WO2014065293A1 - Composé à cristaux liquides, milieu cristallin liquide et élément optique - Google Patents

Composé à cristaux liquides, milieu cristallin liquide et élément optique Download PDF

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WO2014065293A1
WO2014065293A1 PCT/JP2013/078614 JP2013078614W WO2014065293A1 WO 2014065293 A1 WO2014065293 A1 WO 2014065293A1 JP 2013078614 W JP2013078614 W JP 2013078614W WO 2014065293 A1 WO2014065293 A1 WO 2014065293A1
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alkyl
replaced
liquid crystal
compound
coo
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PCT/JP2013/078614
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Japanese (ja)
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長谷場　康宏
弘毅 佐郷
山本　真一
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Jnc株式会社
Jnc石油化学株式会社
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Priority to JP2014543311A priority Critical patent/JP6299020B2/ja
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    • 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
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
    • 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
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/58—Dopants or charge transfer agents
    • C09K19/586—Optically active dopants; chiral dopants
    • 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
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/58—Dopants or charge transfer agents
    • C09K19/586—Optically active dopants; chiral dopants
    • C09K19/588—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0466—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
    • 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

  • the present invention relates to a liquid crystal compound, a liquid crystal composition, an optical element using the liquid crystal composition, and the like useful as a material for an optical element, for example.
  • Liquid crystal display elements using a liquid crystal composition are widely used in displays such as watches, calculators, word processors and the like. These liquid crystal display elements utilize the refractive index anisotropy and dielectric anisotropy of liquid crystal compounds.
  • PC phase change
  • TN twisted nematic
  • STN super twisted nematic
  • BTN Battery twisted nematic
  • ECB mainly using one or more polarizing plates
  • ECB Known are electrically controlled birefringence (OCB), optically compensated bend (OCB), in-plane switching (IPS), and vertical alignment (VA).
  • OCB electrically controlled birefringence
  • OCB optically compensated bend
  • IPS in-plane switching
  • VA vertical alignment
  • a mode in which an electric field is applied in an optically isotropic liquid crystal phase to develop electric birefringence has been studied (Patent Documents 1 to 16, Non-Patent Documents 1 to 3).
  • wavelength tunable filters, wavefront control elements, liquid crystal lenses, aberration correction elements, aperture control elements, optical head devices, etc. using electric birefringence in the blue phase, which is one of the optically isotropic liquid crystal phases have been proposed.
  • Patent Documents 10 to 12 The classification based on the element driving method is PM (passive matrix) and AM (active matrix). PM (passive matrix) is classified into static and multiplex, and AM is classified into TFT (thin film transistor) and MIM (metal insulator metal).
  • liquid crystal medium that exhibits stability against heat, light, etc., a wide liquid crystal phase temperature range, extremely large dielectric anisotropy, and exhibits an optically isotropic liquid crystal phase. Also, various optical elements that can be used in a wide temperature range, have a short response time, a large contrast ratio, and a low driving voltage are required.
  • the present invention includes, for example, the following liquid crystal compounds, liquid crystal media (liquid crystal compositions, polymer / liquid crystal composite materials, etc.), mixtures of polymerization monomers and liquid crystal compositions, optical devices containing liquid crystal media, and liquid crystal compounds. Etc.
  • the present invention provides the following compound, liquid crystal medium (liquid crystal composition or polymer / liquid crystal composite), an optical element containing the liquid crystal medium, and the like.
  • R 1 is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one —CH 2 — in the alkyl is —O—, —S—, —COO—, —OCO—.
  • —CH 2 — in the alkyl and in the alkyl is —O—, —S—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C.
  • At least one —CH 2 —CH 2 — in the group replaced with — may be replaced with —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—,
  • —CH 2 — is replaced by —O—, —S—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C— and at least in the alkyl
  • One —CH 2 —CH 2 — is —CH ⁇ C
  • At least one hydrogen in the group replaced with H—, —CF ⁇ CF— or —C ⁇ C— may be replaced with fluorine or chlorine, provided that —O— and —CH ⁇ CH— in X 1 Are not adjacent to each other, and —CO— and
  • Y 1 and Y 2 are —O—, Z 1 is —CF 2 O—, Z 2 and Z 3 are single bonds, and R 1 is alkyl having 1 to 20 carbons.
  • the compound according to [1] wherein the compound is alkenyl having 2 to 21 carbon atoms and X 1 is fluorine, chlorine, —CF 3 or —OCF 3 .
  • the compound according to [1], wherein the compound represented by the formula (1) is a compound represented by the formula (1-1) or (1-2).
  • R 1 is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one —CH 2 — in the alkyl is —O—, —S—, —COO—, —OCO—, — CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C— may be substituted, and in the alkyl and —CH 2 — in the alkyl may be —O—, —S—, —COO—, —OCO.
  • At least one hydrogen in the group replaced by —, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C— may be replaced by halogen or alkyl having 1 to 3 carbon atoms;
  • X 1 is hydrogen, halogen, —SF 5 or alkyl having 1 to 10 carbons, and at least one —CH 2 — in the alkyl is replaced by —O—, —S—, —COO— or —OCO—.
  • —CH 2 — in the alkyl and in the alkyl is —O—, —S—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C.
  • At least one —CH 2 —CH 2 — in the group replaced with — may be replaced with —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—, In a group in which —CH 2 — is replaced by —O—, —S—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C— and at least in the alkyl
  • One —CH 2 —CH 2 — is —CH ⁇ C
  • At least one hydrogen in the group replaced with H—, —CF ⁇ CF— or —C ⁇ C— may be replaced with fluorine or chlorine, provided that —O— and —CH ⁇ CH— in X 1 Are not adjacent to each other, and —CO— and —CH ⁇ CH— are not adjacent to each other. )
  • R 3 is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one —CH 2 — in the alkyl is —O—, —S—, —COO— or —OCO—.
  • At least one —CH 2 —CH 2 — in the alkyl may be replaced by —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—, and at least one in the alkyl
  • Two hydrogens may be replaced by fluorine or chlorine, provided that —O— and —CH ⁇ CH— and —CO— and —CH ⁇ CH— are not adjacent in R 3 ;
  • Z 31 , Z 32 and Z 33 are each independently a single bond or alkylene having 1 to 4 carbon atoms, and at least one —CH 2 — in the alkylene is —O—, —COO— or —CF May be replaced by 2 O-;
  • L 31 , L 32 , L 33 , L 34 and L 35 are each independently hydrogen or fluorine;
  • X 3 is hydrogen, halogen, —SF 5 or alkyl having 1 to 10 carbon atoms, and at least one —CH 2 — in the alkyl is replaced by —O—, —S—,
  • —CH 2 — in the alkyl and in the alkyl is —O—, —S—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C.
  • At least one —CH 2 —CH 2 — in the group replaced with — may be replaced with —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—,
  • —CH 2 — is replaced by —O—, —S—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C— and at least in the alkyl
  • One —CH 2 —CH 2 — is —CH ⁇ C
  • At least one hydrogen in the group replaced with H—, —CF ⁇ CF— or —C ⁇ C— may be replaced with fluorine or chlorine, provided that in X 3 —O— and —CH ⁇ CH— Are not adjacent to each other, and —CO— and
  • R 7 is alkyl having 1 to 20 carbon atoms, and at least one —CH 2 — in the alkyl is replaced by —O—, —S—, —COO— or —OCO—. And at least one —CH 2 —CH 2 — in the alkyl may be replaced by —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—, and at least one hydrogen in the alkyl.
  • L 71 , L 72 , L 73 , L 74 , L 75 , L 76 , L 77 and L 78 are each independently hydrogen or fluorine;
  • Z 71, Z 72 and Z 73 are each independently a single bond, —COO— or —CF 2 O—, but at least one is —COO— or —CF 2 O—;
  • n71 and n72 are each independently 0 or 1;
  • X 7 is hydrogen, halogen, —SF 5 or alkyl having 1 to 10 carbons, and at least one —CH 2 — in the alkyl is replaced by —O—, —S—, —COO— or —OCO—.
  • —CH 2 — in the alkyl and in the alkyl is —O—, —S—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C.
  • At least one —CH 2 —CH 2 — in the group replaced with — may be replaced with —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—,
  • —CH 2 — is replaced by —O—, —S—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C— and at least in the alkyl
  • One —CH 2 —CH 2 — is —CH ⁇ C
  • At least one hydrogen in the group replaced by H—, —CF ⁇ CF— or —C ⁇ C— may be replaced by fluorine or chlorine, provided that in X 7 —O— and —CH ⁇ CH— Are not adjacent to each other, and —CO— and
  • a liquid crystal composition comprising an achiral component T containing at least one compound according to any one of [1] to [6] and a chiral agent.
  • the liquid crystal composition according to [9] which exhibits an optically isotropic liquid crystal phase.
  • Ring A 21 , Ring A 22 , Ring A 23 , Ring A 24 and Ring A 25 are each independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene 1,4-phenylene in which one or two hydrogens are replaced with fluorine, 1,4-phenylene in which two hydrogens are replaced with fluorine and chlorine, respectively, pyridine-2,5-diyl, pyrimidine-2,5 -Is diyl;
  • Z 21 , Z 22 , Z 23 , Z 24 , Z 25 and Z 26 are each independently a single bond or alkylene having 1 to 4 carbon atoms, and at least one —CH 2 — in the alkylene is — May be replaced by O—, —COO— or —CF 2 O—;
  • Compound 2 has the formula (2-1-1-2), (2-1-2-1), (2-1-3-1), (2-1-3-2), (2-1-1- The liquid crystal composition according to [12], which is one or more selected from the group of compounds represented by 4-2) and (2-1-4-3).
  • R 2A represents alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 to 12 carbons in which at least one hydrogen is replaced by fluorine.
  • Is alkenyl; (F) is each independently hydrogen or fluorine;
  • X 2A is fluorine, chlorine, —CF 3 or —OCF 3 .
  • At least one —CH 2 —CH 2 — in the alkyl may be replaced by —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—, and at least one in the alkyl.
  • Two hydrogens may be replaced by fluorine or chlorine, provided that —O— and —CH ⁇ CH— and —CO— and —CH ⁇ CH— are not adjacent in R 3 ;
  • Z 31 , Z 32 and Z 33 are each independently a single bond or alkylene having 1 to 4 carbon atoms, and at least one —CH 2 — in the alkylene is —O—, —COO— or —CF May be replaced by 2 O-;
  • L 31 , L 32 , L 33 , L 34 and L 35 are each independently hydrogen or fluorine;
  • X 3 is hydrogen, halogen, —SF 5 or alkyl having 1 to 10 carbon atoms, and at least one —CH 2 — in the alkyl is replaced by —O—, —S—
  • —CH 2 — in the alkyl and in the alkyl is —O—, —S—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C.
  • At least one —CH 2 —CH 2 — in the group replaced with — may be replaced with —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—,
  • —CH 2 — is replaced by —O—, —S—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C— and at least in the alkyl
  • One —CH 2 —CH 2 — is —CH ⁇ C
  • At least one hydrogen in the group replaced with H—, —CF ⁇ CF— or —C ⁇ C— may be replaced with fluorine or chlorine, provided that in X 3 —O— and —CH ⁇ CH— Are not adjacent to each other, and —CO— and
  • each R 3A independently represents alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon in which at least one hydrogen may be replaced with fluorine.
  • An alkenyl having the number 2-12; L 31 , L 32 , L 33 , L 34 and L 35 are each independently hydrogen or fluorine;
  • X 3A is fluorine, chlorine, —CF 3 or —OCF 3 .
  • R 4 represents alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon having 2 to 2 carbon atoms in which at least one hydrogen is replaced with fluorine.
  • Each ring B is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro-1, 4-phenylene, 3,5-dichloro-1,4-phenylene or pyrimidine-2,5-diyl;
  • Each Z 41 is independently a single bond, ethylene, —COO—, —OCO—, —CF 2 O— or —OCF 2 —;
  • L 48 and L 49 are each independently hydrogen or fluorine;
  • X 4 is fluorine, chlorine, —CF 3 or —OCF 3 ;
  • n41 is 1, 2, 3 or 4, provided that when n41 is 3 or 4, at least one Z 41 is —CF 2 O— or —OCF 2 —, and when n41 is 3, Not all B is 1,4-phenylene substituted with fluorine.
  • each R 4A independently represents an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, or a carbon number of 2 in which at least one hydrogen is replaced by fluorine.
  • X 4A is fluorine, chlorine, —CF 3 or —OCF 3 ;
  • L 40 to L 49 are each independently hydrogen or fluorine.
  • Two hydrogens may be replaced by fluorine or chlorine, provided that —O— and —CH ⁇ CH— and —CO— and —CH ⁇ CH— are not adjacent in R 5 ;
  • (F) is each independently hydrogen or fluorine;
  • X 5 is hydrogen, halogen, —SF 5 or alkyl having 1 to 10 carbons, and at least one —CH 2 — in the alkyl is replaced by —O—, —S—, —COO— or —OCO—.
  • —CH 2 — in the alkyl and in the alkyl is —O—, —S—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C.
  • At least one —CH 2 —CH 2 — in the group replaced with — may be replaced with —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—, In a group in which —CH 2 — is replaced by —O—, —S—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C— and at least in the alkyl
  • One —CH 2 —CH 2 — is —CH ⁇ C
  • At least one hydrogen in the group replaced by H—, —CF ⁇ CF— or —C ⁇ C— may be replaced by fluorine or chlorine, provided that in X 5 —O— and —CH ⁇ CH— Are not adjacent to each other, and —CO— and —CH ⁇ CH— are not adjacent to each other.
