Difluorochloromethoxy group Group, pentachlorofluoroethoxy group and heparofluoropro Poxy groups and the like can be mentioned.
  • '-Ring A 1 and ring A 2 each independently represent a group selected from the group consisting of formulas (a) to (i) as described above, and the group is a 1,4-phenylene group Those having a fluorine atom or a chlorine atom introduced as a side substituent may be used.
  • the group of the silinane ring represented by the formula (h) or (i) can give a compound having excellent compatibility with other liquid crystal compounds and liquid crystal compositions at a low temperature.
  • the compounds of the present invention each have a fluoroalkyl group and a dioxane ring in combination. Among them, a covalent bond at the 2-position of the dioxane ring, one CH 2 CH 2 — or —CH 2 CH 2 CH 2 A benzene ring, cyclohexane ring or silinane ring, which may be substituted by a fluorine or chlorine atom via CH 2 —, is bonded, and the core consists of 2 to 4 rings including a dioxane ring. It is preferable in that it has a specifically large ⁇ .
  • 3-fluoro 1,4-phenylene group has a relatively large ⁇ ⁇ , exhibits a high liquid crystal phase temperature range and low viscosity. And a compound having good compatibility, and a 3,5-difluorophenylene group having a very large ⁇ and a very good compatibility can be obtained.
  • the liquid crystal compound represented by the general formula (1) of the present invention may include those in which each element in the formula is selected from their isotopes. That is, there is no particular change in the liquid crystal characteristics as compared with the case where the isotope is not contained even when such isotopes are contained, and a similar effect can be obtained.
  • the compound of the present invention is particularly suitable as a component of a liquid crystal composition for TFT.
  • Other applications for example, for ⁇ , guest host mode, polymer dispersed liquid crystal display device , For dynamic scattering mode, for STN, for in-plane switching, for OCB mode or as a component of R-OCB mode liquid crystal composition. Also suitable as a compound for a liquid crystal.
  • the liquid crystal composition provided by the present invention comprises at least one liquid crystal compound represented by the general formula (1) as a first component.
  • the content be 0.1 to 9.9% by weight based on the weight of the liquid crystal composition in order to exhibit excellent characteristics, preferably 1 to 50% by weight, more preferably. 3 to 20% by weight.
  • the liquid crystal composition of the present invention may be composed of only the above-mentioned first component.
  • the second component is selected from the group consisting of the general formulas (2), (3) and (4) referred to above.
  • a mixture of at least one compound (hereinafter, referred to as a second component A) and at least one compound selected from the group consisting of general formulas (5) and / or (6) (hereinafter, referred to as a second component B)
  • Known compounds can also be mixed for the purpose of adjusting the compounds, the threshold voltage, the liquid crystal phase temperature range, ⁇ , ⁇ , the viscosity and the like.
  • preferred examples of the compound included in the general formula (2) include the following formulas (2-1) to (2-9), and preferred examples of the compound included in the general formula (3)
  • Preferred examples of the compounds contained in (3-1) to (3-69) and the general formula (4) include the compounds represented by the formulas (4-1) to (4-24).
  • each element constituting the compound of each formula may include those selected from their isotopes.
  • the compounds represented by these general formulas (2) to (4) have a positive ⁇ , are excellent in thermal stability and chemical stability, and have a high voltage holding ratio (a large specific resistance value). This is an indispensable compound when preparing liquid crystal compositions for TFTs that require high reliability.
  • the amount of the compound used is preferably in the range of 1 to 99% by weight based on the total weight of the liquid crystal composition, but is preferably 10 to 97% by weight. More preferably, it is 40 to 95% by weight. In that case, compounds represented by formulas (7) to (9) may be contained.
  • the compounds represented by the above general formulas (2) to (4) can also be used for preparing a liquid crystal composition for STN display mode or TN display mode.
  • preferred examples of the compound contained in the general formula (5) include the following formulas (5-1) to (5-40); Preferred examples include the compounds represented by the formulas (6-1) to (6-3).
  • each element constituting the compound of each formula may include those selected from their isotopes.
  • the compounds represented by the general formulas (5) and (6) have a large ⁇ and a large ⁇ , and are particularly used for the purpose of reducing the threshold voltage of the liquid crystal composition.
  • for the purpose of widening the nematic range of the liquid crystal composition such as adjusting ⁇ and increasing the clearing point, to improve the steepness of the threshold voltage of the liquid crystal composition for STN display mode and ⁇ display mode.
