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WO2015076093A1 - Composition de cristaux liquides nématiques et élément d'affichage à cristaux liquides l'utilisant - Google Patents

Composition de cristaux liquides nématiques et élément d'affichage à cristaux liquides l'utilisant Download PDF

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WO2015076093A1
WO2015076093A1 PCT/JP2014/079195 JP2014079195W WO2015076093A1 WO 2015076093 A1 WO2015076093 A1 WO 2015076093A1 JP 2014079195 W JP2014079195 W JP 2014079195W WO 2015076093 A1 WO2015076093 A1 WO 2015076093A1
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liquid crystal
crystal composition
ocf
general formula
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Japanese (ja)
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士朗 谷口
河村　丞治
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to CN201480062831.XA priority Critical patent/CN105745306B/zh
Priority to JP2015549053A priority patent/JP6061040B2/ja
Publication of WO2015076093A1 publication Critical patent/WO2015076093A1/fr
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
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    • 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
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C09K19/322—Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring
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    • 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
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0466—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 linking chain being a -CF2O- chain
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
    • C09K2019/124—Ph-Ph-Ph-Ph
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    • 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
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3012—Cy-Cy-Cy-Ph, or more Cy rings
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3019—Cy-Cy-Ph-Ph
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3025—Cy-Ph-Ph-Ph
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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

  • the present invention relates to a nematic liquid crystal composition having a positive dielectric anisotropy ( ⁇ ) useful as an electro-optical liquid crystal display material.
  • Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, watches, advertisement display boards, etc., including clocks and calculators.
  • Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, VA type characterized by vertical alignment using TFT (thin film transistor) and horizontal alignment.
  • the liquid crystal composition used in these liquid crystal display elements is stable against external factors such as moisture, air, heat, light, etc., and exhibits a liquid crystal phase in the widest possible temperature range centering on room temperature, and has low viscosity. And a low driving voltage is required.
  • the liquid crystal composition has several to several tens of kinds of compounds in order to optimize the dielectric anisotropy ( ⁇ ) and the refractive index anisotropy ( ⁇ n) for each display element. It is composed of
  • a liquid crystal composition having a negative ⁇ is used for a vertical alignment type display
  • a liquid crystal composition having a positive ⁇ is used for a horizontal alignment type display such as a TN type, STN type, or IPS type.
  • a driving method has been reported in which a liquid crystal composition having a positive ⁇ is vertically aligned when no voltage is applied and an IPS type / FFS type electric field is applied, and the necessity of a liquid crystal composition having a positive ⁇ is reported. Is growing further. On the other hand, low voltage driving, high-speed response, and a wide operating temperature range are required in all driving systems.
  • ⁇ is positive, the absolute value is large, the viscosity ( ⁇ ) is small, and a high nematic phase-isotropic liquid phase transition temperature (T ni ) is required.
  • T ni nematic phase-isotropic liquid phase transition temperature
  • An object of the present invention is to solve is adjusted to a desired refractive index anisotropy ([Delta] n), nematic phase - suppress reduction and increase of the minimum temperature of a nematic phase of isotropic liquid phase transition temperature (T ni)
  • a liquid crystal composition having a sufficiently low viscosity ( ⁇ ) and a positive dielectric anisotropy ( ⁇ ) without deteriorating the temperature range of the nematic phase.
  • the present inventor has studied various fluorobenzene derivatives and found that the above problem can be solved by combining specific compounds, and has completed the present invention.