  • At least one —CH 2 —CH 2 — in the alkyl may be replaced by —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—,
  • One hydrogen may be replaced by fluorine or chlorine, provided that —O— and —CH ⁇ CH— and —CO— and —CH ⁇ CH— are not adjacent in R 7 ;
  • L 71 , L 72 , L 73 , L 74 , L 75 , L 76 , L 77 and L 78 are each independently hydrogen or fluorine;
  • Z 71, Z 72 and Z 73 are each independently a single bond or -COO -, - CF 2 O- and although at least one is -COO- or -CF 2 O-a and;
  • n71 and n72 are each independently 0 or 1;
  • X 7 is hydrogen, halogen, —SF 5 or alkyl having 1 to 10 carbons, and at least one —CH 2 — in the alkyl is replaced by
  • —CH 2 — in the alkyl and in the alkyl is —O—, —S—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C.
  • At least one —CH 2 —CH 2 — in the group replaced with — may be replaced with —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—,
  • —CH 2 — is replaced by —O—, —S—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C— and at least in the alkyl
  • One —CH 2 —CH 2 — is —CH ⁇ C
  • At least one hydrogen in the group replaced by H—, —CF ⁇ CF— or —C ⁇ C— may be replaced by fluorine or chlorine, provided that in X 7 —O— and —CH ⁇ CH— Are not adjacent to each other, and —CO— and
  • Compound 7 has the formulas (7-1-1), (7-1-2), (7-2-1) to (7-2-5), (7-3-1), (7-3- 2)
  • the liquid crystal composition according to [28] which is one or more selected from the group of compounds represented by (7-4-1), (7-5-1) and (7-5-2) object.
  • R 7A is alkyl having 1 to 12 carbons, alkoxy having 1 to 11 carbons, alkenyl having 2 to 12 carbons, or 2 to 12 carbons in which at least one hydrogen is replaced by fluorine.
  • Z 71 and Z 72 are each independently a single bond, —COO— or —CF 2 O—, but at least one of them is —COO— or —CF 2 O— and has the formula (7-4-1 ), (7-5-1) and (7-5-2), Z 71 is —COO— or —CF 2 O—;
  • X 7A is fluorine, chlorine, —CF 3 or —OCF 3 .
  • Compound 7 is a compound represented by formulas (7-2-2-E), (7-2-5-E), (7-2-2-F) and (7-2-5-F).
  • R 7A is alkyl having 1 to 12 carbons, alkoxy having 1 to 11 carbons, alkenyl having 2 to 12 carbons, or 2 to 12 carbons in which at least one hydrogen is replaced by fluorine.
  • X 7A is fluorine, chlorine, —CF 3 or —OCF 3 .
  • Z is each independently a single bond or alkylene having 1 to 8 carbon atoms, and at least one —CH 2 — in the alkylene is —O—, —S—, —COO—, —OCO—, — CSO—, —OCS—, —N ⁇ N—, —CH ⁇ N— or —N ⁇ CH— may be substituted, and at least one —
  • At least one hydrogen in the group in which at least one —CH 2 —CH 2 — in the alkyl is replaced by —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C— May be replaced by halogen;
  • Each X is independently a single bond, —COO—, —OCO—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, or —CH 2 CH 2 —;
  • mK is each independently an integer of 1 to 4.
  • the chiral agent is at least one selected from the group of compounds represented by formulas (K4-1) to (K4-6) and (K5-1) to (K5-3), [9] to [32 ]
  • composition [36] [9] The liquid crystal composition according to any one of [9] to [35], further including one or more selected from the group consisting of an antioxidant and an ultraviolet absorber. [37] [9] A mixture comprising the liquid crystal composition according to any one of [36] and a polymerizable monomer. [38] [37] A polymer / liquid crystal composite material obtained by polymerizing the mixture according to [37] and used for an element driven in an optically isotropic liquid crystal phase. [39] The polymer / liquid crystal composite material according to [38], wherein the mixture according to [37] is polymerized in a non-liquid crystal isotropic phase or an optically isotropic liquid crystal phase.
  • An optical element comprising an electrode disposed on one or both surfaces, a liquid crystal medium disposed between substrates, and an electric field applying means for applying an electric field to the liquid crystal medium via the electrode, wherein the liquid crystal medium is [9 ]
  • An optical device comprising the liquid crystal composition according to any one of [36] to [36] or the polymer / liquid crystal composite material according to [38] or [39].
  • An electrode is disposed on one or both surfaces, at least one of which is a transparent substrate, a liquid crystal medium disposed between the substrates, and a polarizing plate disposed outside the substrate, and the liquid crystal medium via the electrode
  • An optical device comprising an electric field applying means for applying an electric field to the liquid crystal composition according to any one of [9] to [36], or [38] or [39]
  • An optical element which is the polymer / liquid crystal composite material described.
  • liquid crystal compound represents a compound having a mesogen, and is not limited to a compound that exhibits a liquid crystal phase. Specifically, it is a generic term for a compound that exhibits a liquid crystal phase such as a nematic phase or a smectic phase, and a compound that does not have a liquid crystal phase but is useful as a component of a liquid crystal composition.
  • Liquid crystal medium is a general term for a liquid crystal composition and a polymer / liquid crystal composite.
  • An “achiral component” is an achiral mesogenic compound that does not include an optically active compound and a compound having a polymerizable functional group.
  • the “achiral component” does not include a chiral agent, a monomer, a polymerization initiator, an antioxidant, an ultraviolet absorber, a curing agent, a stabilizer, and the like.
  • the “chiral agent” is an optically active compound and is a component used to be added to give a desired twisted molecular arrangement to the liquid crystal composition.
  • Liquid crystal display element is a general term for liquid crystal display panels and liquid crystal display modules.
  • “Optical element” refers to various elements that perform functions such as light modulation and optical switching by utilizing the electro-optic effect. For example, display elements (liquid crystal display elements), optical communication systems, optical information processing, and the like. And light modulation elements used in various sensor systems.
  • the Kerr effect is known for light modulation using a change in refractive index caused by voltage application to an optically isotropic liquid crystal medium.
  • K Kerr coefficient (Kerr constant), ⁇ : wavelength)
  • the electric birefringence value is a refractive index anisotropy value induced when an electric field is applied to the isotropic medium.
  • Liquid crystal compound”, “liquid crystal composition”, and “liquid crystal display element” may be abbreviated as “compound”, “composition”, and “element”, respectively.
  • the upper limit temperature of the liquid crystal phase is the phase transition temperature of the liquid crystal phase-isotropic phase, and may simply be abbreviated as the clearing point or the upper limit temperature.
  • the lower limit temperature of the liquid crystal phase may be simply abbreviated as the lower limit temperature.
  • the compound represented by Formula (1) may be abbreviated as Compound 1. This abbreviation may also apply to compounds represented by formula (2) and the like. In formulas (2) to (5), symbols such as A 1 , B, and C surrounded by hexagons correspond to ring A 1 , ring B, and ring C, respectively.
  • the amount of the compound expressed as a percentage is a weight percentage (% by weight) based on the total weight of the composition.
  • a plurality of the same symbols such as rings A 1 , Y 1 , and B are described in the same formula or different formulas, but these may be the same or different.
  • alkyl examples include —CH 3 , —C 2 H 5 , —C 3 H 7 , —C 4 H 9 , —C 5 H 11 , —C 6 H 13 , —C 7. H 15 , -C 8 H 17, -C 9 H 19 , -C 10 H 21 , -C 11 H 23 , -C 12 H 25 , -C 13 H 27 , -C 14 H 29 , and -C 15 H 31 .
  • alkoxy examples include —OCH 3 , —OC 2 H 5 , —OC 3 H 7 , —OC 4 H 9 , —OC 5 H 11 , —OC 6 H 13 and —OC 7. H 15 , —OC 8 H 17, —OC 9 H 19 , —OC 10 H 21 , —OC 11 H 23 , —OC 12 H 25 , —OC 13 H 27 , and —OC 14 H 29 are listed.
  • alkoxyalkyl examples include —CH 2 OCH 3 , —CH 2 OC 2 H 5 , —CH 2 OC 3 H 7 , — (CH 2 ) 2 —OCH 3 , — (CH 2 ) 2 -OC 2 H 5 , — (CH 2 ) 2 —OC 3 H 7 , — (CH 2 ) 3 —OCH 3 , — (CH 2 ) 4 —OCH 3 , and — (CH 2 ) 5 —OCH 3 Is mentioned.
  • alkenyloxy examples include —OCH 2 CH ⁇ CH 2 , —OCH 2 CH ⁇ CHCH 3 , and —OCH 2 CH ⁇ CHC 2 H 5 .
  • alkynyl examples include —C ⁇ CH, —C ⁇ CCH 3 , —CH 2 C ⁇ CH, —C ⁇ CC 2 H 5 , —CH 2 C ⁇ CCH 3 , — (CH 2 ) 2 —C ⁇ CH, —C ⁇ CC 3 H 7 , —CH 2 C ⁇ CC 2 H 5 , — (CH 2 ) 2 —C ⁇ CCH 3 , and —C ⁇ C (CH 2 ) 5 It is done.
  • halogen include fluorine, chlorine, bromine and iodine.
  • Preferred compounds of the present invention exhibit liquid crystallinity, have a high clearing point, a wide nematic phase temperature range, and a large dielectric anisotropy.
  • Preferred liquid crystal compositions and polymer / liquid crystal composite materials of the present invention exhibit stability against heat, light, etc., high maximum temperature and low minimum temperature of optically isotropic liquid crystal phase, and large dielectric anisotropy Have sex.
  • the polymer / liquid crystal composite material according to a preferred embodiment of the present invention has an optically isotropic liquid crystal phase having a high upper limit temperature and a lower lower limit temperature, and is driven by an optically isotropic liquid crystal phase. Has a low driving voltage.
  • the optical element driven by the optically isotropic liquid crystal phase can be used in a wide temperature range, can be driven at a low voltage, and can achieve a high-speed electro-optical response. And has a large contrast ratio.
  • the comb-shaped electrode substrate used in the Example is shown.
  • the optical system used in the Example is shown.
  • the compound of this invention is the compound 1 represented by Formula (1), and the said compound is a liquid crystal compound which has liquid crystallinity.
  • the first aspect of the liquid crystal composition of the present invention is a composition that contains compound 1 and exhibits a nematic phase.
  • a second aspect of the liquid crystal composition of the present invention is a composition comprising an achiral component T containing Compound 1 and exhibiting a cholesteric phase (cholesteric liquid crystal composition).
  • a third aspect of the liquid crystal composition of the present invention is a composition comprising an achiral component T containing compound 1 and a chiral agent and exhibiting an optically isotropic liquid crystal phase (optical isotropic liquid crystal).
  • the liquid crystal composition of the present invention may further contain a solvent, a monomer, an initiator, a curing agent, a stabilizer (an antioxidant, an ultraviolet absorber, etc.) and the like.
  • R 1 is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one —CH 2 — in the alkyl is —O—, —S—, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C— may be substituted, and at least one —CH 2 — in the alkyl and in the alkyl is —O—, —S—, —COO.
  • At least one hydrogen in the group replaced by —, —OCO—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C— may be replaced by halogen or alkyl having 1 to 3 carbon atoms.
  • —CH ⁇ CH— in R 1 depends on the position of the double bond. —CH ⁇ CHCH 3 , —CH ⁇ CHC 2 H 5 , —CH ⁇ CHC 3 H 7 , —CH ⁇ CHC 4 H 9 , —C 2 H 4 CH ⁇ CHCH 3 , and —C 2 H 4 CH ⁇ CHC 2
  • the trans configuration is preferable.
  • -CH 2 CH CHCH 3
  • An alkenyl compound having a preferred configuration has a high maximum temperature or a wide temperature range of the liquid crystal phase.
  • Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327 have detailed descriptions.
  • the position of the alkenyl group is preferably a position that does not form a conjugate with the benzene ring.
  • the alkyl in R 1 may be linear or branched, and specific examples of alkyl include —CH 3 , —C 2 H 5 , —C 3 H 7 , —C 4 H 9 , —C 5 H 11 , -C 6 H 13, -C 7 H 15, -C 8 H 17, -C 9 H 19, -C 10 H 21, -C 11 H 23, -C 12 H 25, -C 13 H 27, -C 14 H 29 , and —C 15 H 31 .
  • the alkoxy in R 1 may be linear or branched, and specific examples of alkoxy include —OCH 3 , —OC 2 H 5 , —OC 3 H 7 , —OC 4 H 9 , —OC 5 H 11 , -OC 6 H 13 and -OC 7 H 15 , -OC 8 H 17, -OC 9 H 19 , -OC 10 H 21 , -OC 11 H 23 , -OC 12 H 25 , -OC 13 H 27 , and- OC 14 H 29 .
  • the alkoxyalkyl in R 1 may be linear or branched, and specific examples of alkoxyalkyl include —CH 2 OCH 3 , —CH 2 OC 2 H 5 , —CH 2 OC 3 H 7 , — (CH 2 ) 2 —OCH 3 , — (CH 2 ) 2 —OC 2 H 5 , — (CH 2 ) 2 —OC 3 H 7 , — (CH 2 ) 3 —OCH 3 , — (CH 2 ) 4 —OCH 3 And — (CH 2 ) 5 —OCH 3 .
  • the alkenyl in R 1 may be linear or branched, and specific examples of alkenyl include —CH 2 CH ⁇ CH 2 , —CH 2 CH ⁇ CHCH 3 , — (CH 2 ) 2 —CH ⁇ CH 2. , —CH 2 CH ⁇ CHC 2 H 5 , — (CH 2 ) 2 —CH ⁇ CHCH 3 , and — (CH 2 ) 3 —CH ⁇ CH 2 .