  • This compound can reduce the threshold and voltage of the liquid crystal composition as the amount of the compound is increased, but increases the viscosity. Therefore, as long as the viscosity of the liquid crystal composition satisfies the required characteristics, it is more advantageous to use a large amount of the liquid crystal composition for low voltage driving.
  • the liquid crystal composition for the S ⁇ ⁇ ⁇ ⁇ display method or ⁇ ⁇ display method was prepared.
  • the amount used is suitably in the range of 0.1 to 99% by 9% by weight based on the total weight of the liquid crystal composition, preferably 10 to 97% by weight, more preferably 40 to 97% by weight. It is 95% by weight.
  • the following formulas (7-1) to (7-11) are preferred examples of the compound contained in the general formula (7), and the following formulas (7-11) are preferred examples of the compound contained in the general formula (8).
  • Preferred examples of the compounds included in (8_1) to (8-18) and the general formula (9) include the compounds represented by the formulas (9-1) to (9-16).
  • each element constituting the compound of each formula may include those selected from their isotopes.
  • the compounds represented by the general formulas (7) to (9) are compounds having a small absolute value of ⁇ and close to zero, and among them, the compound represented by the general formula (7) mainly adjusts the viscosity of the liquid crystal composition.
  • the compounds of the general formulas (8) and (9) are used for the purpose of adjusting ⁇ and for expanding the nematic range of the liquid crystal composition such as increasing the clearing point, and for adjusting ⁇ .
  • This compound increases the threshold voltage of the liquid crystal composition as the amount used increases, but decreases the viscosity. Therefore, as long as the threshold voltage of the liquid crystal composition satisfies the required characteristics, the larger the amount used, the better.
  • the above-mentioned amount is suitably at most 40% by weight, preferably at most 35% by weight, based on the total weight of the liquid crystal composition.
  • the amount used is preferably 70% by weight or less, more preferably 60% by weight, based on the total weight of the liquid crystal composition. It is as follows.
  • the optically active compound is generally used in a special case, for example, OCB (0 Ptica 1 iy and omp ensated birefringence). It is added for the purpose of inducing the helical structure of the composition to adjust the required torsion angle, and thereby preventing reverse twist.
  • OCB Ptica 1 iy and omp ensated birefringence
  • This optically active compound is a compound widely selected from known compounds as long as the above object is achieved, preferably an optically active compound represented by the following formulas (Op-1) to ( ⁇ p-8). Can be mentioned. By adding these optically active compounds, the liquid crystal composition is twisted ⁇ pitch
  • the pitch length of this twist is in the range of 40 to 200 ⁇ m if the liquid crystal composition is for TFT or TN, in the range of 6 to 20 ⁇ m for STN, and the bistable TN (Bist ab le TN) If it is for the mode, it is preferable to adjust each in the range of 5 to 4 zm.
  • two or more optically active compounds may be added for the purpose of adjusting the temperature dependence of the pitch length.
  • the liquid crystal composition provided according to the present invention is generally prepared by a method known per se, for example, a method in which various components are mutually dissolved at a high temperature.
  • a dichroic dye such as a merocyanine-based, styryl-based, azo-based, azomethine-based, azoxy-based, quinophthalone-based, anthraquinone-based, or tedrazine-based dye is added during the preparation, a guest-host (GH) mode can be obtained. It can also be used as a liquid crystal composition.
  • the liquid crystal composition according to the present invention is typified by NCAP prepared by encapsulating a nematic liquid crystal in a microcapsule, and a polymer-network liquid crystal display device (PNLCD) prepared by forming a three-dimensional network polymer in the liquid crystal. It can also be used as a liquid crystal composition for birefringence control (ECB) mode and dynamic scattering (DS) mode, including those for polymer dispersed liquid crystal display devices (PDLCD).
  • ECB birefringence control
  • DS dynamic scattering
  • the nematic liquid crystal composition of the present invention is prepared, and the following composition examples 1 to 26 can be shown as examples.
  • the compounds are indicated according to the rules shown in Table 1 below, and the groups shown in the columns of the left terminal group, the bonding group, the ring structure, and the right terminal group are shown in the symbol columns.
  • the hydrogen atom on trans-1,4-cyclohexylene and the trans, trans-bicyclohexane-1,4'-diyl group is replaced by an isotope deuterium atom.