  • the present invention is a liquid crystal composition having positive dielectric anisotropy, wherein the liquid crystal composition contains one or more compounds selected from compounds represented by the general formula (LC0),
  • R 01 represents an alkyl group having 1 to 15 carbon atoms, and one or more CH 2 groups in the alkyl group are —O—, —CH ⁇ CH—, —CO—, —OCO—, —COO—, —C ⁇ C—, —CF 2 O—, —OCF 2 —, which may be substituted with one or more of the alkyl groups
  • the hydrogen atom may be optionally halogen-substituted, and A 01 is independently any one of the following structures
  • X 104 to X 108 each independently represents —H, —Cl, —F, —CF 3 or —OCF 3
  • a 02 represents any of the following structures:
  • X 109 to X 113 each independently represents —H, —Cl, —F, —CF 3 or —OCF 3
  • X 101 to X 103 each independently represent —H , —Cl, —F, —CF 3 or —OCF 3
  • Y 01 and Y 02 each independently represent —Cl, —F, —CF 3 or —OCF 3
  • Z 02 represents —CH 2 O —, —OCH 2 — or —CF 2 O—
  • Z 01 and Z 03 are each independently a single bond, —CH ⁇ CH—, —C ⁇ C—, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCF 2 — or —CF 2 O—
  • each of m 01 and m 02 independently represents an integer of 0 to 2
  • m 01 + m 02 is each independently 0, 1, 2 or represents 3, a 01, X 101, X 102, Z 01 and /
  • R 11 to R 41 each independently represents an alkyl group having 1 to 15 carbon atoms, and one or more of —CH 2 — in the alkyl group is not directly adjacent to an oxygen atom. May be substituted with —O—, —CH ⁇ CH—, —CO—, —OCO—, —COO—, —C ⁇ C—, —CF 2 O— or —OCF 2 —.
  • R 51 and R 52 each independently represents an alkyl group having 1 to 15 carbon atoms, and one of the alkyl groups Or two or more —CH 2 — are substituted with —O—, —CH ⁇ CH—, —CO—, —OCO—, —COO— or —C ⁇ C— so that the oxygen atom is not directly adjacent.
  • a 11 ⁇ A 42 are each independently either the following structures
  • one or more —CH 2 — of the cyclohexane ring may be substituted with —O— so that the oxygen atom is not directly adjacent, and X 61 and X 62 are independently — H, —Cl, —F, —CF 3 or —OCF 3 ), and A 51 to A 53 are each independently one of the following structures:
  • —CH 2 CH 2 — in the cyclohexane ring may be substituted with —CH ⁇ CH—, —CH 2 O— or —OCH 2 —
  • X 11 to X 43 each independently represent —H, —Cl , -F, -CF 3 or -OCF 3
  • Y 11 to Y 41 are -Cl, -F, -CF 3 , -OCF 3 , -CF 2 CF 3 , -CHFCF 3 , -OCF 2 CF 3 , —OCHFCF 3 or —OCF ⁇ CF 2
  • Z 31 to Z 42 are each independently a single bond, —CH ⁇ CH—, —C ⁇ C—, —CH 2 CH 2 —, — (CH 2 ) 4 -, - OCH 2 -, - CH 2
  • one or more —CH 2 — in the cyclohexane ring may be substituted with —O— so that the oxygen atom is not directly adjacent.
  • a liquid crystal display element using the liquid crystal composition.
  • the liquid crystal composition of the present invention is characterized in that ⁇ is positive and its absolute value can be increased. Also, ⁇ is low, rotational viscosity ( ⁇ 1 ) is small, liquid crystallinity is excellent, and a stable liquid crystal phase is exhibited over a wide temperature range. Further, it is a practical and reliable liquid crystal composition that is chemically stable to heat, light, water, and the like and can be driven at a low voltage.
  • the liquid crystal composition in the present invention contains one or more compounds selected from the compounds represented by the general formula (LC0), and further compounds represented by the general formulas (LC1) to (LC5). 1 type, or 2 or more types of compounds chosen from the compound group which consists of these are contained.
  • a liquid crystal composition containing the compound represented by the general formula (LC0) and the compounds represented by the general formula (LC1) to the general formula (LC5) exhibits a stable liquid crystal phase even at a low temperature. It can be said that.
  • R 01 to R 52 each independently represents an alkyl group having 1 to 15 carbon atoms, and one or two or more CH 2 in the alkyl group.
  • the group includes —O—, —CH ⁇ CH—, —CO—, —OCO—, —COO—, —C ⁇ C—, —CF 2 O—, —OCF 2 — so that the oxygen atom is not directly adjacent.
  • one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom, but an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or An alkoxy group having 1 to 8 carbon atoms is preferable, and a straight chain is preferable.
  • any one of R 51 and R 52 is preferably an alkenyl group having 2 to 8 carbon atoms.
  • the black dot in each formula represents the connection point with the ring. It is preferable to be selected from the group represented by any of the above.
