WO2021193708A1 - Composé, composition de cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

Composé, composition de cristaux liquides et élément d'affichage à cristaux liquides Download PDF

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WO2021193708A1
WO2021193708A1 PCT/JP2021/012218 JP2021012218W WO2021193708A1 WO 2021193708 A1 WO2021193708 A1 WO 2021193708A1 JP 2021012218 W JP2021012218 W JP 2021012218W WO 2021193708 A1 WO2021193708 A1 WO 2021193708A1
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diyl
hydrogen
formula
fluorine
carbons
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PCT/JP2021/012218
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Japanese (ja)
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稲垣　順一
木村　敬二
道子 高橋
秀典 相原
林　和史
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Jnc株式会社
Jnc石油化学株式会社
公益財団法人相模中央化学研究所
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Priority to CN202180007071.2A priority Critical patent/CN114787130A/zh
Priority to JP2022510597A priority patent/JPWO2021193708A1/ja
Publication of WO2021193708A1 publication Critical patent/WO2021193708A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C—CHEMISTRY; METALLURGY
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/16—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon double bonds, e.g. stilbenes
    • C—CHEMISTRY; METALLURGY
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
    • C—CHEMISTRY; METALLURGY
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C—CHEMISTRY; METALLURGY
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C—CHEMISTRY; METALLURGY
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C—CHEMISTRY; METALLURGY
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells

Definitions

  • the present invention relates to a liquid crystal compound having a carbazole ring, a liquid crystal composition, and a liquid crystal display element. More specifically, the present invention relates to a liquid crystal compound having a carbazole ring and having a negative dielectric anisotropy, a liquid crystal composition containing the same, and a liquid crystal display element containing the composition.
  • the classification based on the operation mode of the liquid crystal molecule is PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS. (In-plane switching), VA (vertical alignment), FFS (fringe field switching), FPA (field-induced photo-reactive alignment) and other modes.
  • the classifications based on the drive method of the element are PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into TFT (thin film transistor), MIM (metal insulator metal), and the like.
  • a liquid crystal composition is enclosed in this element.
  • the physical characteristics of this composition are related to the properties of the device. Examples of physical properties in the composition are stability to heat and light, temperature range of nematic phase, viscosity, optical anisotropy, dielectric anisotropy, specific resistance, elastic constant and the like.
  • the composition is prepared by mixing many liquid crystal compounds. The physical characteristics required for the compound are high stability to the environment such as water, air, heat and light, wide temperature range of liquid crystal phase, small viscosity, appropriate optical anisotropy, large dielectric anisotropy, appropriate elastic constant. , Good compatibility with other liquid crystal compounds, etc. Compounds with a high upper temperature limit of the nematic phase are preferred.
  • Compounds having a low lower limit temperature in the liquid crystal phase such as the nematic phase and the smectic phase are preferable. Compounds with low viscosities contribute to the short response time of the device.
  • the appropriate value of optical anisotropy depends on the type of operating mode of the device. In order to drive the device at a low voltage, a compound having a large positive or negative dielectric anisotropy is preferable. In order to prepare the composition, a compound having good compatibility with other liquid crystal compounds is preferable. Since the device may be used at a temperature below freezing, a compound having good compatibility at a low temperature is preferable.
  • Patent Document 1 discloses compounds having numbers 53, 54, and 56 in Table 4 on page 41, and compounds having numbers 125 and 127 in Table 8 on page 45.
  • Patent Document 2 discloses the II-a compound of Example 3 on page 10, and the III-a compound of Example 7 on page 14.
  • the first challenge is high stability to heat and light, high transparency (or high upper limit temperature of nematic phase), lower lower limit temperature of liquid crystal phase, small viscosity, proper optical anisotropy, negatively large dielectric constant difference. It is an object of the present invention to provide a liquid crystal compound that satisfies at least one of physical characteristics such as anisotropy, an appropriate elastic constant, and good compatibility with other liquid crystal compounds. It is to provide a compound having a negatively large dielectric anisotropy as compared with a similar compound.
  • the second challenge is that it contains this compound and has high stability to heat and light, high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, proper optical anisotropy, negatively large dielectric constant difference. It is an object of the present invention to provide a liquid crystal composition that satisfies at least one of physical characteristics such as anisotropy, a large specific resistance, and an appropriate elastic constant. The challenge is to provide a liquid crystal composition having an appropriate balance with respect to at least two physical characteristics.
  • a third challenge is a liquid crystal display that contains this composition and has a wide temperature range in which the device can be used, a short response time, a large voltage retention rate, a low threshold voltage, a large contrast ratio, a small flicker rate, and a long life. It is to provide an element.
  • the present invention relates to a compound represented by the formula (1), a liquid crystal composition containing this compound, and a liquid crystal display element containing this liquid crystal composition.