  • the above groups are represented by the formulas (60) and (61), respectively, the hydrogen atoms J 1, J 2, J 3, J 4, J 5, J 6, J 7 And any of J 8 are replaced by only those selected from the corresponding deuterium atoms 1 D, 2 D, 3 D, 4 D, 5 D, 6 D, 7 D and 8 D. H [1D, ⁇ 8D].
  • the compound No. attached to the compound of the present invention is the same as that shown in Examples described later. Yes, the content of the compound means% by weight unless otherwise specified.
  • the characteristic data of the composition examples are T NI (nematic isotropic liquid transition temperature or clearing point), V (viscosity: measurement temperature 20.0 ° C), ⁇ (refractive index anisotropy). : Measurement temperature 25.0), ⁇ (Dielectric anisotropy value: Measurement temperature 25.0 ° C), V th (Threshold voltage: Measurement temperature 25. (TC) and P (Pitch: The measurement temperature was 25 ° C).
  • a liquid crystal composition having the following compound content was prepared.
  • V th 2.26 V
  • a liquid crystal composition having the following compound content was prepared.
  • 6-Py B--53 0% 6-Py B-06 3, 0% 6-Py B-07 3.0% 6-Py B 08 3.0%
  • V th 2.5 1 V
  • a liquid crystal composition having the following compound content was prepared.
  • V th 1.68 V
  • a liquid crystal composition having the following compound content was prepared.
  • a liquid crystal composition having the following compound content was prepared.
  • a liquid crystal composition having the following compound content was prepared.
  • V-HB-C 1 1.0%
  • V 2 -HHB- 1 1 5.0%
  • a liquid crystal composition having the following compound content was prepared.
  • F 4 -HHGB-CF 3 (No. 1 9 1) 5.0% 30 1 -BEB (F) 1 C 1 2.0% 50 1 -BE B (F)-C 4.0% 1 V 2- BEB (F, F) C 1 6.0% 3 -HB-02 1 0.0% 3 -HH- 4 3.0% 3 -HHB-F 3.0% 3 -HHB-1 8.0% 3 HHB-01 4.0% 3 -HBEB-F 4.0% 3 -HHEB-F 7.0% 5 -HHEB-F 7.0% 3 -H2 BTB- 2 4.0% 3 -H 2 BTB- 3 4.0% 3 -H 2 BTB-4 4.0% 3— HB (F ) TB-2 5.0% The properties of this composition were determined and were as follows.
  • V th 1.36 V
  • a liquid crystal composition having the following compound content was prepared.
  • F 3 -GB (F, F) B (F)-F (No. 5 2) 6.0%
  • F 2 -GHB (F) -OCF 3 (No. 95) 6.0%
  • F 3 -HGB ( F, F) -CF 3 (No. 1 3 7) 6.0%
  • V th 1.5 3V
  • a liquid crystal composition having the following compound content was prepared.
  • V lh 2.0 1 V
  • a liquid crystal composition having the following compound content was prepared.
  • a liquid crystal composition having the following compound content was prepared.
  • V th 2.3 1 V
  • a liquid crystal composition having the following compound content was prepared.
  • a liquid crystal composition having the following compound content was prepared.
  • a liquid crystal composition having the following compound content was prepared.
  • optically active compound represented by the formula (Op_8) described above was added to 100 parts of the primary composition to obtain a secondary composition, and the properties of the secondary composition were obtained. It was right.
  • a liquid crystal composition having the following compound content was prepared.
  • F 5 -GB-OCF 3 (No. 13) 4.0% F 3 -GHB B (F)-F (No. 1 5 2) 4.0% F 4 -HHGB-C F 3 (No. 1 9 1) 4.0% 7-HB (F, F)-F 3.0% 3 HB- 02 7.0%
  • a liquid crystal composition having the following compound content was prepared.
  • F 2 -G 4 B (F) — F (No. 2 2) 3.0% F 2 -GHB (F) -OCF 3 (No. 95) 3.0% F 3 -HGB (F, F) -CF 3 (No. 1 3 7) 3.0% F 3 -HG 4 B (F, F)-F (No. 1 5 0) 3.0% 7 -HB (F, F) 1 F 3. 0%
  • a liquid crystal composition having the following compound content was prepared.
  • a liquid crystal composition having the following compound content was prepared.
  • F 2 -G 2 B (CD -CL (No. 20) 40% F 2 -GHB (F) -OCF 3 (No. 95) 70% F 3 -HGB (F, F) -CF 3 ( No. 1 3 7) 0%
  • V th 1.76 V
  • a liquid crystal composition having the following compound content was prepared.