  • a 11 , A 21 , A 31 , A 41 , A 51 , A 53 are trans-1,4-cyclohexylene groups, the formula (R1), the formula (R2), and the formula (R4) are more preferable.
  • at least one of R 51 and R 52 in the general formula (LC5) contains one or more compounds each of which is an alkenyl group of any one of the formulas (R1) to (R5).
  • a 01 is one of the following structures
  • X 104 to X 108 in the above structure each independently represents —H, —Cl, —F, —CF 3, or —OCF 3, and is preferably —H or —F.
  • A02 is one of the following structures
  • X 109 to X 113 in the above structure each independently represent —H, —Cl, —F, —CF 3 or —OCF 3 , preferably —H or —F, preferably —F. Is more preferable.
  • Y 01 and Y 02 in the above structure each independently represent —Cl, —F, —CF 3 or —OCF 3 , preferably —F or —OCF 3 , and more preferably —F. preferable.
  • a 11 to A 42 are each independently a trans-1,4-cyclohexylene group, 1,4-phenylene group, 3-fluoro-1,4-phenylene group, or 3,5-difluoro-1,4-phenylene. Or a tetrahydropyran-2,5-diyl group is preferred.
  • a 11 to A 42 include a tetrahydropyran group, A 11 , A 21 , A 31 and A 32 are preferable.
  • a 51 to A 53 are each independently a trans-1,4-cyclohexylene group, 1,4-phenylene group, 3-fluoro-1,4-phenylene group or 2-fluoro-1,4-phenylene group. preferable.
  • Z 02 represents —OCH 2 — or —CF 2 O—.
  • Z 01 and Z 03 are each independently a single bond, —CH ⁇ CH—, —C ⁇ C—, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCF 2 — or —CF 2 O— Is preferably a single bond, —CH 2 CH 2 —, —OCF 2 — or —CF 2 O—, more preferably a single bond or —CH 2 CH 2 —, and a single bond It is particularly preferred.
  • Z 31 to Z 42 are each independently a single bond, —CH ⁇ CH—, —C ⁇ C—, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—. , —OCF 2 — or —CF 2 O—, wherein at least one of Z 31 and Z 32 present is not a single bond, but is a single bond, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —OCF 2 — or —CF 2 O— is preferred, and one of Z 31 to Z 42 present is —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —OCF 2 — or — When CF 2 O— is represented, the others are preferably single bonds.
  • Z 51 and Z 52 are each independently a single bond, —CH ⁇ CH—, —C ⁇ C—, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—. , -COO -, - OCO -, - OCF 2 - or represents a -CF 2 O-, a single bond, -CH 2 CH 2 -, - OCF 2 - or Z 51 to -CF 2 O-are preferably present When a plurality of Z 52 are present, at least one is preferably a single bond, more preferably all represent a single bond.
  • X 103 represents —H, —Cl, —F, —CF 3, or —OCF 3 , and —F is a large dielectric anisotropy ( ⁇ ) or similar dielectric anisotropy ( ⁇ ). In contrast, the viscosity ( ⁇ ) is remarkably low, which is particularly preferable.
  • X 101 to X 102 each independently represents —H, —Cl, —F, —CF 3 or —OCF 3 , and —H or —F is preferred.
  • Y 01 and Y 02 each independently represent —Cl, —F, —CF 3 or —OCF 3 , preferably —F or —OCF 3 , more preferably —F.
  • Y 11 to Y 41 represent —Cl, —F, —CF 3 , —OCF 3 , —CF 2 CF 3 , —CHFCF 3 , —OCF 2 CF 3 , —OCHFCF 3 or —OCF ⁇ CF 2 , F or —OCF 3 is preferred, and —F is more preferred.
  • m 01 to m 51 can each independently represent an integer of 0 to 3, but m 01 + m 02 is more preferably 1 or 2, m 21 is more preferably 0, and m 31 + m 32 is 1 or 2. Or 3 is more preferable, and m 41 + m 42 is more preferably 1 or 2.