  • Ra is a hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched chain alkyl having 3 to 6 carbon
  • Rings N 1 and N 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2, 6-diyl, 2,6,7-trioxabicyclo [2.2.2] octane-1,4-diyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl , Dihydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, furan-2,4-diyl, furan-2, 5-diyl, thiophene-2,4-diyl,
  • At least one hydrogen may be replaced with fluorine or chlorine;
  • L 1 , L 2 , L 3 , L 4 , L 5 , and L 6 independently hydrogen, fluorine, chlorine, -CF 3 , -CHF 2 , -CH 2 F, -OCF 3 , -OCHF 2 , It is -OCH 2 F, or -C ⁇ N,;
  • L 5 and L 6 are hydrogen, at least one of L 1 , L 2 , L 3 , and L 4 is fluorine, chlorine, -CF 3 , -CHF 2 , -CH 2 F, -OCF 3 , -OCHF 2, be -OCH 2 F, or -C ⁇ N,
  • L 1 , L 2 , L 3 , and L 4 are all hydrogen, at least one of L 5 and L 6 is fluorine, chlorine, -CF 3 , -CHF 2 , -CH 2 F, -OCF 3 , -OCHF 2, be -OCH 2
  • the first advantages are high stability to heat and light, high transparency (or high upper limit temperature of nematic phase), lower lower limit temperature of liquid crystal phase, low viscosity, proper optical anisotropy, negatively large dielectric constant difference. It is an object of the present invention to provide a liquid crystal compound that satisfies at least one of physical characteristics such as anisotropy, an appropriate elastic constant, and good compatibility with other liquid crystal compounds. It is to provide a compound having a negatively large dielectric anisotropy as compared with a similar compound.
  • the second advantage is that it contains this compound and has high stability to heat and light, high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, proper optical anisotropy, negatively large dielectric constant difference. It is an object of the present invention to provide a liquid crystal composition that satisfies at least one of physical characteristics such as anisotropy, a large specific resistance, and an appropriate elastic constant. This advantage is to provide a liquid crystal composition having an appropriate balance with respect to at least two physical characteristics.
  • the third advantage is that the liquid crystal display contains this composition and has a wide temperature range in which the device can be used, a short response time, a large voltage retention rate, a low threshold voltage, a large contrast ratio, a small flicker rate, and a long life. It is to provide an element.
  • liquid crystal compound liquid crystal composition
  • liquid crystal display element may be abbreviated as “compound”, “composition”, and “element”, respectively.
  • the “liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and a compound having no liquid crystal phase but adjusting the physical properties of a composition such as an upper limit temperature, a lower limit temperature, a viscosity, and a dielectric constant anisotropy.
  • Liquid crystal display element is a general term for a liquid crystal display panel and a liquid crystal display module.
  • polymerizable compound is a compound added for the purpose of forming a polymer in the composition. Liquid crystal compounds with alkenyl are not polymerizable in that sense.
  • the liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives are added to this composition for the purpose of further adjusting the physical characteristics. Additives such as polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, and defoamers are added as needed. NS.
  • the liquid crystal compounds and additives are mixed in such a procedure. The ratio (content) of the liquid crystal compound is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive even when the additive is added.
  • the ratio (addition amount) of the additive is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total weight of the liquid crystal compound. Parts per million by weight (ppm) may also be used.
  • the proportions of polymerization initiators and polymerization inhibitors are exceptionally expressed based on the weight of the polymerizable compound.
  • the “transparency point” is the transition temperature between the liquid crystal phase and the isotropic phase in the liquid crystal compound.
  • the “lower limit temperature of the liquid crystal phase” is the transition temperature of the solid-liquid crystal phase (smetic phase, nematic phase, etc.) in the liquid crystal compound.
  • the “upper limit temperature of the nematic phase” is the transition temperature of the nematic phase-isotropic phase in the mixture of the liquid crystal compound and the mother liquid crystal or the liquid crystal composition, and may be abbreviated as the “upper limit temperature”.
  • the “lower limit temperature of the nematic phase” may be abbreviated as the "lower limit temperature”.
  • the expression “increase the dielectric anisotropy” means that when the composition has a positive dielectric anisotropy, its value increases positively, and the composition has a negative dielectric anisotropy. When it is a thing, it means that its value increases negatively.
  • “Large voltage retention” means that the element has a large voltage retention not only at room temperature but also at a temperature close to the upper limit temperature at the initial stage, and after long-term use, it has a large voltage not only at room temperature but also at a temperature close to the upper limit temperature. It means having a retention rate.
  • the characteristics of the composition or device may be examined before and after the aging test (including the accelerated deterioration test).
  • the compound represented by the formula (1) may be abbreviated as the compound (1).
  • At least one compound selected from the group of compounds represented by the formula (1) may be abbreviated as the compound (1).
  • “Compound (1)” means one compound represented by the formula (1), a mixture of two compounds, or a mixture of three or more compounds. These rules also apply to compounds represented by other formulas.
  • symbols such as A 1 , B 1 , and C 1 enclosed in hexagons correspond to rings such as ring A 1 , ring B 1 , and ring C 1, respectively.
  • the hexagon represents a six-membered ring such as cyclohexane or benzene.
  • the hexagon may represent a fused ring such as naphthalene or a crosslinked ring such as adamantane.
  • R 11 In the chemical formulas of the component compounds, with symbols of terminal groups R 11 to a plurality of compounds.
  • two groups represented by any two R 11 may be may be the same or different.
  • R 11 of compound (2) is ethyl and R 11 of compound (3) is ethyl.
  • R 11 of compound (2) is ethyl and R 11 of compound (3) is propyl.
  • This rule also applies to symbols such as R 12 , R 13 , and Z 11.
  • i when i is 2, two rings E 1 is present.
  • the two two wherein the ring E 1 represents the compound may be the same or different.
  • i is greater than 2
  • This rule also applies to other symbols.
  • At least one'A' means that the number of'A's is arbitrary.
  • the expression “at least one'A'may be replaced by'B'” is that when the number of'A's is 1, the position of the'A'is arbitrary and the number of'A's is 2. When more than one, it means that their positions can be selected without limitation. This rule also applies to the expression “at least one'A' has been replaced by a'B'".