  • the alkenyloxy in R 1 may be linear or branched, and specific examples of alkenyloxy include —OCH 2 CH ⁇ CH 2 , —OCH 2 CH ⁇ CHCH 3 , and —OCH 2 CH ⁇ CHC 2 H. 5 .
  • the alkynyl in R 1 may be linear or branched, and specific examples of alkynyl include —C ⁇ CH, —C ⁇ CCH 3 , —CH 2 C ⁇ CH, —C ⁇ CC 2 H 5 , —CH 2.
  • R 1 is preferably a structure represented by the formulas (CHN-1) to (CHN-6). More preferred is (CHN-1) or (CHN-2). (In the above formula, R 1a is hydrogen or alkyl having 1 to 20 carbon atoms.)
  • Z 1 is —CF 2 O— or —COO—
  • Z 2 is a single bond or —CH 2 CH 2 —, and one CH 2 may be replaced by an oxygen atom
  • Z 3 is a single bond, —CH 2 CH 2 —, —CF 2 O— or —COO—.
  • a specific example of preferred Z 1 is —CF 2 O— when importance is placed on good compatibility at low temperatures, and —COO— when importance is placed on the height of the clearing point.
  • Y 1 and Y 2 are each independently —O— or —CH 2 —.
  • Preferred Y 1 and Y 2 are —O— because compound 1 has a large dielectric anisotropy.
  • L 1 , L 2 , L 3 , L 4 , L 5 and L 6 are independently hydrogen or fluorine.
  • L 1 , L 3 , L 5 and L 6 are preferably fluorine because Compound 1 has a large dielectric anisotropy.
  • Compound 1 in which all of the remaining L 2 and L 4 are fluorine A compound in which the rate anisotropy is further increased and both L 2 and L 4 are hydrogen has good compatibility at a low temperature.
  • a compound in which only one of L 2 and L 4 is fluorine has a good balance between dielectric anisotropy and compatibility.
  • alkyl in which at least one hydrogen in alkyl in X 1 of formula (1) is replaced by halogen include —CHF 2 , —CF 3 , —CF 2 CH 2 F, —CF 2 CHF 2 , —CH 2 CF 3 , —CF 2 CF 3 , — (CH 2 ) 3 —F, — (CF 2 ) 3 —F, —CF 2 CHFCF 3 , —CHFCF 2 CF 3 , — (CF 2 ) 4 —F , And-(CF 2 ) 5 -F.
  • Specific examples in which at least one hydrogen in alkoxy in X 1 is replaced by halogen include —OCHF 2 , —OCF 3 , —OCF 2 CH 2 F, —OCF 2 CHF 2 , —OCH 2 CF 3 , — O— (CF 2 ) 3 —F, —OCF 2 CHFCF 3 , —OCHFCF 2 CF 3 , —O— (CF 2 ) 4 —F, and —O— (CF 2 ) 5 —F.
  • Preferred examples of X 1 include fluorine, chlorine, —SF 5 , —CHF 2 , —CF 3 , —CF 2 CH 2 F, —CF 2 CHF 2 , —CH 2 CF 3 , —CF 2 CF 3 , — ( CF 2 ) 3 —F, —CF 2 CHFCF 3 , —CHFCF 2 CF 3 , — (CF 2 ) 4 —F, — (CF 2 ) 5 —F, —OCHF 2 , —OCF 3 , —OCF 2 CH 2 F, —OCF 2 CHF 2 , —OCH 2 CF 3 , —O— (CF 2 ) 3 —F, —OCF 2 CHFCF 3 , —OCHFCF 2 CF 3 , —O— (CF 2 ) 4 —F, —O — (CF 2 ) 5 —F, —CH ⁇ CF 2 , —CF ⁇ CHF, —CH ⁇ CH
  • X 1 More preferred examples of X 1 are fluorine, chlorine, —CF 3 , —CHF 2 , —OCF 3 and —OCHF 2 .
  • the most preferred examples of X 1 are fluorine, chlorine, —CF 3 and —OCF 3 .
  • Compound 1 is particularly preferably a compound represented by formulas (1-1) and (1-2).
  • Compound 1 is extremely physically and chemically stable under the conditions in which the device is normally used, has a high clearing point, and is relatively compatible with other compounds. A composition containing this compound is stable under conditions in which the device is normally used. Therefore, when Compound 1 is used in the liquid crystal composition, the temperature range of the liquid crystal phase can be expanded, and it can be used as a display element in a wide temperature range. In addition, since Compound 1 has a large dielectric anisotropy and a relatively large refractive index anisotropy, Compound 1 reduces the driving voltage of a liquid crystal composition driven in an optically isotropic liquid crystal phase. It is useful as a component of Thus, Compound 1 has an excellent feature that the clearing point can be increased only by using a small amount, or the driving voltage is lowered.
  • Compound 1 can be synthesized by appropriately combining methods in known organic synthetic chemistry. There are a plurality of methods for synthesizing Compound 1, which can be appropriately synthesized from commercially available reagents. In addition, when synthesizing Compound 1, the methods for introducing the desired terminal group, ring and linking group into the starting material are as follows: Organic Syntheses, John Wiley & Sons, Inc., Organic Reactions, John Wiley & Sons, Inc), Comprehensive Organic Synthesis (Pergamon Press), New Experimental Chemistry Course (Maruzen). For example, Compound 1 can be synthesized by applying the method of Japanese Patent No. 2959526 (JP 2959526B).
  • the compound (105) is commercially available or can be prepared with reference to general organic chemistry books.
  • Compound (106) is obtained by allowing compound (105) to react with ethyl bromoacetate using a metal such as Zn and then performing reduction using LAH or the like.
  • Compound (106) is derivatized to compound (107) by reacting a lithium reagent and tosyl chloride with the reaction of compound (106), and compound (107) and compound (108) are converted to LDA (lithium diisopropylamide) and borane trifluoride-ethyl.
  • LDA lithium diisopropylamide
  • borane trifluoride-ethyl The compound (109) can be derived by using an ether complex or the like.
  • the compound (109) is converted to the compound (110) by performing a cyclization reaction using an acid such as trifluoroacetic acid, and then the reduction reaction, the elimination reaction of the hydroxyl group, and the removal of the protecting group give the compound (111). can get.
  • Compound (112) is commercially available.
  • compound (113) is obtained by subjecting compound (112) to a dehydration cyclization reaction using a diol derivative and an acid catalyst.
  • compound (113) is obtained by the same synthesis route as in (ii) in the preceding stage, using compound (112) as a starting material.
  • the liquid crystal composition of the present invention is a composition containing the compound 1 represented by the formula (1), and preferably exhibits a nematic phase.
  • the liquid crystal composition may contain a chiral agent, an antioxidant, an ultraviolet absorber, a stabilizer, and the like.
  • the achiral component T includes a case where the compound 1 is composed of one kind of compound and a case where the compound 1 contains two or more kinds of compounds represented by the formula (1). Furthermore, the achiral component includes one or more compounds selected from the group consisting of compounds 2 to 7 as necessary.
  • the achiral component T preferably includes compounds 2, 3, 5 and 7 in addition to compound 1, particularly preferably includes compounds 3 and 7, and further includes compounds 4 and 6 depending on the properties required. Can do.
  • Compounds 1 to 7 are liquid crystal compounds.
  • compound 1 Since compound 1 has both a high clearing point, a large dielectric anisotropy, and a relatively good compatibility at low temperatures, nematic compositions using compound 1 also have a high clearing point, a wide liquid crystal phase temperature range, or a large dielectric Since it exhibits a rate anisotropy, it is useful as a composition used for an optical element.
  • the total content of the achiral component T is preferably 1 to 30% by weight, more preferably 3 to 20% by weight, and more preferably 5 to 15% by weight. It is particularly preferable to do this.
  • the achiral component of the present invention may further contain at least one compound 2 represented by formula (2). That is, the present invention includes the case where the achiral component T is composed of one compound as the compound 2 and the case where the compound 2 contains two or more compounds represented by the formula (2).
  • R 2 in the formula (2) is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 to 12 carbons in which at least one hydrogen is replaced by fluorine. Are preferred.
  • ring A 21 , ring A 22 , ring A 23 , ring A 24 and ring A 25 in formula (2) are 1,4-phenylene, one or 1,4-phenylene in which two hydrogens are replaced by fluorine is preferred.
  • Z 21 , Z 22 , Z 23 , Z 24 , Z 25 and Z 26 in the formula (2) are each independently a single bond or alkylene having 1 to 4 carbon atoms, and at least one —CH in the alkylene 2 — may be replaced by —O—, —COO— or —CF 2 O—.
  • X 2 in the formula (2) is fluorine, chlorine, —CF 3 , —CHF 2 , —CH 2 F, —OCF 3 , —OCHF 2 , —OCH 2 F, —OCF 2 CFHCF 3 or —CH ⁇ CHCF 3
  • Preferred are fluorine, chlorine, —CF 3 and —OCF 3 .
  • R 2A is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 to 12 carbons in which at least one hydrogen is replaced by fluorine.
  • Z 21 , Z 22 , Z 23 , Z 24 , Z 25 , and Z 26 are each independently a single bond or alkylene having 1 to 4 carbon atoms, and at least one —CH 2 — in the alkylene is May be replaced by —O—, —COO— or —CF 2 O—;
  • X 2A is fluorine, chlorine, —CF 3 and —OCF 3 ;
  • n22, n23, n24 and n25 are each independently 0 or 1, 1 ⁇ n22 + n23 + n24 + n25 ⁇ 2, (F) each independently represents hydrogen or fluorine. )
  • -CH 2 CH CHCH 3
  • An alkenyl compound having a preferred configuration has a high maximum temperature or a wide temperature range of the liquid crystal phase.
  • Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327 have detailed descriptions.
  • the compound 2 is represented by the formula (2-1-1-2), (2-1-2-1), (2-1-3-1), (2-1-3-2) , (2-1-4-2) or (2-1-4-3) is preferred.
  • Compound 2 has good compatibility, large dielectric anisotropy and large refractive index anisotropy.
  • the total amount of compound 2 is preferably 0.5% to 70% by weight, more preferably 5% to 60% by weight, more preferably 10% to 50% by weight based on the total weight of the achiral component T. % Content is particularly preferable.
  • Compound 2 has a chlorobenzene ring.
  • Compound 2 is extremely physically and chemically stable under conditions where the device is normally used, and has good compatibility with other liquid crystal compounds. Furthermore, it is difficult to develop a smectic phase.
  • a composition containing this compound is stable under conditions in which the device is normally used. Accordingly, the temperature range of the cholesteric phase in the composition can be expanded, and the composition can be used as a display element in a wide temperature range. Further, since this compound has a large dielectric anisotropy and refractive index anisotropy, it is useful as a component for increasing the reflectance in order to lower the driving voltage of the composition driven in the cholesteric phase.
  • n22 to n25 in formula (2), the left terminal group R 2A , the group on the rightmost benzene ring and its substitution position ((F) and X 2A ), or the linking groups Z 22 to Z 26 are It is possible to arbitrarily adjust physical properties such as clearing point, refractive index anisotropy and dielectric anisotropy.
  • the effect of the combination of n22, n23, n24 and n25, the left terminal group R 2A , the right terminal group X 2A , the linking groups Z 21 to Z 26 and (F) on the physical properties of the compound 2 will be described below.
  • R 2A in formula (2) is alkenyl
  • the preferred configuration depends on the position of the double bond. —CH ⁇ CHCH 3 , —CH ⁇ CHC 2 H 5 , —CH ⁇ CHC 3 H 7 , —CH ⁇ CHC 4 H 9 , —C 2 H 4 CH ⁇ CHCH 3 , and —C 2 H 4 CH ⁇ CHC 2
  • the trans configuration is preferable.
  • -CH 2 CH CHCH 3
  • An alkenyl compound having a preferred configuration has a high maximum temperature or a wide temperature range of the liquid crystal phase.
  • Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327 have detailed descriptions. Since the bonding groups Z 21 to Z 26 in the formula (2) are a single bond or —CF 2 O—, they are chemically relatively stable and relatively hardly deteriorated.
  • the bonding group is a single bond, the viscosity is small. Further, when the bonding group is —CF 2 O—, the dielectric anisotropy is large.
  • the right terminal group X 2 in the formula (2) is fluorine, chlorine or —OCF 3 , the compatibility with other liquid crystal compounds at low temperature is excellent, and when it is —CF 3 , the driving voltage lowering effect Is big.
  • (F) in the formula (2) is hydrogen, the melting point is low, and when it is fluorine, the dielectric anisotropy is large.
  • a compound having desired physical properties can be obtained by appropriately selecting the kind of the ring structure, terminal group, bonding group and the like in the formula (2).
  • the achiral component of the present invention may further contain at least one compound 3 represented by formula (3). That is, the present invention includes a case where the achiral component T is composed of one compound as the compound 3 and a case where the compound 3 contains two or more compounds represented by the formula (3).
  • the liquid crystal composition of the present invention may contain one or more selected from the group consisting of compounds 2 and 4 to 7 in addition to compound 1 and compound 3.
  • the preferred configuration of alkenyl —CH ⁇ CH— in R 3 depends on the position of the double bond. —CH ⁇ CHCH 3 , —CH ⁇ CHC 2 H 5 , —CH ⁇ CHC 3 H 7 , —CH ⁇ CHC 4 H 9 , —C 2 H 4 CH ⁇ CHCH 3 , and —C 2 H 4 CH ⁇ CHC 2
  • the trans configuration is preferable.