  • F 3 -GB (F) -CF 3 No. 7
  • F 5-GB-OCF 3 No. 1 3
  • F 2 -G 2 B (F) B (F) F No. 1 24
  • F 3 -HGB (F, F) _CF 3 No. 1 37
  • V th 1.50V
  • a liquid crystal composition having the following compound content was prepared.
  • F 2-GHB (F) -OCF 3 (No. 95) 7.0% F 5 -GB-OCF 3 (No. 1 3) 5.0% F 2-G 2 B (F) B (F) F (thing N 0.1 2 4) 5.0% 5 HB-F 1 2.0%
  • a liquid crystal composition having the following compound content was prepared.
  • a liquid crystal composition having the following compound content was prepared.
  • a liquid crystal composition having the following compound content was prepared.
  • the compound represented by the general formula (1) according to the present invention has the formulas (11a) and (1—b) to (L-d), (1-e) and (1-f)-(l-h) are expanded to those known in the literature, for example, the fourth edition of Experimental Chemistry (Maruzen) , J. Org.Chem., _4_2_, 1821 (1977) and J. Chem.Soc.Perkin Tran s. 2, 204 1 (1899) It can be easily manufactured by making full use of the methods described in, for example.
  • Fluoroalkyl bromide (17) and getyl malonate (18) were allowed to act in the presence of lithium carbonate in an alcoholic solvent to give compound (19), which was then treated with lithium aluminum hydride ( (Hereinafter abbreviated as LAH) can be reacted in a non-protonic solvent such as tetrahydrofuran (hereinafter abbreviated as THF) to obtain the 1,3-propanediol derivative (20) for the title use.
  • LAH lithium aluminum hydride
  • THF tetrahydrofuran
  • the compound (25) was obtained by adding the ethyl phosphonoacetate and sodium hydride to this mixture and conducting the Itti-Hea Horner reaction (see the 4th edition Experimental Chemistry Lecture (Maruzen) 19: 74-77). Hydrogenate this to ethyl ester After the derivative (26), a compound (27) is obtained by reacting lithium diisopropyl pyramide (hereinafter abbreviated as LDA) and methyl methyl carbonate in this order in a non-protonic solvent such as THF. By applying LAH to this, the 1,3-propanediol derivative (28) for the title use can be obtained.
  • LDA lithium diisopropyl pyramide
  • THF non-protonic solvent
  • the compound of the present invention can be suitably obtained by using the thus obtained 1,3-propanediol derivative as one of the raw materials.
  • benzaldehyde derivative (31) ethyl acetylethyl phosphonoacetate and sodium hydride, these were subjected to the Wittig-Hiehorner reaction described above to obtain the compound (32), which was hydrogenated to give the ethyl ester derivative.
  • a aldehyde derivative (34) is obtained by the action of a reducing agent such as diisobutylaluminum hydride (hereinafter abbreviated as DI BAL).
  • DI BAL diisobutylaluminum hydride
  • a 1,3-propanediol derivative (20) was reacted with a benzaldehyde derivative (36) in the presence of an acid catalyst such as paratoluenesulfonic acid to obtain a phenyldioxane derivative (37), which was then treated with butyllithium.
  • Bu Li is allowed to act at about ⁇ 50 ° C. to obtain lithoide (38).
  • the title compound can be obtained by subjecting it to a known method for synthesizing a homobiaryl compound, and there are usually two methods.
  • the other one is a method described in J. Chem. Soc. Perkin Trans. 2, 2, 41 (1 89 9), and (i) converting iodide (38) to iodine. And (bor) a boronic acid derivative (40) obtained from the Grignard reagent prepared from the bromobenzene derivative (39) and a trialkyl borate, such as Pd (0) or the like. In this method, a coupling reaction is performed in the presence of a catalyst.
  • the title compound can be obtained in the same manner as in the method for obtaining a compound in which Zb is a single bond, except that the compound (50) is used in place of the Grignard reagent compound (45).
  • the title compound was prepared in the same manner as in the production of the compound represented by the formula (1-1a) except that the 1,3-propanediol derivative (30) was replaced with the 1,3-propanediol derivative (20). Can be obtained.
  • a compound having a silanane ring typified by 11-sila or 4-sila14-cyclohexylene can be produced by applying the method described in JP-A-7770148.