  • liquid crystal compounds represented by the general formula (LC0) are specifically the following general formulas (LC0-1) to (LC0-36)
  • X 114 to X 117 each independently represents —H, —Cl, —F, —CF 3 or —OCF 3 , and R 01 , X 101 to X 113 , Y 101 are the same as in claim 1) It is preferably a compound represented by
  • the compounds represented by general formula (LC2) are specifically the following general formula (LC2-1) to general formula (LC2-14)
  • X 23 , X 24 , X 25 and X 26 each independently represent a hydrogen atom, Cl, F, CF 3 or OCF 3 , and X 22 , R 21 and Y 21 in the general formula (LC2) It is more preferable that it is a compound represented by the same meaning.
  • the compound groups represented by general formula (LC2-1) to general formula (LC2-4) and general formula (LC2-9) to general formula (LC2-11) are more preferable.
  • the compounds represented by the general formula (LC3) are specifically the following general formulas (LC3-1) to (LC3-58)
  • X 33 to X 38 each independently represent H, Cl, F, CF 3 or OCF 3 , and R 31 , X 321 and Y 31 represent the same meaning as in claim 1). It is preferable that it is a compound.
  • the compounds represented by the general formula (LC4) are specifically the following general formulas (LC4-1) to (LC4-14)
  • X 44 to X 47 each independently represent H, Cl, F, CF 3 or OCF 3 , and X 42 , X 43 , R 41 and Y 41 represent the same meaning as in claim 1). It is preferable that it is a compound represented by these.
  • R 51 and R 52 represent the same meanings in general formula (LC5)), and are preferably compounds represented by Of these, from general formula (LC5-1) to general formula (LC5-8), general formula (LC5-14), general formula (LC5-16), and general formula (LC5-18) to general formula (LC5-26) It is more preferable to use together the compound group represented by general formula (LC0) which is an essential component of this invention.
  • a compound group in which at least one of R 51 and R 52 in formulas (LC5-1) and (LC5-4) is an alkenyl group, particularly any one of the following alkenyl groups of formulas (R1) to (R5) More preferably.
  • One or more compounds represented by the general formula (LC5) are contained, and the content is preferably 20 to 70% by mass, and more preferably 30 to 70% by mass.
  • the liquid crystal composition of the present invention contains a compound represented by general formula (LC0) and a compound selected from the group of compounds represented by general formula (LC1) to general formula (LC5). It is preferable that the compound represented by the compound group represented by the compound represented by the compound represented by the compound represented by General formula (LC4) and General formula (LC5) and the compound represented by General formula (LC5).
  • the liquid crystal composition of the present invention preferably has a viscosity ⁇ at 20 ° C. of 20 mPa ⁇ s or less.
  • the liquid crystal composition of the present invention can contain one or more optically active compounds. Any optically active compound can be used as long as the liquid crystal molecules can be twisted and aligned. Usually, since this twist changes with temperature, a plurality of optically active compounds can be used to obtain a desired temperature dependency. In order not to adversely affect the temperature range and viscosity of the nematic liquid crystal phase, it is preferable to select and use an optically active compound having a strong twist effect. As such an optically active compound, specifically, liquid crystals such as cholesteric nonanate and compounds represented by the following general formulas (Ch-1) to (Ch-6) are preferable.
  • R c1 , R c2 , and R * each independently represents an alkyl group having 1 to 15 carbon atoms, and one or two or more —CH 2 — in the alkyl group has a direct oxygen atom May be substituted with —O—, —CH ⁇ CH—, —CO—, —OCO—, —COO—, —C ⁇ C—, —CF 2 O— or —OCF 2 — so as not to be adjacent,
  • One or more hydrogen atoms in the alkyl group may be optionally substituted with halogen, provided that R * has at least one branched chain group or halogen substituent having optical activity, and Z c1 Z c2 each independently a single bond, —CH ⁇ CH—, —C ⁇ C—, —CH 2 CH 2 —, — (CH 2 ) 4 —, —COO—, —OCO—, —OCH 2 —.