  • -CH 2 CH CHCH 3
  • cis configuration in the alkenyl having an even position to the double bond, such as -CH 2 CH CHC 2 H 5
  • An alkenyl compound having a preferred configuration has a high maximum temperature or a wide temperature range of the liquid crystal phase.
  • Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327 have detailed descriptions.
  • Z 31 , Z 32 and Z 33 are each independently a single bond, —COO— or —CF 2 O—, but at least one is —CF 2 O—.
  • Preferred examples of Z 31 , Z 32 and Z 33 are a single bond and —CF 2 O—.
  • L 31 , L 32 , L 33 , L 34 and L 35 are independently hydrogen or fluorine.
  • Z 32 is —COO— or —CF 2 O—
  • L 32 , L 34 and L 35 are preferably fluorine
  • Z 33 is —COO— or —CF 2 O—
  • L 33 , L 34 and L 35 are preferably fluorine.
  • alkyl in which one or more hydrogens in X 3 of formula (3) are replaced by halogen include —CH 2 F, —CHF 2 , —CF 3 , — (CH 2 ) 2 —F, —CF 2 CH 2 F, —CF 2 CHF 2 , —CH 2 CF 3 , —CF 2 CF 3 , — (CH 2 ) 3 —F, — (CF 2 ) 3 —F, —CF 2 CHFCF 3 , —CHFCF 2 CF 3 , — (CH 2 ) 4 —F, — (CF 2 ) 4 —F, — (CH 2 ) 5 —F, and — (CF 2 ) 5 —F.
  • alkoxy in which one or more hydrogens are replaced by halogen include —OCH 2 F, —OCHF 2 , —OCF 3 , —O— (CH 2 ) 2 —F, —OCF 2 CH 2 F, — OCF 2 CHF 2 , —OCH 2 CF 3 , —O— (CH 2 ) 3 —F, —O— (CF 2 ) 3 —F, —OCF 2 CHFCF 3 , —OCHFCF 2 CF 3 , —O (CH 2 ) 4 -F, -O- (CF 2 ) 4 -F, -O- (CH 2 ) 5 -F, and -O- (CF 2 ) 5 -F.
  • X 3 is preferably fluorine, chlorine, —CF 3 , —CHF 2 , —OCF 3 and —OCHF 2, and more preferably fluorine, chlorine, —CF 3 and —OCF 3 .
  • compound 3 it is preferable to use compounds represented by formulas (3-1) to (3-3), and it is more preferable to use compounds represented by formulas (3-2) and (3-3). More preferably, the compounds represented by formulas (3-2A) to (3-2H) and (3-3A) to (3-3D) are used, and formulas (3-2A) to (3-2D)
  • the compounds represented by (3-3A) and (3-3B) are particularly preferably used, and the compounds represented by formulas (3-2A), (3-2C) and (3-3A) are preferably used. Most preferred.
  • each R 3A independently represents an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, or a carbon number in which at least one hydrogen may be replaced by fluorine
  • L 31 to L 35 are each independently hydrogen or fluorine
  • X 3A is fluorine, chlorine, —CF 3 , or —OCF 3 .
  • R 3A is independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon 2 having at least one hydrogen substituted with fluorine.
  • X 3A is fluorine, chlorine, —CF 3 or —OCF 3 .
  • Compound 3 has a relatively high clearing point, and has a large dielectric anisotropy and a large refractive index anisotropy.
  • the total amount of compound 3 is preferably 0.5% to 70% by weight, more preferably 5% to 60% by weight, more preferably 10% to 50% by weight based on the total weight of the achiral component T. % Content is particularly preferred.
  • Compound 3 has four benzene rings and at least one —CF 2 O— linking group.
  • Compound 3 is extremely physically and chemically stable under the conditions in which the device is normally used, and has good compatibility with other liquid crystal compounds.
  • a composition containing this compound is stable under conditions in which the device is normally used. Accordingly, the temperature range of the cholesteric phase in the composition can be expanded, and the composition can be used as a display element in a wide temperature range.
  • this compound has large dielectric anisotropy and refractive index anisotropy, it is useful as a component for lowering the driving voltage of a composition driven in the cholesteric phase and for increasing the reflectance.
  • the left terminal group R 3 in formula (3) By appropriately selecting the left terminal group R 3 in formula (3), the groups on the benzene ring (L 31 to L 35 and X 3 ), or the linking groups Z 31 to Z 33 , the clearing point, the refractive index anisotropic It is possible to arbitrarily adjust physical properties such as property and dielectric anisotropy.
  • the effect of the left terminal group R 3 , the group on the benzene ring (L 31 to L 35 and X 3 ), or the type of the linking group Z 31 to Z 33 on the physical properties of the compound (3) will be described below.
  • R 3 in formula (3) is alkenyl
  • the preferred configuration of —CH ⁇ CH— in alkenyl depends on the position of the double bond.
  • the trans configuration is preferable.
  • -CH 2 CH CHCH 3
  • cis configuration in the alkenyl having an even position to the double bond, such as -CH 2 CH CHC 2 H 5
  • An alkenyl compound having a preferred configuration has a high maximum temperature or a wide temperature range of the liquid crystal phase.
  • Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327 have detailed descriptions.
  • the bonding groups Z 31 , Z 32 and Z 33 in the formula (3) are single bonds or —CF 2 O—, the viscosity is small.
  • the bonding group is Z 31 , Z 32 and Z 33 is —CF 2 O—, the dielectric anisotropy is large.
  • Z 31 , Z 32 and Z 33 in the formula (3) are a single bond or —CF 2 O—, they are chemically relatively stable and relatively difficult to deteriorate.
  • Dielectric constant when right end group X 3 in formula (3) is fluorine, chlorine, —SF 5 , —CF 3 , —CHF 2 , —CH 2 F, —OCF 3 , —OCHF 2 or —OCH 2 F High anisotropy.
  • X 3 is fluorine, —OCF 3 , or —CF 3 , it is chemically stable.
  • a compound having desired physical properties can be obtained by appropriately selecting the type of terminal group, bonding group, and the like.
  • the achiral component of the present invention may further contain at least one compound 4 represented by the formula (4) in addition to the compound 1. That is, the present invention includes a case where the achiral component T is composed of one compound as the compound 4 and a case where the compound 4 contains two or more compounds represented by the formula (4).
  • the liquid crystal composition of the present invention may contain one or more selected from the group consisting of compounds 2, 3 and 5 to 7 in addition to compound 1 and compound 4.
  • R 4 in Formula (4) is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 to 12 carbons in which at least one hydrogen is replaced by fluorine.
  • Desirable R 4 in formula (4) is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or for the stability to heat.
  • R 4 in the formula (4) is preferably an alkenyl having 2 to 12 carbons from the viewpoint of decreasing the viscosity, and an alkyl having 1 to 12 carbons from the viewpoint of increasing the stability to ultraviolet rays or the stability to heat. Is preferred.
  • Preferred alkyl for R 4 in formula (4) is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl, and more preferred alkyl is ethyl, propyl, butyl, pentyl for decreasing the viscosity. Or heptyl.
  • Preferred alkoxy for R 4 in formula (4) is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy, and more preferred alkoxy is methoxy or ethoxy for decreasing the viscosity.
  • Preferred alkenyl for R 4 in the formula (4) is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl. , 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl, and more preferable alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for decreasing the viscosity. is there.
  • the preferred configuration of —CH ⁇ CH— in alkenyl at R 4 in formula (4) depends on the position of the double bond.
  • trans is preferable in alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl.
  • Cis is preferred for alkenyl such as 2-butenyl, 2-pentenyl, and 2-hexenyl.
  • linear alkenyl is preferable to branching.
  • alkenyl in which one or more hydrogens are replaced by fluorine in R 4 in the formula (4) include 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro- 3-butenyl, 5,5-difluoro-4-pentenyl, and 6,6-difluoro-5-hexenyl are listed, and in order to reduce the viscosity of the liquid crystal composition, 2,2-difluorovinyl, and 4 , 4-difluoro-3-butenyl is preferred.
  • the alkyl in R 4 in formula (4) does not include cyclic alkyl.
  • Alkoxy does not include cyclic alkoxy.
  • Alkenyl does not include cyclic alkenyl.
  • Alkenyl in which at least one hydrogen is replaced with fluorine does not include cyclic alkenyl in which at least one hydrogen is replaced with fluorine.
  • Ring B in formula (4) is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5 -Difluoro-1,4-phenylene, 3,5-dichloro-1,4-phenylene, or pyrimidine-2,5-diyl, and when n 41 is 2 or more, at least two of the rings B are the same Or different.
  • Ring B in formula (4) is 1,4-phenylene or 3-fluoro-1,4-phenylene for increasing the optical anisotropy, and 1,4-cyclohexylene for decreasing the viscosity. Is preferred.
  • Z 41 in formula (4) is independently a single bond, ethylene, —COO—, —OCO—, —CF 2 O— or —OCF 2 —, provided that when n 41 is 3 or 4, One Z 41 is —CF 2 O—. When n 41 is 2 or more, at least two of the Z 41 may be the same or different.
  • Z 41 in formula (4) is preferably a single bond for decreasing the viscosity.
  • Z 41 in formula (4) is preferably —CF 2 O— in order to increase the dielectric anisotropy and to improve the compatibility.
  • L 48 and L 49 in the formula (4) are independently hydrogen or fluorine.
  • both L 48 and L 49 are preferably fluorine, and in order to increase the clearing point, L 48 And L 49 is preferably hydrogen.
  • X 4 in the formula (4) is fluorine, chlorine, —CF 3 or —OCF 3 .
  • —CF 3 is preferable.
  • fluorine and —OCF 3 are preferable.
  • chlorine is preferable.
  • compound 4 it is preferable to use compounds represented by formulas (4-1) to (4-9).
  • the compounds represented by the formulas (4-1) to (4-3) have a high clearing point and excellent compatibility as a pentacyclic compound.
  • the compounds represented by formulas (4-4) to (4-6) have a high clearing point and a large ⁇ n.
  • the compounds represented by formulas (4-7) to (4-9) are excellent in compatibility.
  • Compound 4 is suitable for the preparation of a composition having large dielectric anisotropy or good compatibility at low temperatures.
  • the total amount of compound 4 is preferably 5% to 40% by weight, more preferably 5% to 30% by weight, more preferably 5% to 20% by weight, based on the total weight of the achiral component T. It is particularly preferable to do this.
  • the achiral component of the present invention may further contain at least one compound 3 represented by formula (5). That is, the present invention includes the case where the achiral component T is composed of one compound as the compound 5 and the case where the compound 5 contains two or more compounds represented by the formula (5).
  • the liquid crystal composition of the present invention may contain one or more selected from the group consisting of compounds 2 to 4, 6 and 7 in addition to compound 1 and compound 5.
  • R 5 in formula (5) the preferred configuration of —CH ⁇ CH— in alkenyl depends on the position of the double bond. Specifically, —CH ⁇ CHCH 3 , —CH ⁇ CHC 2 H 5 , —CH ⁇ CHC 3 H 7 , —CH ⁇ CHC 4 H 9 , —C 2 H 4 CH ⁇ CHCH 3 , and —C 2 H
  • a trans configuration is preferable
  • —CH 2 CH ⁇ CHCH 3 , —CH 2 CH ⁇ CHC 2 H 5 , and —CH 2 CH ⁇ A cis configuration is preferable in an alkenyl having a double bond at an even-numbered position such as CHC 3 H 7 .
  • the alkenyl compound having a preferred configuration in the formula (5) has a high maximum temperature or a wide temperature range of the liquid crystal phase.
  • Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327 have detailed descriptions.
  • alkyl in which at least one hydrogen is replaced with fluorine or chlorine in R 5 and X 5 in formula (5) are —CHF 2 , —CF 3 , —CF 2 CH 2 F, —CF 2 CHF 2 , —CH 2 CF 3 , —CF 2 CF 3 , — (CH 2 ) 3 —F, — (CF 2 ) 3 —F, —CF 2 CHFCF 3 , and —CHFCF 2 CF 3 .
  • alkoxy in which at least one hydrogen is replaced with fluorine or chlorine in R 5 and X 5 in formula (5) are —OCHF 2 , —OCF 3 , —OCF 2 CH 2 F, —OCF 2 CHF 2 , —OCH 2 CF 3 , —O— (CF 2 ) 3 —F, —OCF 2 CHFCF 3 , and —OCHFCF 2 CF 3 .
  • X 5 in formula (5) include fluorine, chlorine, —CF 3 , —CHF 2 , —OCF 3 and —OCHF 2 , and fluorine, chlorine, —CF 3 and —OCF 3 are preferable.
  • X 5 in the formula (5) is chlorine or fluorine, the melting point of the compound 5 is relatively low, and the compatibility with other liquid crystal compounds is particularly excellent.
  • X 5 in Formula (5) is —CF 3 , —CHF 2 , —OCF 3 and —OCHF 2 , Compound 5 exhibits a relatively large dielectric anisotropy.
  • X 5 in the formula (5) is fluorine, chlorine, —SF 5 , —CF 3 , —OCF 3 , or —CH ⁇ CH—CF 3 , the dielectric anisotropy of the compound 5 is relatively large, When X 5 is fluorine, —CF 3 , or —OCF 3 , it is relatively chemically stable.
  • R 5A is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine. Yes; (F) is each independently hydrogen or fluorine; X 5A is fluorine, chlorine, —CF 3 or —OCF 3 . )
  • Compound 5 is suitable for preparing a composition having a large dielectric anisotropy.
  • the total amount of Compound 5 is about 1.0% by weight or more based on the total weight of the achiral component T.
  • the compound 5 is preferably contained in an amount of 1 to 25% by weight, more preferably 1 to 15% by weight, based on the total weight of the achiral component T.