  • C indicates a crystal
  • S indicates a smectic phase
  • N indicates a nematic phase
  • I indicates an isotropic liquid phase.
  • the reaction solution was filtered using celite, the solvent in the filtrate was distilled off, and the residue was extracted with hexane.
  • the extract was washed with water, dried over magnesium sulfate, and then the solvent was distilled off to obtain 223 g (l.01mo1) of diethyl 3-fluoropropylmalonate. Its yield from 3-fluorobutene mopropane was 61.6%.
  • THF11 was added to 7.6 g (1.52mo1) of LAH, and the mixture was cooled to 5 ° C.
  • a 100 ml THF solution of 223 g (1.01 mo 1) of dimethyl 2-fluoropropylmalonate was added dropwise so as not to exceed 20 ° C.
  • 5 Om1 of water was added dropwise so as not to exceed 20 ° C, and the mixture was stirred for 10 minutes, and 2N-NaOH 8 Oml was added dropwise.
  • 5 g of magnesium sulfate was added, and the mixture was filtered using celite. The solvent was distilled off to obtain 2- (3-fluoropropyl) -1,3-propanediol. 7 g (1.01 m01) were obtained. This reaction proceeded almost quantitatively.
  • liquid crystal composition A 1 Nematic liquid crystal composition containing a cyanophenylcyclohexane-based liquid crystal compound (hereinafter sometimes referred to as liquid crystal composition A 1):
  • the physical properties of the above compound No. 52 were calculated from the physical properties of the above liquid crystal compositions and the mixing ratios of the contained compounds by the external method, and the results were as follows.
  • the liquid crystal compound of the present invention has an extremely large ⁇ , a high specific resistance value, is electrically and chemically stable, and has good compatibility with existing liquid crystal compounds. is there.
  • liquid crystal compound of the present invention when used as a component of a liquid crystal composition, low voltage driving of a liquid crystal display device, particularly, a TF F type liquid crystal display device can be achieved.
  • the liquid crystal display device using the liquid crystal composition containing the liquid crystal compound of the present invention is used for watches, calculators, various measuring instruments, automobile panels, word processors, electronic notebooks, printers, convenience stores, televisions, and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Liquid Crystal Substances (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)

Abstract

Composés de cristaux liquides présentant des valeurs de Δε considérablement importantes et des valeurs de résistance extrêmement spécifiques, une compatibilité excellente avec des composés existants de cristaux liquides et qui sont particulièrement appropriés pour l'attaque à basse tension d'éléments d'écran à cristaux liquides de type TFT; compositions de cristaux liquides contenant lesdits composés. Ces composés sont des dérivés de dioxane représentés par la formule (1), dans laquelle n0 est un entier de 2 à 10; n1 et n2 sont chacun indépendamment un entier de 0 à 2; n3 et n4 sont chacun indépendamment 0 ou 1, n1, n3 et n4 répondent aux rapports suivants: n3≥n4 et n1 + n3 + n4≤2; Q1 et Q2 représentent chacun indépendamment hydrogène, fluoro ou chloro; Za, Zb et Zc représentent chacun indépendamment une liaison simple, -CH2CH2-, -CH2CH2CH2CH2-, -COO- ou -CF2O-; A1 et A2 sont chacun sélectionnés dans les groupes (a) à (i), et Y représente hydrogène, halogéno ou haloalkyle C1-C5.