  • -CH 2 O -, - OCF 2 - or -CF 2 O-a represents, D 1
  • D 2 is Cyclohexane represents a ring or a benzene ring
  • one or two or more -CH 2 in the cyclohexane ring - may have an oxygen atom which may be substituted with -O- so as not to directly adjacent
  • Two or more —CH 2 CH 2 — may be substituted with —CH ⁇ CH—, —CF 2 O— or —OCF 2 —
  • one or more —CH 2 in the benzene ring ⁇ may be substituted with —N ⁇ such that the nitrogen atom is not directly adjacent
  • D 3 and D 4 represent a cyclohexane ring or a benzene ring, and one or more of —CH 2 — in the cyclohexane ring is substituted with —O— so that the oxygen atom is not directly adjacent.
  • one or more of —CH 2 CH 2 — in the ring note may be substituted with —CH ⁇ CH—, —CF 2 O— or —OCF 2 —.
  • One or more —CH ⁇ may be substituted with —N ⁇ so that the nitrogen atoms are not directly adjacent, and one or more hydrogen atoms in the ring are substituted with F, Cl, CH 3 May be used).
  • the liquid crystal composition of the present invention may contain one or more polymerizable compounds, and the polymerizable compound contains a benzene derivative, a triphenylene derivative, a truxene derivative, a phthalocyanine derivative or a cyclohexane derivative at the center of the molecule. And a discotic liquid crystal compound having a structure in which a linear alkyl group, a linear alkoxy group or a substituted benzoyloxy group is radially substituted as its side chain.
  • the polymerizable compound is represented by the general formula (PC)
  • P 1 represents a polymerizable functional group
  • Sp 1 represents a spacer group having 0 to 20 carbon atoms
  • Q p1 represents a single bond, —O—, —NH—, —NHCOO—, —OCONH— , —CH ⁇ CH—, —CO—, —COO—, —OCO—, —OCOO—, —OOCO—, —CH ⁇ CH—, —CH ⁇ CH—COO—, —OCO—CH ⁇ CH— or — C ⁇ C—
  • p 1 and p 2 each independently represent 1, 2 or 3
  • MG p represents a mesogenic group or a mesogenic support group
  • R p1 represents a halogen atom, a cyano group or a carbon atom Represents an alkyl group of 1 to 25, and one or more CH 2 groups in the alkyl group are —O—, —S—, —NH—
  • MG p in the polymerizable compound general formula (PC) has the following structure:
  • C 01 to C 03 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3 -Dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2 , 5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene -2,7-diyl group, 9,10-dihydrophenanthrene-2,7
  • Z p1 and Z p2 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH ⁇ CH—, —C ⁇ C—.
  • -CH CHCOO -
  • - OCOCH CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, - CONH -, - NHCO- Or a single bond
  • 3 represents 0, 1 or 2.
  • Sp 1 and Sp 2 are each independently an alkylene group
  • the alkylene group may be substituted by one or more halogen atoms or CN, and one or two present in the group
  • the above CH 2 groups are —O—, —S—, —NH—, —N (CH 3 ) —, —CO—, —COO—, —OCO—, —
  • R p2 to R p6 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms.
  • PC polymerizable compound general formula
  • p 4 are each independently represents 1, 2 or 3.
  • Sp 1 , Sp 2 , Q p1 and Q p2 are preferably a single bond
  • P 1 and P 2 are preferably the formula (PC0-a), and are an acryloyloxy group and a methacryloyloxy group. More preferably, p 1 + p 4 is preferably 2, 3 or 4, and R p1 is preferably H, F, CF 3 , OCF 3 , CH 3 or OCH 3 .
  • compounds represented by general formula (PC1-2), general formula (PC1-3), general formula (PC1-4) and general formula (PC1-8) are preferred.
  • MG p in the general formula (PC) is a discotic liquid crystal compound represented by the general formula (PC1) -9.
  • R 7 independently represents P 1 -Sp 1 -Q p 1 or a substituent of the general formula (PC1-e), and R 81 and R 82 each independently represents a hydrogen atom, a halogen atom or methyl
  • R 83 represents an alkoxy group having 1 to 20 carbon atoms, and at least one hydrogen atom in the alkoxy group is a substituent represented by the general formulas (PC0-a) to (PC0-d). Has been replaced.
  • the amount of the polymerizable compound used is preferably 0.05 to 2.0% by mass.
  • the liquid crystal composition of the present invention may further contain one or more antioxidants, and may further contain one or more UV absorbers.