  • Compound 5 has a dioxane ring and three benzene rings. Compound 5 is physically and chemically very stable under the conditions under which the device is normally used, and has a relatively good compatibility with other liquid crystal compounds despite its high clearing point. The composition containing compound 5 is stable under conditions in which the device is normally used. Therefore, the composition containing the compound 5 can expand the temperature range of the optically isotropic liquid crystal phase and can be used as a display element in a wide temperature range. Compound 5 is useful as a component for lowering the driving voltage of a composition driven in an optically isotropic liquid crystal phase.
  • composition of a preferred embodiment including the chiral agent and the compound 5 When a blue phase is expressed in the composition of a preferred embodiment including the chiral agent and the compound 5, a uniform blue phase without coexistence with the N * phase or the isotropic phase is obtained.
  • the composition of the preferable aspect containing the compound 5 tends to express a uniform blue phase.
  • the clearing point of the liquid crystal composition tends to increase.
  • the compound of the formula (5) of the present application can be synthesized even if the method of Japanese Patent No. 2959526 (JP 2959526B) is applied mutatis mutandis.
  • the achiral component of the present invention may further contain at least one compound 6 represented by the formula (6) in addition to the compound 1. That is, the present invention includes a case where the achiral component T is composed of one compound as the compound 6 and a case where the compound 6 contains two or more compounds represented by the formula (6).
  • the liquid crystal composition of the present invention may contain one or more selected from the group consisting of compounds 2 to 5 and 7 in addition to compound 1 and compound 6.
  • Compound 6 is a compound having a small absolute value of dielectric anisotropy and close to neutrality.
  • a compound in which r is 1 in the formula (6) mainly has an effect of adjusting viscosity or refractive index anisotropy, and a compound in which r is 2 or 3 in the formula (6) has a high clearing point. This has the effect of expanding the temperature range of the optically isotropic liquid crystal phase or adjusting the refractive index anisotropy value.
  • the content of the compound 6 of the achiral component T is preferably 0% to 40% by weight, more preferably 1% to 40% by weight, more preferably 1% by weight with respect to the total weight of the achiral component T. It is particularly preferable that the content is from 20 to 20% by weight.
  • R 6A and R 6B in the formula (6) are each independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen being fluorine. Substituted alkenyl having 2 to 12 carbon atoms. In order to reduce the viscosity of the compound 6, R 6A and R 6B in the formula (6) are preferably alkenyl having 2 to 12 carbon atoms. In order to increase stability to ultraviolet light or heat, R 6A and R 6B in formula (6) are preferably alkyl having 1 to 12 carbon atoms.
  • alkyl is preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl.
  • ethyl, propyl, butyl, Pentyl or heptyl is preferred.
  • alkoxy is preferably methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy, and methoxy or ethoxy is preferable for decreasing the viscosity.
  • R 6A and R 6B in the formula (6) the preferred configuration of —CH ⁇ CH— in alkenyl depends on the position of the double bond.
  • the trans configuration is preferable.
  • -CH 2 CH CHCH 3
  • cis configuration in the alkenyl having an even position to the double bond, such as -CH 2 CH CHC 2 H 5
  • An alkenyl compound having a preferred configuration has a high maximum temperature or a wide temperature range of the liquid crystal phase.
  • Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327 have detailed descriptions.
  • alkenyl in which at least one hydrogen is replaced by fluorine is 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3 -Butenyl, 5,5-difluoro-4-pentenyl, and 6,6-difluoro-5-hexenyl are preferred.
  • R 6A and R 6B are preferably 2,2-difluorovinyl and 4,4-difluoro-3-butenyl.
  • Ring C and Ring D in formula (6) are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene or When 2,5-difluoro-1,4-phenylene and r is 2 or more, at least two of the rings C may be the same or different.
  • ring C and ring D are preferably 1,4-phenylene or 3-fluoro-1,4-phenylene.
  • Ring C and Ring D are 1,4-cyclohexylene.
  • Z 61 in formula (6) is each independently a single bond, ethylene, or —COO— or —OCO—, and when r is 2 or more, at least two of Z 13 are the same. May be different. Desirable Z 61 is a single bond for decreasing the viscosity.
  • compound 6 it is preferable to use compounds represented by formulas (6-1) to (6-13).
  • the compounds represented by (6-1) to (6-3) have relatively low viscosity, and the compounds represented by (6-4) to (6-8) have a clear point comparison.
  • the compounds represented by (6-9) to (6-13) have a relatively high clearing point.
  • Compound 6 is used to lower the viscosity or raise the clearing point as necessary. However, since the drive voltage is increased, when importance is attached to the drive voltage, it is preferably not used or used in a small amount.
  • the total amount of compound 6 is preferably 0 to 30% by weight, more preferably 0 to 20% by weight, and particularly preferably 0 to 10% by weight.
  • the achiral component of the present invention may further contain at least one compound 7 represented by formula (7). That is, the present invention includes a case where the achiral component T is composed of one compound as the compound 7 and a case where the compound 7 contains two or more compounds represented by the formula (7).
  • the liquid crystal composition of the present invention may contain one or more selected from the group consisting of compounds 2 to 6 in addition to compound 1 and compound 7.
  • R 7 and X 7 in Formula (7) the preferred configuration of —CH ⁇ CH— in alkenyl depends on the position of the double bond. —CH ⁇ CHCH 3 , —CH ⁇ CHC 2 H 5 , —CH ⁇ CHC 3 H 7 , —CH ⁇ CHC 4 H 9 , —C 2 H 4 CH ⁇ CHCH 3 , and —C 2 H 4 CH ⁇ CHC 2
  • the trans configuration is preferable.
  • -CH 2 CH CHCH 3
  • cis configuration in the alkenyl having an even position to the double bond, such as -CH 2 CH CHC 2 H 5
  • An alkenyl compound having a preferred configuration has a high maximum temperature or a wide temperature range of the liquid crystal phase.
  • Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327 have detailed descriptions.
  • alkyl in which at least one hydrogen is replaced with fluorine at X 7 in formula (7) include —CHF 2 , —CF 3 , —CF 2 CH 2 F, —CF 2 CHF 2 , — CH 2 CF 3 , —CF 2 CF 3 , — (CH 2 ) 3 —F, — (CF 2 ) 3 —F, —CF 2 CHFCF 3 , and —CHFCF 2 CF 3 .
  • alkoxy in which at least one hydrogen is replaced by fluorine in X 7 in formula (7) include —OCHF 2 , —OCF 3 , —OCF 2 CH 2 F, —OCF 2 CHF 2 , — OCH 2 CF 3 , —O— (CF 2 ) 3 —F, —OCF 2 CHFCF 3 , and —OCHFCF 2 CF 3 .
  • X 7 preferred specific examples include fluorine, chlorine, —CF 3 , —CHF 2 , —OCF 3 and —OCHF 2 , and fluorine, chlorine, —CF 3 and —OCF 3 are Further preferred.
  • X 7 in the formula (7) is chlorine or fluorine, the melting point of the compound 7 is relatively low, and the compatibility with other liquid crystal compounds is particularly excellent.
  • Formula (7) X 7 is —CF 3 , —SF 5, —CHF 2 , —OCF 3 and —OCHF 2 , Compound 7 exhibits a relatively large dielectric anisotropy.
  • X 7 is fluorine, —CF 3 , or —OCF 3 , it is chemically stable.
  • compound 7 it is preferable to use compounds represented by formulas (7-1) to (7-8).
  • Formulas (7-1-1), (7-1-2), (7-2-1) ) To (7-2-5), (7-3-1), (7-3-2), (7-4-1), (7-5-1) and (7-5-2) It is more preferable to use a compound represented by formulas (7-2-1) to (7-2-5), and it is more preferable to use (7-2-2-E), (7 The compounds represented by 7-2-5-E), (7-2-2-F) and (7-2-5-F) are particularly preferred.
  • R 7A is alkyl having 1 to 12 carbons, alkoxy having 1 to 11 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine
  • Is wherein R 7A is alkyl having 1 to 12 carbons, alkoxy having 1 to 11 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine
  • X 7A is fluorine, chlorine, —CF 3 or —OCF 3 .
  • Compound 7 is suitable for preparing a composition having a large dielectric anisotropy, and can reduce the driving voltage in the device of the present invention.
  • the total content of compound 7 is preferably 5% to 80% by weight, more preferably 20% to 75% by weight, and more preferably 30% to 70% by weight, based on the total weight of the achiral component T. It is particularly preferable to do this.
  • Compound 7 has a dioxane ring and three benzene rings, and has at least one —CF 2 O— linking group.
  • Compound 7 is physically and chemically very stable under the conditions under which the device is normally used, and has a relatively good compatibility with other liquid crystal compounds despite its high clearing point.
  • the composition containing Compound 7 is relatively stable under conditions in which the device is normally used. Therefore, the temperature range of the optically isotropic liquid crystal phase in the composition containing the compound 7 can be expanded, and can be used as a display element in a wide temperature range. Further, the compound 7 is useful as a component for lowering the driving voltage of a composition driven with an optically isotropic liquid crystal phase.
  • the compound 7 is a compound that easily develops a uniform blue phase. In addition, it exhibits extremely large dielectric anisotropy.
  • the liquid crystal composition of the present invention includes an embodiment of a composition containing an achiral component T and a chiral agent and exhibiting a cholesteric phase (cholesteric liquid crystal composition).
  • the achiral component T contained in the cholesteric liquid crystal composition of the present invention includes the compound 1, and optionally includes one or more compounds selected from the group consisting of the compounds 2 to 7.
  • the achiral component T contained in the cholesteric liquid crystal composition of the present invention preferably includes compounds 2, 3, 5 and 7 in addition to compound 1, particularly preferably includes compounds 3 and 7, and further required properties. Depending on the compound 4 and 6 can be included. Since Compound 1 has a relatively high clearing point, a relatively large dielectric anisotropy, and a relatively good compatibility at low temperatures, a cholesteric liquid crystal composition using Compound 1 also has a high clearing point and a wide liquid crystal phase temperature range.
  • a display element using a selective sales company of a cholesteric phase is known.
  • a selective reflection wavelength at room temperature of a preferable cholesteric phase is 400 nm to 750 nm.
  • the compounds 1 to 7 include a case where one compound is included and a case where two or more compounds are included. That is, the liquid crystal composition of the present invention may include a plurality of types of compounds 1 represented by the formula (1) and having different structures. The same applies to compounds 2 to 7.
  • the liquid crystal composition of the present invention includes an embodiment of a composition containing an achiral component T and a chiral agent and exhibiting an optically isotropic liquid crystal phase (optical Isotropic liquid crystal composition).
  • the achiral component T contained in the optically isotropic liquid crystal composition of the present invention includes compound 1, and optionally includes one or more selected from the group consisting of compounds 2 to 7.
  • the achiral component T preferably includes compounds 2, 3, 5 and 7 in addition to compound 1, particularly preferably includes compounds 3 and 7, and further includes compounds 4 and 6 depending on the properties required. Can do.
  • Compound 1 Since Compound 1 has a relatively high clearing point, a relatively large dielectric anisotropy, and a relatively good compatibility at low temperature, a liquid crystal composition that exhibits optical isotropy using Compound 1 is also high. Since it exhibits a clearing point, a wide liquid crystal phase temperature range, or a large dielectric anisotropy, it is useful as a composition used in an optical element.
  • the optically isotropic liquid crystal composition containing the compound 1 simultaneously exhibits a high clearing point and a low driving voltage.
  • the chiral agent contained in the cholesteric liquid crystal composition, the optically isotropic liquid crystal composition, etc. of the present invention is an optically active compound and comprises a compound selected from compounds having no radical polymerizable group. Is preferred.
  • a compound having a large twisting power is preferable.
  • a compound having a large torsional force can reduce the amount of addition necessary to obtain a desired pitch, so that an increase in driving voltage can be suppressed and is practically advantageous.
  • compounds represented by formulas (K1) to (K5) are preferable.
  • chiral agents added to the liquid crystal composition include those represented by formulas (K2-1) to (K2-8) and formula (K4) included in formula (K2).
  • 1) to formula (K4-6) and formula (K5-1) to formula (K5-3) included in formula (K5) are preferred, and formula (K4-1) to formula (K4-6) and formula (K More preferred are K5-1) to formula (K5-3).
  • a chiral agent that does not have a relatively large twisting force examples include compounds represented by the following formulas (Op-1) to (Op-13).
  • one compound may be used, or two or more compounds may be used.
  • the chiral agent is preferably contained in an amount of 1 to 40% by weight based on the total weight of the liquid crystal composition of the present invention. It is more preferably contained, and particularly preferably 5 to 15% by weight.
  • pitch based on microscopic order of liquid crystal composition (hereinafter, sometimes referred to as pitch)” is preferably 700 nm or less, more preferably 500 nm or less, and 350 nm or less. Is most preferred.
  • non-liquid crystal isotropic phase is a generally defined isotropic phase, that is, a disordered phase, and even if a region where the local order parameter is not zero is generated, the cause is due to fluctuations.
  • Isotropic phase For example, an isotropic phase appearing on the high temperature side of the nematic phase corresponds to a non-liquid crystal isotropic phase in this specification.
  • the same definition shall apply to the chiral liquid crystal in this specification.
  • the “optically isotropic liquid crystal phase” refers to a phase that expresses an optically isotropic liquid crystal phase instead of fluctuations, for example, a phase that expresses a platelet structure (a blue phase in a narrow sense). ) Is an example.