  • the expression "at least one'A' may be replaced by'B','C',or'D'" is any'if any'A' is replaced by a'B'.
  • Alkyl such as in, -CH 2 methyl moiety (-CH 2 -H) - by is replaced by -O- is not preferred also be the -O-H.
  • R 11 and R 12 are independently alkyls with 1 to 10 carbons or alkenyl with 2 to 10 carbons, in which at least one -CH 2- is replaced with -O-. Often, in these groups, at least one hydrogen may be replaced by fluorine.
  • in these groups may be interpreted literally.
  • these groups means alkyl, alkenyl, alkoxy, alkenyloxy and the like. That is, “these groups” refers to all of the groups described prior to the term “in these groups”. This common-sense interpretation also applies to the terms “in these monovalent groups” and “in these divalent groups”. For example, “these monovalent groups” refers to all of the groups described prior to the term “in these monovalent groups”.
  • Halogen means fluorine, chlorine, bromine, and iodine. Preferred halogens are fluorine and chlorine. A more preferred halogen is fluorine.
  • the alkyl of the liquid crystal compound is linear or branched and does not contain cyclic alkyl. Linear alkyl is generally preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl.
  • the configuration for 1,4-cyclohexylene is preferably trans over cis in order to raise the upper temperature limit.
  • 2-Fluoro-1,4-phenylene means the following two divalent groups.
  • fluorine may be left-facing (L) or right-facing (R). This rule also applies to asymmetric divalent groups generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl.
  • the present invention includes the following items.
  • Item 1 A compound represented by the formula (1).
  • Ra is a hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched chain alkyl having 3 to 6 carbon
  • Rings N 1 and N 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2, 6-diyl, 2,6,7-trioxabicyclo [2.2.2] octane-1,4-diyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl , Dihydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, furan-2,4-diyl, Fran-2,5-diyl, thiophene-2,4-diyl,
  • At least one hydrogen is fluorine, chlorine, -C ⁇ N, -CF 3 , -CHF 2 , -CH 2 F, -OCF 3 , -OCHF 2 , or -OCH 2.
  • At least one hydrogen may be replaced with fluorine or chlorine;
  • L 1 , L 2 , L 3 , L 4 , L 5 , and L 6 independently hydrogen, fluorine, chlorine, -CF 3 , -CHF 2 , -CH 2 F, -OCF 3 , -OCHF 2 , It is -OCH 2 F, or -C ⁇ N,;
  • L 5 and L 6 are hydrogen, at least one of L 1 , L 2 , L 3 , and L 4 is fluorine, chlorine, -CF 3 , -CHF 2 , -CH 2 F, -OCF 3 , -OCHF 2, be -OCH 2 F, or -C ⁇ N,
  • L 1 , L 2 , L 3 , and L 4 are all hydrogen, at least one of L 5 and L 6 is fluorine, chlorine, -CF 3 , -CHF 2 , -CH 2 F, -OCF 3 , -OCHF 2, be -OCH 2
  • Item 2. The compound according to Item 1, represented by the formulas (1-1) to (1-13).
  • R 1 is hydrogen, an alkyl having 1 to 15 carbon atoms, an alkoxy having 1 to 14 carbon atoms, an alkoxy alkyl having 2 to 14 carbon atoms, an alkenyl having 2 to 15 carbon atoms, or an alkenyloxy having 2 to 14 carbon atoms.
  • R 2 is hydrogen, fluorine, chlorine, -CF 3, -OCF 3, -C ⁇ N, alkyl of from 1 to 15 carbon atoms, alkoxy having 1 to 14 carbon atoms, from 2 to 14 carbon atoms in the alkoxyalkyl, carbon atoms 2 to 15 alkenyl, or 2 to 14 carbon alkenyloxy;
  • Ra is a hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched chain alkyl having 3 to 6 carbon atoms;
  • Rings A 1 and A 2 are independently cycloalkylenes having 3 to 5 carbon atoms, and in the rings A 1 and A 2 , at least one -CH 2- can be replaced with -O-.
  • Rings N 1 and N 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2, 6-diyl, 2,6,7-trioxabicyclo [2.2.2] octane-1,4-diyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl , Dihydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, furan-2,4-diyl, furan-2, 5-diyl, thiophene-2,4-diyl,
  • At least one hydrogen may be replaced with fluorine or chlorine;
  • L 1 , L 2 , L 3 , and L 4 are independently hydrogen, fluorine, chlorine, -CF 3 , -CHF 2 , -CH 2 F, -OCF 3 , -OCHF 2 , -OCH 2 F, or -C ⁇ N, and at least one of L 1 , L 2 , L 3 , and L 4 is fluorine, chlorine, -CF 3 , -CHF 2 , -CH 2 F, -OCF 3 , -OCHF 2 , It is -OCH 2 F, or -C ⁇ N,;
  • R 1 does not become hydrogen
  • R 2 does not become hydrogen.
  • R 1 and R 2 are independently from hydrogen, alkyl with 1 to 10 carbons, alkoxy with 1 to 9 carbons, alkoxyalkyl with 2 to 9 carbons, alkenyl with 2 to 10 carbons, or from 2 carbons.
  • Ra is a hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched chain alkyl having 3 to 6 carbon atoms
  • Rings A 1 and A 2 are independently 1,2-cyclopropylene, 1,3-cyclobutylene, or 1,3-cyclopentylene
  • Rings N 1 and N 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, furan-2,4-diyl, furan-2,5-diyl, thiophene-2,4- Diyl, thiophene-2,5-diyl, benzofuran-2,5-diy
  • Item 4. The compound according to Item 1, which is represented by the formulas (1-14) to (1-26).