  • the antioxidant is preferably selected from those represented by the following general formula (E-1) and / or general formula (E-2).
  • R e1 represents an alkyl group having 1 to 15 carbon atoms, and one or two or more —CH 2 — in the alkyl group is —O—, —
  • One or more of the alkyl groups may be substituted with CH ⁇ CH—, —CO—, —OCO—, —COO—, —C ⁇ C—, —CF 2 O— or —OCF 2 —.
  • the hydrogen atom of may be optionally substituted with halogen
  • Z e1 and Z e2 are each independently a single bond, —CH ⁇ CH—, —C ⁇ C—, —CH 2 CH 2 —, — (CH 2 ) 4 —, —COO—, —OCO—, —OCH 2 —, —CH 2 O—, —OCF 2 — or —CF 2 O—
  • E 1 represents a cyclohexane ring or a benzene ring
  • one or more —CH 2 — in the cyclohexane ring represents an oxygen atom May be substituted with —O— so that they are not directly adjacent to each other
  • one or more —CH 2 CH 2 — in the ring note may be —CH ⁇ CH—, —CF 2 O— or —OCF 2 - as can be substituted
  • one or more -CH nitrogen atom in the benzene ring are not directly adjacent with may be substituted
  • the liquid crystal composition of the present invention can be used as a liquid crystal display element, particularly an active matrix driving liquid crystal display element, for example, TN mode, OCB mode, ECB mode, IPS (including FFS electrode) mode or VA-IPS mode (including FFS electrode).
  • TN mode for example, TN mode, OCB mode, ECB mode, IPS (including FFS electrode) mode or VA-IPS mode (including FFS electrode).
  • VA-IPS mode refers to a pixel electrode arranged on the same substrate surface by aligning a liquid crystal material ( ⁇ > 0) having a positive dielectric anisotropy perpendicular to the substrate surface when no voltage is applied. This is a method of driving liquid crystal molecules by a common electrode.
  • Vc threshold voltage of Fredericks transition in TN and ECB systems
  • the VA system is represented by the formula (III).
  • Vc is the Frederick transition (V)
  • ⁇ is the circumference
  • d cell is the distance between the first substrate and the second substrate ( ⁇ m)
  • d gap is the distance between the pixel electrode and the common electrode ( ⁇ m)
  • d ITO is the pixel electrode and / or common electrode width ( ⁇ m)
  • ⁇ r1>, ⁇ r2>, and ⁇ r3> are extrapolated lengths ( ⁇ m)
  • K11 is the spray elastic constant (N)
  • K22 is the twist elasticity.
  • Constant (N) represents the elastic constant (N) of the bend
  • ⁇ represents the anisotropy of the dielectric constant.
  • the formula (IV) is applied.
  • Vc is the Frederick transition (V)
  • ⁇ is the circumference
  • d cell is the distance between the first substrate and the second substrate ( ⁇ m)
  • d gap is the distance between the pixel electrode and the common electrode ( ⁇ m)
  • d ITO is the width of the pixel electrode and / or common electrode ( ⁇ m)
  • ⁇ r>, ⁇ r ′>, ⁇ r3> are extrapolation lengths ( ⁇ m)
  • K33 is the bend elastic constant (N)
  • ⁇ is the dielectric constant (Expression of anisotropy) From the formula (IV), the cell configuration is as small as possible for d gap and as large as possible for d ITO, and the absolute value of ⁇ of the liquid crystal composition to be used is increased. , K33 can be selected to reduce the drive voltage.
  • the liquid crystal composition of the present invention can be adjusted to preferable ⁇ , K11, and K33.
  • the product ( ⁇ n ⁇ d) of the refractive index anisotropy ( ⁇ n) of the liquid crystal composition and the distance (d) between the first substrate and the second substrate of the display device is strongly related to viewing angle characteristics and response speed. . Therefore, the interval (d) tends to be as thin as 3 to 4 ⁇ m.
  • the product ( ⁇ n ⁇ d) is preferably 0.31 to 0.33 in the TN mode, ECB mode, and IPS mode. In the VA-IPS mode, 0.20 to 0.59 is preferable in the case of vertical alignment with respect to both substrates, and 0.30 to 0.40 is particularly preferable.