  • optically isotropic liquid crystal composition of the present invention although it is an optically isotropic liquid crystal phase, a platelet structure typical of a blue phase may not be observed under a polarizing microscope. Therefore, in this specification, a phase that develops a platelet structure is referred to as a blue phase, and an optically isotropic liquid crystal phase including the blue phase is referred to as an optically isotropic liquid crystal phase. That is, the blue phase is included in the optically isotropic liquid crystal phase.
  • the blue phase is classified into three types of blue phase I, blue phase II, and blue phase III, and these three types of blue phases are all optically active and isotropic.
  • the blue phase I or blue phase II two or more types of diffracted light caused by Bragg reflection from different lattice planes are observed.
  • the blue phase is generally observed between the non-liquid crystal isotropic phase and the chiral nematic phase.
  • the state in which the optically isotropic liquid crystal phase does not show diffracted light of two or more colors means that the platelet structure observed in the blue phase I and the blue phase II is not observed and is generally monochromatic. To do. In an optically isotropic liquid crystal phase that does not show diffracted light of two or more colors, it is not necessary until the color brightness is uniform in the plane.
  • An optically isotropic liquid crystal phase that does not show diffracted light of two or more colors has an advantage that the reflected light intensity due to Bragg reflection can be suppressed or shifted to the lower wavelength side.
  • color may be a problem when used as a display element.
  • the reflection wavelength is shifted by a low wavelength. Therefore, the reflection of visible light can be eliminated at a pitch longer than the narrowly defined blue phase (phase that expresses the platelet structure).
  • the chiral agent is preferably added at a concentration such that the pitch is 700 nm or less.
  • the composition which expresses a nematic phase contains the compound 1 and another component as needed.
  • the optically isotropic liquid crystal composition of the present invention can also be obtained by adding a chiral agent to a composition having a chiral nematic phase and not having an optically isotropic liquid crystal phase.
  • the composition which has a chiral nematic phase and does not have an optically isotropic liquid crystal contains the compound 1, an optically active compound, and another component as needed.
  • the chiral agent is preferably added at a concentration such that the pitch is 700 nm or more.
  • the compounds (K1) to (K5) which are compounds having a large torsional force, can be used, and more preferably, the compounds of the formulas (K2-1) to (K2-8) and (K4- Compounds represented by 1) to (K4-6) or formulas (K5-1) to (K5-3) are used.
  • the added chiral agent may be a compound that does not have a very large twisting force. Examples of such a compound include compounds added to liquid crystal compositions for devices driven in a nematic phase (TN mode, STN mode, etc.). And a compound represented by (Op-13).
  • the temperature range in which the liquid crystal composition of the preferred embodiment of the present invention exhibits an optically isotropic liquid crystal phase is a nematic phase or a liquid crystal composition having a wide coexistence temperature range of a chiral nematic phase and an isotropic phase. It can be widened by adding an optically isotropic liquid crystal phase.
  • a liquid crystal compound having a high clearing point and a liquid crystal compound having a low clearing point are mixed to prepare a liquid crystal composition having a wide coexistence temperature range of a nematic phase and an isotropic phase over a wide temperature range, and a chiral agent is added thereto.
  • a composition that exhibits an optically isotropic liquid crystal phase in a wide temperature range can be prepared.
  • the difference between the maximum temperature and the minimum temperature at which the chiral nematic phase and the non-liquid crystal isotropic phase coexist is 3 to 150 ° C.
  • a liquid crystal composition is preferable, and a liquid crystal composition having a difference of 5 to 150 ° C. is more preferable.
  • a liquid crystal composition in which the difference between the upper limit temperature and the lower limit temperature at which the nematic phase and the non-liquid crystal isotropic phase coexist is 3 to 150 ° C. is preferable.
  • the liquid crystal composition of the present invention has a solvent, monomer, polymer substance, polymerization initiator, antioxidant, ultraviolet absorber, curing, as long as it does not significantly affect the properties of the composition.
  • dichroic dye used in the liquid crystal composition of the present invention include merocyanine series, styryl series, azo series, azomethine series, azoxy series, quinophthalone series, anthraquinone series, and tetrazine series.
  • the polymer / liquid crystal composite material of the present invention is a composite material containing a liquid crystal composition and a polymer, and exhibits optical isotropy and is optically isotropic. It can be used for an optical element driven in the liquid crystal phase.
  • the liquid crystal composition contained in the polymer / liquid crystal composite material of the present invention is the liquid crystal composition of the present invention.
  • the “polymer / liquid crystal composite material” is not particularly limited as long as it is a composite material including both a liquid crystal composition and a polymer compound. A state where the polymer is phase-separated from the liquid crystal composition without being dissolved in a solvent or the like may be used.
  • a nematic phase means a nematic phase in a narrow sense that does not include a chiral nematic phase.
  • the optically isotropic polymer / liquid crystal composite material according to a preferred embodiment of the present invention can exhibit an optically isotropic liquid crystal phase in a wide temperature range. Further, the polymer / liquid crystal composite material according to a preferred embodiment of the present invention has an extremely fast response speed. Moreover, the polymer / liquid crystal composite material according to a preferred embodiment of the present invention can be suitably used for an optical element such as a display element based on these effects.
  • the composite material of the present invention can be produced by mixing an optically isotropic liquid crystal composition and a polymer obtained by polymerization in advance. It is preferable that the monomer, macromonomer, oligomer, etc. (hereinafter collectively referred to as “monomer etc.”) and the liquid crystal composition CLC are mixed and then subjected to a polymerization reaction in the mixture.
  • a mixture containing a monomer or the like and a liquid crystal composition is referred to as a “polymerizable monomer / liquid crystal mixture”.
  • the “polymerizable monomer / liquid crystal mixture” includes a polymerization initiator, a curing agent, a catalyst, a stabilizer, a dichroic dye, or a photochromic compound, which will be described later, as necessary, as long as the effects of the present invention are not impaired. But you can.
  • the polymerizable monomer / liquid crystal mixture of the present invention may contain a polymerization initiator in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the polymerizable monomer, if necessary.
  • the “polymerizable monomer / liquid crystal mixture” must be a liquid crystal medium when polymerized in the blue phase, but is not necessarily a liquid crystal medium when polymerized in the isotropic phase.
  • the polymerization temperature is preferably a temperature at which the polymer / liquid crystal composite material exhibits high transparency and isotropic properties. More preferably, the polymerization is terminated at a temperature at which the mixture of the monomer and the liquid crystal material develops an isotropic phase or a blue phase, and at the isotropic phase or the optically isotropic liquid crystal phase. That is, after polymerization, the polymer / liquid crystal composite material is preferably set to a temperature that does not substantially scatter light on the longer wavelength side than visible light and develops an optically isotropic state.
  • low molecular weight monomers, macromonomers, and oligomers can be used as the polymer raw materials constituting the composite material of the present invention.
  • the high molecular weight raw material monomers are low molecular weight monomers, macromonomers.
  • the obtained polymer has a three-dimensional crosslinked structure. Therefore, it is preferable to use a polyfunctional monomer having two or more polymerizable functional groups as a raw material monomer for the polymer.
  • the polymerizable functional group is not particularly limited, and an acrylic group, a methacryl group, a glycidyl group, an epoxy group, an oxetanyl group, a vinyl group, and the like can be raised, but an acrylic group and a methacryl group are preferable from the viewpoint of polymerization rate.
  • a monomer having two or more polymerizable functional groups in the polymer raw material monomer is contained in an amount of 10% by weight or more, high transparency and isotropy are easily exhibited in the composite material of the present invention. This is preferable.
  • the polymer preferably has a mesogen moiety, and a raw material monomer having a mesogen moiety can be used as a part or all of the polymer as a polymer raw material monomer.
  • the monofunctional or bifunctional monomer having a mesogen moiety is not particularly limited in terms of structure. For example, it is represented by the following formula (M1) or (M2): Can be mentioned.
  • R a is hydrogen, halogen, —C ⁇ N, —N ⁇ C ⁇ O, —N ⁇ C ⁇ S, or alkyl having 1 to 20 carbons, and in these alkyls, at least 1 Two —CH 2 — may be replaced by —O—, —S—, —CO—, —COO—, or —OCO—, and at least one —CH 2 —CH 2 — in the alkyl is — CH ⁇ CH—, —CF ⁇ CF—, or —C ⁇ C— may be substituted, and in these alkyl groups, at least one —CH 2 — in the alkyl is —O—, —S—, In a group replaced by —COO— or —OCO—, or at least one —CH 2 —CH 2 — in the alkyl is replaced by —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—. At least one hydrogen in the radical formed is halogen The other may be
  • R a is hydrogen, halogen, —C ⁇ N, —CF 3 , —CF 2 H, —CFH 2 , —OCF 3 , —OCF 2 H, alkyl having 1 to 20 carbons, or alkyl having 1 to 19 carbons. Alkoxy, alkenyl having 2 to 21 carbons, and alkynyl having 2 to 21 carbons. Particularly preferred R a is —C ⁇ N, alkyl having 1 to 20 carbons and alkoxy having 1 to 19 carbons.
  • each R b is independently a polymerizable group of the formulas (M3-1) to (M3-7).
  • R d in formulas (M3-1) to (M3-7) is each independently hydrogen, halogen, or alkyl having 1 to 5 carbon atoms, and in these alkyls, at least one hydrogen is replaced with halogen. May be.
  • Preferred R d is hydrogen, halogen and methyl.
  • Particularly preferred R d is hydrogen, fluorine and methyl.
  • the formula (M3-2), the formula (M3-3), the formula (M3-4), and the formula (M3-7) are preferably polymerized by radical polymerization.
  • the formulas (M3-1), (M3-5), and (M3-6) are preferably polymerized by cationic polymerization.
  • a polymerization initiator can be used for the purpose of accelerating the generation of active species. For example, light or heat can be used to generate the active species.
  • a M is each independently an aromatic or non-aromatic 5-membered ring, 6-membered ring, or condensed ring having 9 or more carbon atoms.
  • CH 2 — may be —O—, —S—, —NH—, or —NCH 3 —, and —CH ⁇ in the ring may be replaced by —N ⁇ , the hydrogen atom on the ring is halogen, and carbon number It may be replaced with 1 to 5 alkyls or alkyl halides.
  • a M 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4 -Phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2-trifluoromethyl-1,4-phenylene, 2 , 3-bis (trifluoromethyl) -1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7- Diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, and pyrimidine-2,5-diyl.
  • the steric configuration of 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl is preferably trans rather than cis. Since 2-fluoro-1,4-phenylene is structurally identical to 3-fluoro-1,4-phenylene, the latter was not exemplified. This rule also applies to the relationship between 2,5-difluoro-1,4-phenylene and 3,6-difluoro-1,4-phenylene.
  • each Y is independently a single bond or alkylene having 1 to 20 carbon atoms, and in these alkylenes, at least one —CH 2 — is —O— or —S—. At least one —CH 2 —CH 2 — in the alkyl may be replaced with —CH ⁇ CH—, —C ⁇ C—, —COO—, or —OCO—.
  • Preferred Y is a single bond, — (CH 2 ) m2 —, —O (CH 2 ) m2 —, and — (CH 2 ) m2 O— (wherein m2 is an integer of 1 to 20) .
  • Y is a single bond, — (CH 2 ) m2 —, —O (CH 2 ) m2 —, and — (CH 2 ) m2 O— (wherein m2 is an integer of 1 to 10). is there.
  • —Y—R a and —Y—R b may be —O—O—, —O—S—, —S—O—, or —S—S in their groups. It is preferable not to have-.
  • Z M each independently represents a single bond, — (CH 2 ) m3 —, —O (CH 2 ) m3 —, — (CH 2 ) m3 O—, —O ( CH 2 ) m 3 O—, —CH ⁇ CH—, —C ⁇ C—, —COO—, —OCO—, — (CF 2 ) 2 —, — (CH 2 ) 2 —COO—, —OCO— (CH 2 ) 2 —, —CH ⁇ CH—COO—, —OCO—CH ⁇ CH—, —C ⁇ C—COO—, —OCO—C ⁇ C—, —CH ⁇ CH— (CH 2 ) 2 —, — (CH 2 ) 2 —CH ⁇ CH—, —CF ⁇ CF—, —C ⁇ C—CH ⁇ CH—, —CH ⁇ CH—C ⁇ C—, —OCF 2 — (CH 2 ) 2 —,
  • Preferred Z M is a single bond, — (CH 2 ) m3 —, —O (CH 2 ) m3 —, — (CH 2 ) m3 O—, —CH ⁇ CH—, —C ⁇ C—, —COO—, — OCO—, — (CH 2 ) 2 —COO—, —OCO— (CH 2 ) 2 —, —CH ⁇ CH—COO—, —OCO—CH ⁇ CH—, —OCF 2 —, and —CF 2 O— It is.
  • m1 is an integer of 1 to 6.
  • Preferred m1 is an integer of 1 to 3.
  • m1 is 1, it is a bicyclic compound having two rings such as a 6-membered ring.
  • m1 is 2 or 3, they are tricyclic and tetracyclic compounds, respectively.
  • two A M may be may be the same or different.
  • three A M or two Z M ) may be the same or different.
  • m1 is 3-6.
  • R a , R b , R d , Z M , A M and Y The same applies.
  • the compound (M1) represented by the formula (M1) and the compound (M2) represented by the formula (M2) contain isotopes such as 2 H (deuterium) and 13 C in an amount larger than the natural abundance. However, since it has the same characteristics, it can be preferably used.
  • More preferred examples of the compound (M1) and the compound (M2) include the compounds (M1-1) represented by the formulas (M1-1) to (M1-41) and the formulas (M2-1) to (M2-27). To (M1-41) and compounds (M2-1) to (M2-27).
  • R a , R b , R d , Z M , A M , Y and p are the same as those in formula (M1) and formula (M2) described in the embodiments of the present invention.