  • R 1 is hydrogen, an alkyl having 1 to 15 carbon atoms, an alkoxy having 1 to 14 carbon atoms, an alkoxy alkyl having 2 to 14 carbon atoms, an alkenyl having 2 to 15 carbon atoms, or an alkenyloxy having 2 to 14 carbon atoms.
  • R 2 is hydrogen, fluorine, chlorine, -CF 3, -OCF 3, -C ⁇ N, alkyl of from 1 to 15 carbon atoms, alkoxy having 1 to 14 carbon atoms, from 2 to 14 carbon atoms in the alkoxyalkyl, carbon atoms 2 to 15 alkenyl, or 2 to 14 carbon alkenyloxy;
  • Ra is a hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched chain alkyl having 3 to 6 carbon atoms;
  • Rings A 1 and A 2 are independently cycloalkylenes having 3 to 5 carbon atoms, and in the rings A 1 and A 2 , at least one -CH 2- can be replaced with -O-.
  • Rings N 1 and N 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2, 6-diyl, 2,6,7-trioxabicyclo [2.2.2] octane-1,4-diyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl , Dihydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, furan-2,4-diyl, furan-2, 5-diyl, thiophene-2,4-diyl,
  • Z 1 , Z 2 , Z 3 , and Z 4 are independently single-bonded or alkylenes with 1 to 6 carbon atoms, and in this Z 1 , Z 2 , Z 3 , and Z 4 , at least one -CH.
  • At least one hydrogen may be replaced with fluorine or chlorine;
  • L 5 and L 6 are independently hydrogen, fluorine, chlorine, -CF 3 , -CHF 2 , -CH 2 F, -OCF 3 , -OCHF 2 , -OCH 2 F, or -C ⁇ N.
  • At least one of L 5 and L 6 is fluorine, chlorine, -CF 3 , -CHF 2 , -CH 2 F, -OCF 3 , -OCHF 2 , -OCH 2 F, or -C ⁇ N;
  • formula (1-14) formula (1-16), formula (1-18), formula (1-20), formula (1-22), formula (1-24), and formula (1-26).
  • R 1 does not become hydrogen
  • formulas (1-14) to (1-18) formula (1-21), formula (1-22), formula (1-25), and formula (1).
  • R 2 does not become hydrogen.
  • R 1 and R 2 are independently from hydrogen, alkyl with 1 to 10 carbons, alkoxy with 1 to 9 carbons, alkoxyalkyl with 2 to 9 carbons, alkenyl with 2 to 10 carbons, or from 2 carbons.
  • Ra is a hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched chain alkyl having 3 to 6 carbon atoms
  • Rings A 1 and A 2 are independently 1,2-cyclopropylene, 1,3-cyclobutylene, or 1,3-cyclopentylene
  • Rings N 1 and N 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, furan-2,4-diyl, furan-2,5-diyl, thiophene-2,4- Diyl, thiophene-2,5-diyl, benzofuran-2,5-diy
  • At least one of L 5 and L 6 is fluorine, chlorine, -CF 3 , -CHF 2 , -CH 2 F, -OCF 3 , -OCHF 2 , -OCH 2 F, or -C ⁇ N;
  • R 1 does not become hydrogen
  • formulas (1-14) to (1-18) formula (1-21), formula (1-22), formula (1-25), and formula (1).
  • Item 4 The compound according to Item 4, wherein R 2 does not become hydrogen in ⁇ 26).
  • R 1 and R 2 are independently alkyl with 1 to 10 carbons, alkoxy with 1 to 9 carbons, alkoxyalkyl with 2 to 9 carbons, alkenyl with 2 to 10 carbons, or alkenyl with 2 to 9 carbons.
  • Ra is a hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched chain alkyl having 3 to 6 carbon atoms
  • Z 2 and Z 3 are independently single-bonded, -O-, -COO-, -OCO-, -CH 2 O-, -OCH 2- , -CF 2 O-, -OCF 2 -,-(CH).
  • R 1 and R 2 are independently alkyl with 1 to 10 carbons, alkoxy with 1 to 9 carbons, alkoxyalkyl with 2 to 9 carbons, alkenyl with 2 to 10 carbons, or alkenyl with 2 to 10 carbons.
  • Ra is a hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched chain alkyl having 3 to 6 carbon atoms
  • L 1 , L 2 , L 3 , and L 4 are independently hydrogen, fluorine, chlorine, -CF 3 or -OCF 3 , and at least one of L 1 , L 2 , L 3 , and L 4.
  • X 1 and X 2 are independently hydrogen, fluorine, or chlorine.
  • R 1 and R 2 are independently alkyl with 1 to 10 carbons, alkoxy with 1 to 9 carbons, alkoxyalkyl with 2 to 9 carbons, alkenyl with 2 to 10 carbons, or alkenyl with 2 to 9 carbons.
  • Ra is a hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched chain alkyl having 3 to 6 carbon atoms
  • Z 2 and Z 3 are independently single-bonded, -O-, -COO-, -OCO-, -CH 2 O-, -OCH 2- , -CF 2 O-, -OCF 2 -,-(CH).