  • the tilt angle in the TN mode and ECB mode where the liquid crystal alignment when no voltage is applied needs to be substantially horizontal is preferably 0.5 to 7 °, and the liquid crystal alignment when no voltage is applied needs to be approximately perpendicular to the substrate surface.
  • the tilt angle is preferably 85 to 90 °.
  • an alignment film made of polyimide (PI), polyamide, chalcone, cinnamate, cinnamoyl, or the like can be provided. Further, it is preferable to use an alignment film prepared by using a photo-alignment technique.
  • the liquid crystal composition of the present invention containing the compound in which X 103 in the general formula (LC0) is F can be easily aligned on the easy axis of the alignment film and can easily control a desired tilt angle.
  • liquid crystal composition of the present invention containing the compound represented by the general formula (PC) as the polymerizable compound is obtained by polymerizing the polymerizable compound contained in the liquid crystal composition with voltage applied or without voltage applied.
  • the produced polymer stabilized liquid crystal display element for TN mode, OCB mode, ECB mode, IPS mode or VA-IPS mode can be provided.
  • T NI Nematic phase-isotropic liquid phase transition temperature (° C) ⁇ : dielectric constant in the direction perpendicular to the molecular long axis direction at 25 ° C. ⁇ : dielectric anisotropy at 25 ° C. no: refractive index for ordinary light at 25 ° C. ⁇ n: refractive index anisotropic at 25 ° C. sex Vth: Applied voltage (V) in a cell having a cell thickness of 6 ⁇ m in which the transmittance changes by 10% when a rectangular wave with a frequency of 1 KHz is applied at 25 ° C. ⁇ 20 : Bulk viscosity at 20 ° C. (mPa ⁇ s) ⁇ 1 : rotational viscosity (mPa ⁇ s) The following abbreviations are used in compound descriptions.
  • Example 1 and Comparative Example 1 The content ratio and physical property values of the compound of the prepared liquid crystal composition of the present invention (Example 1) and the liquid crystal composition prepared for comparison (Comparative Example 1) are shown below.
  • the liquid crystal composition of Comparative Example 1 does not contain the compound represented by the general formula (LC0), but is substituted with a compound other than the compound represented by the general formula (LC0).
  • the dielectric anisotropy ( ⁇ ) is made substantially the same, and TN-I and ⁇ n are made almost the same, but the liquid crystal composition of Example 1 has a lower viscosity. It can be seen that the combination of the present invention is very excellent.
  • Example 2 to Example 4 The liquid crystal compositions (Examples 2 to 4) prepared so as to have substantially the same ⁇ as Example 1 and their physical properties are shown below.
  • Example 5 Similar to the liquid crystal composition of Example 1, the viscosity was low.
  • Example 5 and Comparative Example 2 The content ratio and physical property values of the compound of the prepared liquid crystal composition of the present invention (Example 5) and the liquid crystal composition prepared for comparison (Comparative Example 2) are shown below.
  • the liquid crystal composition of Comparative Example 2 does not include the compound represented by the general formula (LC0), but is substituted with a compound other than the compound represented by the general formula (LC0).
  • the dielectric anisotropy ( ⁇ ) is made substantially the same, and TN-I and ⁇ n are made almost the same, but the liquid crystal composition of Example 5 has a lower viscosity. It can be seen that the combination of the present invention is very excellent.
  • Examples 6 to 8 The liquid crystal compositions (Examples 6 to 8) prepared so as to have substantially the same ⁇ as Example 5 and their physical properties are shown below.
  • Example 9 Similar to the liquid crystal composition of Example 5, the viscosity was low.
  • Example 9 and Comparative Example 3 The content ratios and physical properties of the compounds of the prepared liquid crystal composition of the present invention (Example 9) and the liquid crystal composition prepared for comparison (Comparative Example 3) are shown below.
  • the liquid crystal composition of Comparative Example 3 does not include the compound represented by the general formula (LC0), but is substituted with a compound other than the compound represented by the general formula (LC0).
  • the dielectric anisotropy ( ⁇ ) is made substantially the same, and TN and ⁇ n are made almost the same, but the liquid crystal composition of Example 9 has a lower viscosity. It can be seen that the combination of the present invention is very excellent.