  • the partial structure (a1) represents 1,4-phenylene in which at least one hydrogen is replaced by fluorine.
  • the partial structure (a2) represents 1,4-phenylene in which at least one hydrogen may be replaced by fluorine.
  • the partial structure (a3) represents 1,4-phenylene in which at least one hydrogen may be replaced with either fluorine or methyl.
  • the partial structure (a4) represents fluorene in which the hydrogen at the 9-position may be replaced with methyl.
  • a monomer having no mesogen moiety and a polymerizable compound other than the monomers (M1) and (M2) having a mesogen moiety can be used as necessary.
  • a monomer having a mesogenic moiety and having three or more polymerizable functional groups may be used.
  • known compounds can be suitably used. Examples thereof include (M4-1) to (M4-3).
  • Examples thereof include compounds described in JP-A No. 2000-327632 (JP 2000-327632A), JP-A No. 2004-182949 (JP 2004-182949A), JP-A No. 2004-59772 (JP 2004-59772A).
  • R b , Z M , Y, and (F) have the same meaning as described above.
  • Monomer having a polymerizable functional group not having a mesogen moiety for example, a linear or branched acrylate having 1 to 30 carbon atoms, carbon
  • a monomer having 1 to 30 linear or branched diacrylates and three or more polymerizable functional groups include glycerol / propoxylate (1PO / OH) triacrylate, pentaerythritol / propoxylate / triacrylate, pentaerythritol / Triacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane propoxylate triacrylate, trimethylolpropane triacrylate, di (trimethylolpropane) tetraacrylate, pentaerythritol Examples thereof include, but are not limited to, tetraacrylate, di (pentaerythritol) pentaacrylate,
  • the polymerization reaction in the production of the polymer constituting the composite material of the present invention is not particularly limited, and for example, photo radical polymerization, thermal radical polymerization, photo cation polymerization and the like are performed.
  • radical photopolymerization initiators examples include DAROCUR 1173 and 4265 (both trade names, BASF Japan Ltd.), Irgacure 184, 369, 500, 651, and 784. , 819, 907, 1300, 1700, 1800, 1850, and 2959 (all trade names, BASF Japan Ltd.), and the like.
  • thermal radical polymerization examples include benzoyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate , T-butyl peroxydiisobutyrate, lauroyl peroxide, dimethyl 2,2′-azobisisobutyrate (MAIB), di-t-butyl peroxide (DTBPO), azobisisobutyronitrile (AIBN), azobiscyclohexanecarbox Nitrile (ACN) and the like.
  • MAIB dimethyl 2,2′-azobisisobutyrate
  • DTBPO di-t-butyl peroxide
  • AIBN azobisisobutyronitrile
  • ACN azobiscyclohexanecarbox Nitrile
  • photocationic polymerization initiator examples include diaryliodonium salts (hereinafter referred to as “DAS”), triarylsulfonium salts (hereinafter referred to as “TAS”), and the like.
  • DAS diaryliodonium salts
  • TAS triarylsulfonium salts
  • DAS includes diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodoniumtetra (pentafluorophenyl) ) Borate, 4-methoxyphenyl phenyl iodonium tetrafluoroborate, 4-methoxyphenyl phenyl iodonium hexafluorophosphonate, 4-methoxyphenyl phenyl iodonium hexafluoroarsenate, 4-methoxyphenyl phenyl iodonium trifluoromethanesulfonate, 4-methoxyphen
  • Sensitivity can be increased by adding a photosensitizer such as thioxanthone, phenothiazine, chlorothioxanthone, xanthone, anthracene, diphenylanthracene, rubrene to DAS.
  • a photosensitizer such as thioxanthone, phenothiazine, chlorothioxanthone, xanthone, anthracene, diphenylanthracene, rubrene to DAS.
  • TAS includes triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, Triphenylsulfonium tetra (pentafluorophenyl) borate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethane Sulfona
  • cationic photopolymerization initiator examples include Cyracure UVI-6990, Cyracure UVI-6974, Cyracure UVI-6922 (trade names, UCC Co., Ltd.), Adekaoptomer SP-150, SP-152, SP-170, SP-172 (Product name, ADEKA Corporation), Rhodorsil® Photoinitiator 2074 (Product name, Rhodia Japan Co., Ltd.), Irgacure (IRGACURE) 250 (Product name, BASF Japan Co., Ltd.) ), UV-9380C (trade name, GE Toshiba Silicone Co., Ltd.).
  • the polymer constituting the composite material of the present invention such as a curing agent
  • one or more other suitable components such as a curing agent, a catalyst, etc. , Stabilizers and the like may be added.
  • the curing agent a conventionally known latent curing agent that is usually used as a curing agent for epoxy resins can be used.
  • the latent epoxy resin curing agent include amine curing agents, novolak resin curing agents, imidazole curing agents, and acid anhydride curing agents.
  • amine curing agents include aliphatic polyamines such as diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, and isophoronediamine.
  • 1,3-bisaminomethylcyclohexane bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, alicyclic polyamines such as laromine, fragrances such as diaminodiphenylmethane, diaminodiphenylethane, metaphenylenediamine Group polyamines and the like.
  • novolak resin-based curing agents examples include phenol novolac resins and bisphenol novolac resins.
  • the imidazole curing agent include 2-methylimidazole, 2-ethylhexylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, and the like.
  • acid anhydride curing agents examples include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexene tetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride Acid, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride and the like can be mentioned.
  • a curing accelerator for accelerating the curing reaction between the polymerizable compound having a glycidyl group, an epoxy group, or an oxetanyl group and the curing agent may be further used.
  • the curing accelerator include tertiary amines such as benzyldimethylamine, tris (dimethylaminomethyl) phenol, dimethylcyclohexylamine, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methyl.
  • Imidazoles such as imidazole, organophosphorus compounds such as triphenylphosphine, quaternary phosphonium salts such as tetraphenylphosphonium bromide, 1,8-diazabicyclo [5.4.0] undecene-7, and organic acid salts thereof
  • examples include diazabicycloalkenes, quaternary ammonium salts such as tetraethylammonium bromide and tetrabutylammonium bromide, and boron compounds such as boron trifluoride and triphenylborate.
  • These curing accelerators can be used alone or in admixture of two or more.
  • a stabilizer is preferably added to prevent undesired polymerization during storage. All compounds known to those skilled in the art can be used as stabilizers. Representative examples of stabilizers include 4-ethoxyphenol, hydroquinone, butylated hydroxytoluene (BHT) and the like.
  • composition of polymer / liquid crystal composite material The content of the liquid crystal composition in the polymer / liquid crystal composite material of the present invention is possible as long as the composite material can express an optically isotropic liquid crystal phase. It is preferable that the content is as high as possible. This is because the electric birefringence value of the composite material of the present invention increases as the content of the liquid crystal composition is higher.
  • the content of the liquid crystal composition is preferably 60 to 99% by weight, more preferably 60% to 98% by weight, and more preferably 80% to 97% by weight with respect to the composite material. Weight percent is particularly preferred.
  • the polymer content is preferably 1% to 40% by weight, more preferably 2% to 40% by weight, more preferably 3% by weight to the composite material. % To 20% by weight is particularly preferred.
  • the optical element of the present invention is a liquid crystal composition or a polymer / liquid crystal composite material (hereinafter, the liquid crystal composition of the present invention and the polymer / liquid crystal composite material may be collectively referred to as a liquid crystal medium).
  • a liquid crystal medium is an optical element driven in an optically isotropic liquid crystal phase.
  • the liquid crystal medium is optically isotropic, but when an electric field is applied, the liquid crystal medium exhibits optical anisotropy, and light modulation by the electric field becomes possible.
  • the liquid crystal composition of the present invention can be used for an optical element. Since the liquid crystal composition of the present invention exhibits a low driving voltage and a short response time, the optical element according to a preferred embodiment of the present invention can be driven at a low voltage and can respond at high speed.
  • DRX-500 (trade name, Bruker BioSpin Co., Ltd.) was used. The measurement was carried out by dissolving the sample produced in Examples and the like in a deuterated solvent in which a sample such as CDCl 3 is soluble, and at room temperature under conditions of 500 MHz and 24 times of integration.
  • s is a singlet
  • d is a doublet
  • t is a triplet
  • q is a quartet
  • m is a multiplet.
  • Tetramethylsilane (TMS) was used as a reference material for the zero point of the chemical shift ⁇ value.
  • GC -14B type gas chromatograph manufactured by Shimadzu Corporation was used as the GC analyzer .
  • a capillary column CBP1-M25-025 (length: 25 m, inner diameter: 0.22 mm, film thickness: 0.25 ⁇ m) manufactured by Shimadzu Corporation; dimethylpolysiloxane; nonpolar) as the stationary liquid phase was used.
  • Helium was used as the carrier gas, and the flow rate was adjusted to 1 ml / min.
  • the temperature of the sample vaporizing chamber was set to 300 ° C.
  • the temperature of the detector (FID) portion was set to 300 ° C.
  • the sample was dissolved in toluene to prepare a 1% by weight solution, and 1 ⁇ l of the resulting solution was injected into the sample vaporization chamber.
  • a recorder a C-R6A type Chromatopac manufactured by Shimadzu Corporation or an equivalent thereof was used.
  • the obtained gas chromatogram shows the peak retention time and peak area value corresponding to the component compounds.
  • capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m) manufactured by Agilent Technologies Inc.
  • HP-1 length 30 m, inner diameter 0
  • Rtx-1 from Restek Corporation (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m)
  • BP-1 from SGE International Corporation Pty. Ltd (length 30 m, inner diameter) 0.32 mm, film thickness of 0.25 ⁇ m) or the like
  • SGE International Corporation Pty. Ltd length 30 m, inner diameter 0.32 mm, film thickness of 0.25 ⁇ m
  • the peak area ratio in the gas chromatogram corresponds to the ratio of the component compounds.
  • the weight% of the component compound of the analysis sample is not completely the same as the area% of each peak of the analysis sample.
  • the correction factor is substantially 1. Therefore, the weight% of the component compound in the analysis sample substantially corresponds to the area% of each peak in the analysis sample. This is because there is no significant difference in the correction coefficients of the component liquid crystal compounds.
  • an internal standard method based on the gas chromatogram is used.
  • the liquid crystal compound component (test component) weighed in a certain amount accurately and the reference liquid crystal compound (reference material) are simultaneously measured by gas chromatography, and the area ratio between the peak of the obtained test component and the peak of the reference material Is calculated in advance.
  • the composition ratio of the liquid crystal compound in the liquid crystal composition can be determined more accurately from gas chromatography analysis.
  • Samples for measuring physical property values of liquid crystal compounds include two types: a case where the compound itself is used as a sample, and a case where a compound is mixed with a mother liquid crystal to form a sample.
  • the measurement is performed by the following method. First, 15% by weight of the obtained liquid crystal compound and 85% by weight of the mother liquid crystal are mixed to prepare a sample. Then, an extrapolated value is calculated from the measured value of the obtained sample according to the extrapolation method based on the following calculation formula. This extrapolated value is taken as the physical property value of this compound.
  • ⁇ Extrapolated value> (100 ⁇ ⁇ Measured value of sample> ⁇ ⁇ Weight% of mother liquid crystal> ⁇ ⁇ Measured value of mother liquid crystal>) / ⁇ Weight% of liquid crystal compound>
  • the ratio between the liquid crystal compound and the mother liquid crystal is this ratio, when the smectic phase or crystal is precipitated at 25 ° C., the ratio between the liquid crystal compound and the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight. %: 95% by weight, 1% by weight: 99% by weight, and the physical properties of the sample were measured with a composition in which the smectic phase or crystals did not precipitate at 25 ° C., and extrapolated according to the above formula. This is taken as the physical property value of the liquid crystal compound.
  • mother liquid crystals A There are various types of mother liquid crystals used for measurement.
  • the composition (% by weight) of the mother liquid crystals A is as follows.
  • Phase structure and phase transition temperature Measurement was performed by the following methods (1) and (2).
  • a compound is placed on a hot plate (Mettler FP-52 type hot stage) of a melting point measuring apparatus equipped with a polarizing microscope, and a phase state and its change are observed with a polarizing microscope while heating at a rate of 3 ° C./min. , Identified the type of liquid crystal phase.
  • (2) Using a scanning calorimeter DSC-7 system or Diamond DSC system manufactured by PerkinElmer Inc., the temperature is raised and lowered at a rate of 3 ° C./min, and the start point of the endothermic peak or exothermic peak accompanying the phase change of the sample is extrapolated. To determine the phase transition temperature.
  • the crystal is expressed as K, and when the crystal can be distinguished, it is expressed as K 1 or K 2 , respectively.
  • the smectic phase is represented as Sm
  • the nematic phase is represented as N
  • the chiral nematic phase is represented as N * .
  • the liquid (isotropic) was designated as I.
  • the smectic phase can be distinguished from the smectic B phase or the smectic A phase, it is expressed as SmB or SmA, respectively.
  • BP represents a blue phase or an optically isotropic liquid crystal phase.
  • the coexistence state of two phases may be expressed in the form of (N * + I) and (N * + BP).
  • (N * + I) represents a phase in which a non-liquid crystal isotropic phase and a chiral nematic phase coexist
  • (N * + BP) represents a BP phase or an optically isotropic liquid crystal phase.
  • Un represents an unidentified phase that is not optically isotropic.
  • K 50.0 N 100.0 I means that the phase transition temperature (KN) from the crystal to the nematic phase is 50.0 ° C., and the phase from the nematic phase to the liquid
  • the transition temperature (NI) is 100.0 ° C. The same applies to other notations.