  • R 1 and R 2 are independently alkyl with 1 to 10 carbons, alkoxy with 1 to 9 carbons, alkoxyalkyl with 2 to 9 carbons, alkenyl with 2 to 10 carbons, or alkenyl with 2 to 9 carbons.
  • Ra is a hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched chain alkyl having 3 to 6 carbon atoms
  • L 5 and L 6 are independently hydrogen, fluorine, chlorine, -CF 3 , -CHF 2 , -OCF 3 , -OCHF 2 , or -OCH 2 F, and at least one of L 5 and L 6
  • Item 10. The compound according to any one of Items 1 to 3, 6 and 7, represented by the formula (1-1-1) or the formulas (1-3-1) to (1-3-6).
  • R 1 and R 2 are independently alkyl with 1 to 10 carbons, alkoxy with 1 to 9 carbons, alkoxyalkyl with 2 to 9 carbons, alkenyl with 2 to 10 carbons, or alkenyl with 2 to 9 carbons.
  • Ra is a hydrogen, a linear alkyl having 1 to 4 carbon atoms, or a branched chain alkyl having 3 or 4 carbon atoms
  • Item 11 Item 2. The item 1, 4, 5, 8 and 9, which is represented by the formula (1-14-1) or the formula (1-16-1) to the formula (1-16-6). Compound.
  • R 1 and R 2 are independently alkyl with 1 to 10 carbons, alkoxy with 1 to 9 carbons, alkoxyalkyl with 2 to 9 carbons, alkenyl with 2 to 10 carbons, or alkenyl with 2 to 9 carbons.
  • Ra is a hydrogen, a linear alkyl having 1 to 4 carbon atoms, or a branched chain alkyl having 3 or 4 carbon atoms
  • L 5 and L 6 are independently hydrogen, fluorine, chlorine, -CF 3 or -OCF 3 , and at least one of L 5 and L 6 is fluorine, chlorine, -CF 3 or -OCF 3 Is;
  • R 1 and R 2 are independently alkyl with 1 to 10 carbons, alkoxy with 1 to 9 carbons, alkoxyalkyl with 2 to 9 carbons, alkenyl with 2 to 10 carbons, or alkenyl with 2 to 9 carbons.
  • Ra is a hydrogen, a linear alkyl having 1 to 4 carbon atoms, or a branched chain alkyl having 3 or 4 carbon atoms
  • L 1 , L 2 , L 3 , and L 4 are independently hydrogen, fluorine, -CF 3 , or -OCF 3 , and at least two of L 1 , L 2 , L 3 , and L 4 are , Fluorine, -CF 3 , or -OCF 3 , and at least one of L 1 , L 2 , L 3 , and L 4 is hydrogen
  • X 1 and X 2 are independently hydrogen or fluorine.
  • R 1 and R 2 are independently alkyl with 1 to 10 carbons, alkoxy with 1 to 9 carbons, alkoxyalkyl with 2 to 9 carbons, alkenyl with 2 to 10 carbons, or alkenyl with 2 to 9 carbons.
  • Ra is a hydrogen, a linear alkyl having 1 to 4 carbon atoms, or a branched chain alkyl having 3 or 4 carbon atoms
  • L 5 and L 6 are independently hydrogen, fluorine, -CF 3 or -OCF 3 , and at least one of L 5 and L 6 is fluorine, -CF 3 or -OCF 3 .
  • X 1 and X 2 are independently hydrogen or fluorine.
  • Item 14 The compound according to any one of Items 1 to 3, 6, 7, 10, and 12, represented by the formulas (1-1-1-1) to (1-1-1-7).
  • R 1 and R 2 are independently alkyl with 1 to 7 carbons, alkoxy with 1 to 6 carbons, alkoxyalkyl with 2 to 6 carbons, alkenyl with 2 to 7 carbons, or alkenyl with 2 to 7 carbons.
  • Ra is hydrogen, a linear alkyl having 1 to 4 carbon atoms, or a branched chain alkyl having 3 or 4 carbon atoms.
  • Item 15 The item according to any one of Items 1, 4, 5, 8, 9, 11, and 13, which is represented by the formula (1-14-1-1) or the formula (1-14-1-2). Compound.
  • R 1 and R 2 are independently alkyl with 1 to 7 carbons, alkoxy with 1 to 6 carbons, alkoxyalkyl with 2 to 6 carbons, alkenyl with 2 to 7 carbons, or alkenyl with 2 to 7 carbons.
  • Ra is hydrogen, a linear alkyl having 1 to 4 carbon atoms, or a branched chain alkyl having 3 or 4 carbon atoms.
  • Item 16 A liquid crystal composition containing at least one of the compounds according to any one of Items 1 to 15.
  • Item 17 The liquid crystal composition according to Item 16, which contains at least one compound selected from the group of compounds represented by the formulas (2) to (4).
  • R 11 and R 12 are independently alkenyl alkyl carbon atoms or 2 to 10 1 to 10 carbons, and in the R 11 and R 12, at least one -CH 2 - is replaced by -O- At least one hydrogen may be replaced with fluorine;
  • Ring B 1 , Ring B 2 , Ring B 3 and Ring B 4 are independent, 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene, or pyrimidine-2,5-diyl;
  • Item 18. The liquid crystal composition according to Item 16 or 17, further containing at least one compound selected from the group of compounds represented by formulas (5) to (13).