  • Example 10 to Example 12 The liquid crystal compositions (Examples 10 to 12) prepared so as to have substantially the same ⁇ as Example 9 and their physical properties are shown below.
  • Example 13 Similar to the liquid crystal composition of Example 9, the viscosity was low.
  • Example 13 and Comparative Example 4 The content ratios and physical properties of the compounds of the prepared liquid crystal composition of the present invention (Example 13) and the liquid crystal composition prepared for comparison (Comparative Example 4) are shown below.
  • the liquid crystal composition of Comparative Example 4 does not include the compound represented by the general formula (LC0), but is substituted with a compound other than the compound represented by the general formula (LC0).
  • the dielectric anisotropy ( ⁇ ) is made substantially the same, and TN-I and ⁇ n are made almost the same, but the liquid crystal composition of Example 13 has a lower viscosity. It can be seen that the combination of the present invention is very excellent.
  • Example 14 to Example 16 The liquid crystal compositions (Examples 14 to 16) prepared so as to have substantially the same ⁇ as Example 13 and their physical properties are shown below.
  • Example 17 Similar to the liquid crystal composition of Example 13, the viscosity was low.
  • Example 17 Using a first substrate in which a pair of transparent electrodes having a comb-shaped electrode structure is provided on the same substrate and a second substrate not having an electrode structure, a vertical alignment film is formed on each substrate, and the first substrate and An IPS empty cell having a gap interval of 4.0 microns was fabricated on the second substrate.
  • the liquid crystal composition shown in Example 1 was injected into this empty cell to produce a liquid crystal display element.
  • the applied voltage at which the transmittance changed by 10% was 2.88v.
  • the response speed when 7v was applied was 6.9 milliseconds, and the response speed when the voltage was turned off was 14.4 milliseconds.
  • a polymerizable liquid crystal composition CLC-A was prepared by adding 1% and uniformly dissolving.
  • the physical properties of CLC-A were almost the same as those of the liquid crystal composition shown in Example 1.
  • UV light is irradiated to the liquid crystal cell by a high-pressure mercury lamp through a filter that cuts UV light of 300 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 KHz. did.
  • the cell surface was adjusted to have an irradiation intensity of 20 mW / cm 2 and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized.
  • the applied voltage at which the transmittance changed by 10% was 2.98 v.
  • the response speed when 7v was applied was 4.8 milliseconds. Further, the response speed when the voltage was turned off was 5.0 milliseconds, which was very fast as compared with the liquid crystal display element produced only with the liquid crystal composition shown in Example 1.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne une composition de cristaux liquides qui est caractérisée en ce qu'elle présente une anisotropie (∆n) de réfraction ajustée, tout en ayant une viscosité (η) suffisamment faible et une anisotropie (∆ε) diélectrique positive ayant une grande valeur absolue, sans détérioration de la plage de températures d'une phase nématique. La composition de cristaux liquides est chimiquement stable en termes de chaleur, lumière et similaires et peut être entraînée à basse tension, ce qui lui permet d'être hautement fiable et pratique, tout en ayant d'excellentes caractéristiques d'affichage. Par conséquent, ladite composition de cristaux liquides est utile pour un élément d'affichage, tel qu'un terminal mobile, une télévision à cristaux liquides et un écran.
PCT/JP2014/079195 2013-11-19 2014-11-04 Composition de cristaux liquides nématiques et élément d'affichage à cristaux liquides l'utilisant Ceased WO2015076093A1 (fr)

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WO2012161178A1 (fr) * 2011-05-26 2012-11-29 Dic株式会社 Composé ayant une structure de 2-fluorophényloxyméthane
WO2013018796A1 (fr) * 2011-08-02 2013-02-07 Dic株式会社 Composition de cristaux liquides nématiques
JP2013170248A (ja) * 2012-02-22 2013-09-02 Dic Corp ネマチック液晶組成物
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JP6268562B1 (ja) * 2016-04-20 2018-01-31 Dic株式会社 組成物及びそれを使用した液晶表示素子

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JP6061040B2 (ja) 2017-01-18
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