PCT/JP1997/004069 1996-11-07 1997-11-07 Derives de dioxane fluoroalkyle, compositions de cristaux liquides et elements d'ecran a cristaux liquides WO1998020006A1 (fr)

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JP8311405A JPH10139778A (ja) 1996-11-07 1996-11-07 フルオロアルキル基を有するジオキサン誘導体、液晶組成物および液晶表示素子
JP8/311405 1996-11-07

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US20140132868A1 (en) * 2012-05-28 2014-05-15 Jnc Petrochemical Corporation Optically isotropic liquid crystal medium and optical device
CN104099105A (zh) * 2014-06-30 2014-10-15 北京八亿时空液晶科技股份有限公司 一种含有二噁烷环的液晶化合物及其应用
CN106635058A (zh) * 2015-11-02 2017-05-10 江苏和成显示科技股份有限公司 液晶组合物及其显示器件
WO2019120101A1 (fr) * 2017-12-21 2019-06-27 江苏和成显示科技有限公司 Composé à cristaux liquides, composition de cristaux liquides et composant d'affichage photoélectrique

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* Cited by examiner, † Cited by third party
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JP2000002873A (ja) 1998-06-16 2000-01-07 Nec Corp 液晶表示装置
DE10111572B4 (de) * 2000-03-23 2009-11-12 Merck Patent Gmbh Flüssigkristallines Medium und seine Verwendung
DE10340534B4 (de) * 2002-09-24 2015-06-25 Merck Patent Gmbh Flüssigkristallines Medium und seine Verwendung
EP2457975B1 (fr) * 2010-11-29 2014-06-25 Merck Patent GmbH Mélanges à base de cristaux liquides
TWI544063B (zh) * 2012-12-04 2016-08-01 捷恩智股份有限公司 液晶組成物及其用途、液晶顯示元件
CN104610979B (zh) * 2013-11-05 2017-02-08 江苏和成显示科技股份有限公司 液晶组合物及其液晶显示器件
CN104130781B (zh) * 2014-07-03 2016-05-11 北京八亿时空液晶科技股份有限公司 一种液晶组合物及其应用
JP6524699B2 (ja) * 2015-02-24 2019-06-05 Jnc株式会社 ビニレン基を有する液晶性化合物、液晶組成物および液晶表示素子
CN113736478B (zh) * 2020-05-27 2023-04-07 江苏和成显示科技有限公司 一种液晶组合物及液晶显示元器件
CN113736476B (zh) * 2020-05-27 2023-04-07 江苏和成显示科技有限公司 一种液晶组合物及液晶显示元器件

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4102847C1 (fr) * 1991-01-31 1992-03-26 J.M. Voith Gmbh, 7920 Heidenheim, De
JPH0717889A (ja) * 1991-07-05 1995-01-20 Chisso Corp 光学活性ｐ−（１−メチルアルキルオキシ）フェノール
JPH0776536A (ja) * 1993-09-06 1995-03-20 Chisso Corp ハロゲン化ビニル誘導体およびこれを原料とする液晶化合物の製造方法
US5494606A (en) * 1990-04-26 1996-02-27 Merck Patent Gesellscaft Mit Beschrankter Haftung 1,3-dioxane derivatives, and liquid-crystalline medium

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5494606A (en) * 1990-04-26 1996-02-27 Merck Patent Gesellscaft Mit Beschrankter Haftung 1,3-dioxane derivatives, and liquid-crystalline medium
DE4102847C1 (fr) * 1991-01-31 1992-03-26 J.M. Voith Gmbh, 7920 Heidenheim, De
JPH0717889A (ja) * 1991-07-05 1995-01-20 Chisso Corp 光学活性ｐ−（１−メチルアルキルオキシ）フェノール
JPH0776536A (ja) * 1993-09-06 1995-03-20 Chisso Corp ハロゲン化ビニル誘導体およびこれを原料とする液晶化合物の製造方法

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140132868A1 (en) * 2012-05-28 2014-05-15 Jnc Petrochemical Corporation Optically isotropic liquid crystal medium and optical device
CN104334687A (zh) * 2012-05-28 2015-02-04 捷恩智株式会社 光学等向性液晶媒体及光元件
US9175222B2 (en) * 2012-05-28 2015-11-03 Jnc Corporation Optically isotropic liquid crystal medium and optical device
CN104334687B (zh) * 2012-05-28 2016-08-17 捷恩智株式会社 液晶组合物与其用途及混合物、高分子/液晶复合材料及光元件
CN104099105A (zh) * 2014-06-30 2014-10-15 北京八亿时空液晶科技股份有限公司 一种含有二噁烷环的液晶化合物及其应用
CN106635058A (zh) * 2015-11-02 2017-05-10 江苏和成显示科技股份有限公司 液晶组合物及其显示器件
CN106635058B (zh) * 2015-11-02 2018-11-02 江苏和成显示科技有限公司 液晶组合物及其显示器件
WO2019120101A1 (fr) * 2017-12-21 2019-06-27 江苏和成显示科技有限公司 Composé à cristaux liquides, composition de cristaux liquides et composant d'affichage photoélectrique
CN109942538A (zh) * 2017-12-21 2019-06-28 江苏和成显示科技有限公司 一种液晶化合物及其液晶组合物和光电显示器件
TWI694139B (zh) * 2017-12-21 2020-05-21 大陸商江蘇和成顯示科技有限公司 一種液晶化合物及其液晶組合物和光電顯示器件

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