  • R 13 and R 14 are independently alkenyl alkyl carbon atoms or 2 to 10 1 to 10 carbons, and in the R 13 and R 14, at least one -CH 2 - is replaced by -O- At least one hydrogen may be replaced with fluorine;
  • R 15 is hydrogen, fluorine, alkenyl alkyl carbon atoms or 2 to 10 from 10 1 carbon atoms, in the R 15, at least one -CH 2 - may be replaced by -O-, at least One hydrogen may be replaced by fluorine;
  • Ring C 1 , Ring C 2 , Ring C 3 , and Ring C 4 may independently replace 1,4-cyclohexylene, 1,4-cyclohexenylene, and at least one hydrogen with fluorine 1, 4-Phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl;
  • Ring C 5 and ring C 6 are each independently 1,4-cyclohexylene, 1, 1,4
  • Item 19 The liquid crystal composition according to any one of Items 16 to 18, further containing at least one compound selected from the group of compounds represented by the formulas (21) to (23).
  • R 16 is an alkenyl alkyl carbon atoms or 2 to 10 1 to 10 carbons, and in this R 16, at least one -CH 2 - may be replaced by -O-, at least one hydrogen , May be replaced with fluorine;
  • X 11 is fluorine, chlorine, -CF 3 , -CHF 2 , -CH 2 F, -OCF 3 , -OCHF 2 , -OCF 2 CHF 2 , or -OCF 2 CHFCF 3 ;
  • Ring D 1 , Ring D 2 , and Ring D 3 are independently 1,4-cyclohexylene, 1,4-phenylene, where at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl.
  • Item 20 The liquid crystal composition according to any one of Items 16 to 19, further containing at least one compound selected from the group of compounds represented by the formula (24).
  • R 17 is an alkenyl alkyl carbon atoms or 2 to 10 1 to 10 carbons, and in this R 17, at least one -CH 2 - may be replaced by -O-, at least one hydrogen May be replaced with fluorine;
  • X 12 is -C ⁇ N or -C ⁇ C-C ⁇ N;
  • Ring E 1 is 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl.
  • Z 21 is a single bond, -COO-, -CH 2 O-, -CF 2 O-, -OCF 2 -,-(CH 2 ) 2- , or -C ⁇ C-;
  • L 15 and L 16 are independently hydrogen or fluorine; i is 1, 2, 3, or 4.
  • Item 21 A liquid crystal display device containing the liquid crystal composition according to any one of Items 16 to 20.
  • the present invention also includes the following items.
  • the present invention also includes the following items.
  • C One selected from the group of polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, and defoamers.
  • the composition described above further comprising two or at least three additives.
  • D The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C.) is 0.08 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C.). ) Is -2 or less, the above composition.
  • the present invention also includes the following items.
  • E A device containing the above composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, FPA, or PSA.
  • F AM device containing the above composition.
  • G A transmissive device containing the above composition.
  • H Use of the above composition as a composition having a nematic phase.
  • I Use as an optically active composition by adding an optically active compound to the above composition.
  • Compound (1) is characterized by having a divalent group represented by the following formula.
  • X is hydrogen or a substituent.
  • This compound 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. Compositions containing this compound are stable under the conditions in which the device is commonly used. This composition has a negatively large dielectric anisotropy. This compound has the general physical properties required for the components of the composition, the appropriate optical anisotropy, and the appropriate dielectric anisotropy.
  • a preferred embodiment of side groups L 1, L 2, L 3 , L, 4, L 5 and L 6 are as follows. This example also applies to the sub-formula of compound (1).
  • the physical properties can be arbitrarily adjusted by appropriately combining these groups. Because large difference is not in the physical properties of the compound, the compound (1) is, 2 H (deuterium), an isotope such as 13 C may contain more than the amount of natural abundance.
  • the definition of the symbol of compound (1) is as described in Item 1.
  • One hydrogen may be replaced with fluorine or chlorine.
  • R 1 or R 2 are alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkylthio, alkylthioalkoxy, acyl, acylalkyl, acyloxy, acyloxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alkenyl, alkenyloxy, alkenyloxyalkyl, alkoxy. Alkoxy, alkynyl, and alkynyloxy.
  • at least one hydrogen may be replaced with fluorine or chlorine.
  • This example contains a group in which at least two hydrogens have been replaced with both fluorine and chlorine.
  • R 1 or R 2 Groups in which at least one hydrogen is replaced with fluorine alone are even more preferred.
  • R 1 or R 2 a straight chain is preferable to a branched chain. Even if R 1 or R 2 is a branched chain, it is preferable when it is optically active. More preferred R 1 or R 2 are alkyl, alkoxy, alkoxyalkyl, alkenyl, monofluoroalkyl, polyfluoroalkyl, monofluoroalkoxy, and polyfluoroalkoxy.
  • R 2 may be fluorine, chlorine, -C ⁇ N, or -C ⁇ C-C ⁇ N in addition to the above groups.
  • Trans-configuration is preferred for alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl.
  • the cis configuration is preferred for alkenyl such as 2-butenyl, 2-pentenyl, 2-hexenyl.
  • R 1 or R 2 are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, methoxymethyl.
  • Methoxyethyl methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl, butoxymethyl, butoxyethyl, pentoxymethyl, pentoxyethyl, vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-Buthenyl, 3-Butenyl, 1-Pentenyl, 2-Pentenyl, 3-Pentenyl, 4-Pentenyl, 1-Hexenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl, 5-Hexenyl, 1-Heptenyl, 2 -Heptenyl, 3-heptenyl, 4-heptenyl, 5-heptenyl, 6-heptenyl, 2-propenyloxy, 2-butenyloxy, 2-pentenyloxy, 2-hexenyloxy, and 1-propynyl.