  • T NI Maximum temperature of nematic phase
  • a sample mixture of liquid crystal compound and mother liquid crystal
  • a hot plate Metal FP-52 type hot stage
  • a melting point measuring apparatus equipped with a polarizing microscope and heat the polarizing microscope while heating at a rate of 1 ° C./min.
  • the temperature at which a part of the sample changed from a nematic phase to an isotropic liquid was defined as the upper limit temperature of the nematic phase.
  • the upper limit temperature of the nematic phase may be simply abbreviated as “upper limit temperature”.
  • Viscosity (bulk viscosity; ⁇ ; measured at 20 ° C .; mPa ⁇ s) A mixture of the liquid crystal compound and the mother liquid crystal was measured using an E-type viscometer.
  • the pitch of cholesteric liquid crystals having a reflection wavelength in the longer wavelength region than visible light is proportional to the reciprocal of the concentration of the optically active compound in the region where the optically active compound concentration is low.
  • the length was measured at several points and determined by a linear extrapolation method.
  • the “optically active compound” corresponds to the chiral agent in the present invention.
  • the characteristic value of the liquid crystal composition can be measured according to the following method. Many of them are the methods described in the Standard of Electronics Industry Association of Japan EIAJ ED-2521A, or a modified method thereof. No TFT was attached to the TN device used for measurement.
  • nematic phase 1-11 Maximum temperature of nematic phase (NI; ° C) A sample was placed on a hot plate of a melting point measurement apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when a part of the sample changed from a nematic phase to an isotropic liquid.
  • the upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”.
  • nematic phase lower limit temperature T C; °C
  • T C nematic phase lower limit temperature
  • Viscosity (Rotational viscosity; ⁇ 1; measured at 25 ° C .; mPa ⁇ s) 1) Sample having positive dielectric anisotropy: Measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was put in a TN device having a twist angle of 0 ° and a distance (cell gap) between two glass substrates of 5 ⁇ m. The voltage was applied to the TN device stepwise in the range of 16 to 19.5 volts every 0.5 volts.
  • Threshold voltage (Vth; measured at 25 ° C .; V) 1) A composition having a positive dielectric anisotropy: a normally white mode (normally white mode) in which a distance (gap) between two glass substrates is (0.5 / ⁇ n) ⁇ m and a twist angle is 80 degrees. A sample was put in a liquid crystal display element in white mode). ⁇ n is a value of refractive index anisotropy measured by the above method. A rectangular wave having a frequency of 32 Hz was applied to this element. The voltage of the rectangular wave was increased and the value of the voltage when the transmittance of light passing through the element reached 90% was measured.
  • composition having a negative dielectric anisotropy For a normally black mode liquid crystal display element in which the distance (gap) between two glass substrates is about 9 ⁇ m and processed in homeotropic alignment A sample was placed. A rectangular wave having a frequency of 32 Hz was applied to this element. The voltage of the rectangular wave was raised, and the value of the voltage when the transmittance of light passing through the element reached 10% was measured.
  • VHR Voltage holding ratio
  • the TN device used for the measurement has a polyimide alignment film, and the distance (cell gap) between the two glass substrates is 6 ⁇ m. This element was sealed with an adhesive polymerized by ultraviolet rays after putting a sample.
  • the TN device was charged by applying a pulse voltage (60 microseconds at 5 V).
  • the decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined.
  • the area B is an area when it is not attenuated.
  • the voltage holding ratio is a percentage of the area A with respect to the area B.
  • the pitch length was measured using selective reflection (Liquid Crystal Manual 196, 2000, Maruzen).
  • ⁇ n> represents an average refractive index and is given by the following equation.
  • ⁇ n> ⁇ (n ⁇ 2 + n ⁇ 2 ) / 2 ⁇ 1/2 .
  • the selective reflection wavelength was measured with a microspectrophotometer (JEOL Ltd., trade name MSV-350). The pitch was obtained by dividing the obtained reflection wavelength by the average refractive index.
  • the pitch of a cholesteric liquid crystal having a reflection wavelength in the longer wavelength region than visible light is proportional to the reciprocal of the concentration of the chiral agent in a region where the chiral agent concentration is low, so the pitch length of a liquid crystal having a selective reflection wavelength in the visible light region is increased.
  • the ratio (percentage) of the component or liquid crystal compound is a weight percentage (% by weight) based on the total weight of the liquid crystal compound.
  • the composition is prepared by measuring the weight of components such as a liquid crystal compound and then mixing them. Therefore, it is easy to calculate the weight percentage of the component.
  • Step 1-1 Synthesis of Compound (S102) Under a nitrogen stream, a commercially available compound (S101) (10.0 g, 47.1 mmol) in THF (100 mL) was cooled to ⁇ 78 ° C., and LHMDS (lithium Bis (trimethylsilyl) amide) / THF solution (1.08 mol / L) (65.4 mL, 70.7 mmol) was slowly added dropwise and stirred at the same temperature for 1 hour. Next, ethyl cyanoformate (7.00 g, 70.7 mmol) was slowly added dropwise and stirred at the same temperature for 1 hour, and further stirred at room temperature for 5 hours.
  • LHMDS lithium Bis (trimethylsilyl) amide
  • reaction solution was poured into an aqueous ammonium chloride solution, extracted with ethyl acetate (500 mL), washed 3 times with brine, and the organic phase was concentrated under reduced pressure.
  • Step 1-2 Synthesis of Compound (S103) Under a nitrogen stream, boron tribromide (100 mL) was added to a solution of the compound (S102) (11.0 g, 38.7 mmol) obtained in the previous step in dichloromethane (100 mL) at ⁇ 10 ° C. 12.6 g, 50.3 mmol) was slowly added and stirred at room temperature for 1 hour. The reaction solution was poured into water, dichloromethane (100 mL) was added, and the mixture was washed 3 times with water, and then the organic phase was concentrated under reduced pressure.
  • Step 1-3 Synthesis of Compound (S104) Under a nitrogen stream, LAH (2.07 g, 54.6 mmol) in THF (30 mL) was added to the compound (S103) obtained in the previous step at 0 ° C. (7.39 g, 27.3). mmol) in THF was slowly added dropwise and stirred at room temperature for 2 hours. Next, the reaction solution was cooled to 0 ° C., and 2N-HCl aqueous solution (30 mL) was slowly added dropwise, followed by extraction with ethyl acetate (200 mL), filtration of the suspension, and concentration of the organic phase under reduced pressure.
  • Step 1-4 Synthesis of Compound (S105) Under a nitrogen stream, Compound (S104) obtained in the previous step (1.17 g, 6.28 mmol), 3,4,5-trifluorobenzaldehyde (0.910 g, 5.68 mmol) , P-toluenesulfonic acid monohydrate (35.1 mg, 0.18 mmol), magnesium sulfate (2.34 g, 0.019 mmol), and dichloromethane (10 mL) were heated and stirred at 60 ° C. for 3 hours. The reaction solution was filtered, extracted twice with ethyl acetate (200 mL), washed three times with water, and then the organic phase was concentrated under reduced pressure.
  • Step 1-5) Synthesis of Compound (1-2-S1) Under a nitrogen stream, compound (S105) (1.00 g, 3.05 mmol), potassium carbonate (0.88 g, 6.40 mmol), TBAB ( A mixed solution of tetrabutylammonium bromide) (0.29 g, 0.910 mmol) in DMF (10 mL) was stirred with heating at 40 ° C. for 30 minutes. Next, a DMF (10 mL) solution of compound (S106) (1.46 g, 3.05 mmol (purity: 75%)) was slowly added dropwise at the same temperature, and the mixture was heated and stirred at 65 ° C. for 3 hours.
  • a liquid crystal composition AS1 composed of the base liquid crystal A (85% by weight) and the compound (1-2-S1) (15% by weight) obtained in Example 1 was prepared.
  • the physical property value of the obtained liquid crystal composition AS1 was measured, and the extrapolated value of the physical property of the compound (1-2-S1) was calculated by extrapolating the measured value.
  • Example 2 Preparation of nematic liquid crystal composition (NLC) As shown in Table 1, nematic liquid crystal compositions NLC-A, NLC-B and NLC containing the compound (1-2-S1) synthesized in Example 1 were used. -C was prepared (Table 1). Similarly, as shown in Table 1, liquid crystal compositions NLC-AR and NLC-BR containing no compound (1-2-S1) were prepared. In Table 1, each compound showed correspondence with the general formula of this specification. In addition, the phase transition point of each nematic liquid crystal composition was as shown in Table 2.
  • Example 3 Preparation of chiral liquid crystal composition (CLC) Next, each nematic liquid crystal composition shown in Table 1 was mixed with chiral agents BN-H4 and BN-H5 shown below to obtain a chiral liquid crystal composition CLC. -A, CLC-B, CLC-C, CLC-AR and CLC-BR were prepared. Table 3 shows the composition and phase transition point of the chiral liquid crystal composition.
  • Example 4 Preparation of liquid crystal composition (MLC) as a mixture with a polymerizable monomer
  • MLC liquid crystal composition
  • Example 3 Each chiral liquid crystal composition (CLC) prepared in Example 3 was heated and mixed in a isotropic phase with a mixture of a polymerizable monomer.
  • liquid crystal compositions MLC-A, MLC-B, MLC-C, MLC-AR and MLC-BR were prepared. Table 4 shows the composition and phase transition of these liquid crystal compositions.
  • LCA-6, LCA-12 and DMPA described in Table 4 are 1,4-di (4- (6- (acryloyloxy) hexyloxy) benzoyloxy) -2-methylbenzene (LCA-6), 1 , 4-di (4- (6- (acryloyloxy) dodecyloxy) benzoyloxy) -2-methylbenzene (LCA-12), 2,2′-dimethoxyphenylacetophenone, DMPA is a photopolymerization initiator .
  • Example 5 Cell in which preparation of polymer / liquid crystal composite material is held
  • the liquid crystal composition (MLC) which is a mixture of a chiral liquid crystal composition (CLC) and a polymerizable monomer, is not subjected to alignment treatment. It was sandwiched between a comb-shaped electrode substrate and a counter glass substrate (non-electrode provided) and heated to a blue phase.
  • ultraviolet light (ultraviolet light intensity: 23 mWcm-2 (365 nm)) is irradiated for 1 minute to conduct a polymerization reaction, and polymer / liquid crystal composite materials PSBP-A, PSBP-B, PSBP-C, PSBP-AR And a cell in which PSBP-BR was sandwiched was prepared (cell thickness 7-8 ⁇ m).
  • the polymerization temperature was as shown in Table 5.
  • the polymer / liquid crystal composite material (PSBP) thus obtained maintained an optically isotropic liquid crystal phase even when cooled to room temperature.
  • Example 6 Optical System Using Cell
  • the cell sandwiched with the polymer / liquid crystal composite material obtained in Example 5 was set in the optical system shown in FIG. Specifically, a white light source of a polarization microscope (Nikon Eclipse LV100POL) is used as the light source, the incident angle to the cell is perpendicular to the cell surface, and the line direction of the comb-shaped electrode is Polarizer and Analyzer polarizer A cell in which the polymer / liquid crystal composite material obtained in Example 5 was held so as to be 45 ° with respect to each other was set (FIG. 2). Using this optical system, the relationship between the applied voltage and the transmittance of the polymer / liquid crystal composite material obtained in Example 5 at room temperature was examined. Table 5 shows the physical property values of the polymer / liquid crystal composite material (PSBP) sandwiched between the cells. Note that the response time data are those when applying and removing the saturation voltage.
  • PSBP polymer / liquid crystal composite material
  • CLC-A is a composition obtained by adding Compound 1 to CLC-AR.
  • CLC-A has a higher clearing point of about 15 ° C. Therefore, when PSBP is prepared using CLC-A, it becomes PSBP having a clearing point that is about 15 ° C. higher than CLC-AR.
  • the saturation voltage (Vmax) of PSBP-A and PSBP-AR is almost equal to 43 V, and it can be seen that compound 1 is a compound that greatly increases the clearing point without increasing Vmax.
  • the composition using this has a high clearing point and a low driving voltage.
  • the optical element of the present invention is superior to the prior art because it has a high upper limit temperature of the liquid crystal phase and can be driven at a high voltage with a high contrast.
  • Examples of the utilization method of the present invention include optical elements such as display elements using a polymer / liquid crystal composite.

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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)
  • Liquid Crystal (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)

Abstract

L'invention concerne une composition à cristaux liquides présentant une phase à cristaux liquides optiquement isotrope et contenant un agent chiral et un constituant achiral (T) qui contient un ou plusieurs types d'un composé (1) présentant : un cycle dioxane qui est non substitué ou substitué par un groupe méthyle ; et au moins un groupe de liaison -COO- ou -CF2O-. Cette composition à cristaux liquides est utile comme milieu cristallin liquide qui présente une stabilité à la chaleur et à la lumière, une large plage de température de phase à cristaux liquides, une anisotropie diélectrique extrêmement grande et permet d'obtenir une phase à cristaux liquides optiquement isotrope.
PCT/JP2013/078614 2012-10-23 2013-10-22 Composé à cristaux liquides, milieu cristallin liquide et élément optique WO2014065293A1 (fr)

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JPWO2016174968A1 (ja) * 2015-04-28 2018-02-22 Jnc株式会社 液晶組成物および液晶表示素子
CN110079335A (zh) * 2018-01-26 2019-08-02 夏普株式会社 液晶组成物、高分子/液晶复合材料及其制造方法
CN111040781A (zh) * 2018-10-15 2020-04-21 Dic株式会社 向列液晶组合物和使用其的液晶显示元件

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