  • R 1 or R 2 is 2-fluoroethyl, 3-fluoropropyl, 2,2,2-trifluoroethyl, 2-fluorovinyl, 2,2-difluorovinyl, 2-fluoro-2-vinyl, 3-Fluoro-1-propenyl, 3,3,3-trifluoro-1-propenyl, 4-fluoro-1-propenyl, and 4,4-difluoro-3-butenyl.
  • R 2 is, in addition to the above groups, fluorine, chlorine, -C ⁇ N, -CF 3 , -CHF 2 , -CH 2 F, -CF 2 CF 3 , -CF 2 CHF 2 , -CF. 2 CH 2 F, -CF 2 CF 2 CF 3 , -CF 2 CHFCF 3 , -CHFCF 2 CF 3 , -OCF 3 , -OCHF 2 , -OCH 2 F, -OCF 2 CF 3 , -OCF 2 CHF 2 , It may be -OCF 2 CH 2 F, -OCF 2 CF 2 CF 3 , -OCF 2 CHFCF 3 , and -OCHFCF 2 CF 3.
  • R 1 or R 2 are ethyl, propyl, butyl, pentyl, hexyl, heptyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, methoxymethyl, ethoxymethyl, ethoxyethyl, propoxymethyl, propoxyethyl, Butoxymethyl, pentoxymethyl, 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, 5-hexenyl, 2-propenyloxy, 2-butenyloxy, and 2-pentenyloxy.
  • R 2 is, -OCF 3, -OCHF 2, -OCH 2 F, -OCF 2 CF 3, -OCF 2 CHF 2, -OCF 2 CH 2 F, -OCF 2 CF 2 CF 3, - OCF 2 CHFCF 3 , -OCHFCF 2 CF 3 , fluorine, chlorine, and -C ⁇ N.
  • R 1 or R 2 are ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, vinyl, 1-propenyl, 3 -Butenyl, and 3-pentenyl.
  • the most preferred R 2 is, -OCF 3, -OCHF 2, -CF 3, -CHF 2, -CH 2 F, -OCF 2 CHF 2, -OCF 2 CHFCF 3, fluorine, and -C ⁇ N be.
  • Ra is hydrogen, a linear alkyl having 1 to 6 carbon atoms, or a branched chain alkyl having 3 to 6 carbon atoms.
  • Ras are methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, sec-butyl, pentane-2-yl, hexane-2-yl, pentane-3-yl, hexane-3-yl, tert-butyl. , Tert-pentyl, 3-methylpentane-3-yl, and 3-ethylpentane-3-yl. More preferred Ra are methyl, ethyl, propyl, butyl, isopropyl, sec-butyl, and tert-butyl. Particularly preferred Ra are methyl, ethyl, propyl, and isopropyl. The most preferred Ra are methyl and ethyl.
  • An example of a preferred ring A 1 or ring A 2 is a divalent group represented by the following formulas (25-1) to (25-27).
  • a more preferable example is a divalent group represented by the formulas (25-1) to (25-17).
  • Particularly preferred examples are divalent groups represented by formulas (25-1) to (25-3) and formulas (25-13) to formulas (25-17).
  • the most preferable example is a divalent group represented by the formulas (25-1) to (25-3).
  • ring N 1 and ring N 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4. -Tetrahydronaphthalene-2,6-diyl, 2,6,7-trioxabicyclo [2.2.2] octane-1,4-diyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran -2,5-diyl, dihydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, furan-2,4- Diyl, furan-2,5-diyl, thiophene-2,4-diyl, thiophene-2,5-diyl, benzofur
  • At least one hydrogen is fluorine, chlorine, -C ⁇ N, -CF 3 , -CHF 2 , -CH 2 F, -OCF 3 , -OCHF 2 , or -OCH 2.
  • a preferred example of “may be replaced by F” is a divalent group represented by the following formulas (26-1) to (26-71). More preferred examples are equations (26-1) to (26-4), equations (26-6), equations (26-10) to (26-15), and equations (26-54) to (26). It is a divalent group represented by -59).
  • More preferred ring N 1 or ring N 2 is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 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, 2,3,5-trifluoro-1 , 4-Phenylene, pyridine-2,5-diyl, 3-fluoropyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-2,5-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, and naphthalene-2,6-diyl.
  • Particularly preferred ring N 1 or ring N 2 is 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 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, pyridine-2,5-diyl, and pyrimidine-2,5-diyl. ..
  • the most preferred ring N 1 or ring N 2 is 1,4-cyclohexylene and 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene.
  • Z 1 , Z 2 , Z 3 , and Z 4 are independently single-bonded or alkylenes with 1 to 6 carbon atoms, in Z 1 , Z 2 , Z 3 , and Z 4 .
  • At least one -CH 2- may be replaced with -O-, -S-, -CO-, or -SiH 2-
  • at least one- (CH 2 ) 2 -is -CH CH.
  • -Or -C ⁇ C- may be replaced, and at least one hydrogen may be replaced with fluorine or chlorine.
  • the most preferred Z 1 , Z 2 , Z 3 or Z 4 are single bonds, -CH 2 O- or -OCH 2- .
  • L 1 , L 2 , L 3 , L 4 , L 5 , and L 6 independently contain hydrogen, fluorine, chlorine, -CF 3 , -CHF 2 , -CH 2 F, and -OCF. 3, -OCHF 2, a -OCH 2 F or -C ⁇ N,.
  • L 1 , L 2 , L 3 , and L 4 when both L 5 and L 6 are hydrogen, at least one of L 1 , L 2 , L 3 , and L 4 is fluorine, chlorine, -CF 3 , -CHF 2 , -CH. 2 F, -OCF 3 , -OCHF 2 , -OCH 2 F, or -C ⁇ N, and at least one of L 1 , L 2 , L 3 , and L 4 may be hydrogen. More preferred L 1 , L 2 , L 3 and L 4 are fluorine or -CF 3 . Particularly preferred L 1 , L 2 , L 3 and L 4 are fluorine.
  • L 5 and L 6 when L 1 , L 2 , L 3 , and L 4 are all hydrogen, at least one of L 5 and L 6 is fluorine, chlorine, -CF 3 , -CHF 2 , -CH. 2 F, -OCF 3 , -OCHF 2 , -OCH 2 F, or -C ⁇ N, and at least one of L 5 and L 6 may be hydrogen. More preferred L 5 and L 6 are fluorine or -CF 3 . Particularly preferred L 5 and L 6 are fluorine.
  • l and o are independently 0, or 1 and m, and n are independently 0, 1, or 2, and the sum of l, m, n, and o. Is an integer from 0 to 4.
  • Compound (1) has five rings from one part. These rings include fused rings and crosslinked 6-membered rings in addition to the usual 6-membered rings. When the compound (1) has one or two rings, the compatibility with other liquid crystal compounds is good and the viscosity is low. When compound (1) has three or four rings, the upper limit temperature is high. When compound (1) has four rings, the temperature range of the liquid crystal phase is wide.
  • terminal group By appropriately selecting the terminal group, ring and bonding group of compound (1), it is possible to arbitrarily adjust physical properties such as optical anisotropy and dielectric anisotropy.
  • the effects of the types of terminal groups R 1 and R 2 , rings A 1 and A 2 , binding groups Z 1 , Z 2 , Z 3 and Z 4 on the physical properties of compound (1) will be described below.
  • Ring A 1 or ring A 2 may have at least one hydrogen substituted with fluorine or chlorine 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, or pyridazine-3. When it is 6,6-diyl, the optical anisotropy is large. When the ring is 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,3-dioxane-2,5-diyl, the optical anisotropy is small.
  • the upper limit temperature is high, the optical anisotropy is small, and the viscosity is small.
  • the optical anisotropy is relatively large and the orientation parameter is large.
  • the optical anisotropy is large, the temperature range of the liquid crystal phase is wide, and the upper limit temperature is high.
  • the temperature range of the liquid crystal phase is wide, and the elastic constant ratio K 33 / K 11 (K 33 : bend elastic constant, K 11 : spray elastic constant) is large.
  • the bonding group is ⁇ C ⁇ C ⁇ , the optical anisotropy is large.
  • compound (1) When compound (1) has one or two rings, the viscosity is low. When compound (1) has four or five rings, the upper limit temperature is high. As described above, a compound having the required physical properties can be obtained by appropriately selecting the type of terminal group, ring, and bonding group, and the number of rings. Therefore, compound (1) is useful as a component of compositions used in devices having modes such as PC, TN, STN, ECB, OCB, IPS, and VA.
  • this compound is when both L 5 and L 6 are hydrogen, and when L 1 , L 2 , L 3 or L 4 is fluorine, chlorine, -CF 3 , or -CHF 2. preferable. This compound is even more preferred when both L 5 and L 6 are hydrogen and when L 1 , L 2 , L 3 or L 4 is fluorine or chlorine. This compound is most preferred when both L 5 and L 6 are hydrogen and when L 1 , L 2 , L 3 or L 4 is fluorine.
  • Preferred examples of the compound (1) are the compounds (1-1) to (1-26) described in Items 2 and 4.
  • a more preferable example is the compound represented by the lower formula in Items 6 and 8.
  • Compound (1) is suitable for devices having modes such as VA, IPS, and PSA.
  • MSG 1 (or MSG 2 ) is a monovalent organic group having at least one ring.
  • the monovalent organic groups represented by the plurality of MSG 1 (or MSG 2 ) used in the scheme may be the same or different.
  • Compounds (1A) to (1J) correspond to compound (1).
  • Decahydronaphthalen-2,6-dione (64) is a starting material for compounds having decahydronaphthalen-2,6-diyl.
  • This compound (64) is obtained by catalytically reducing diol (63) with ruthenium oxide in the presence of ruthenium oxide and further oxidizing with chromium oxide according to the method described in JP-A-2000-239564.
  • This compound is converted to compound (1) by a usual method.
  • the structural unit of 2,3- (bistrifluoromethyl) phenylene is synthesized by the method described in Org. Lett., 2000, 2 (21), 3345.
  • Aniline (66) is synthesized by reacting furan (65) with 1,1,1,4,4,4-hexafluoro-2-butin at a high temperature in a Diels-Alder type reaction. This compound is subjected to a Sandmeyer-type reaction according to the method described in Org. Synth. Coll., Vol. 2, 1943, 355 to obtain an iodide (67). This compound is converted to compound (1) by a usual method.
  • the structural unit of 2-difluoromethyl-3-fluorophenylene is synthesized by the following method.
  • the hydroxyl group of compound (68) is protected with an appropriate protecting group to obtain compound (69).
  • P means protecting group.
  • Compound (69) is reacted with s-butyllithium followed by N, N-dimethylformamide (DMF) to give aldehyde (70).
  • This compound is fluorinated with diethylaminosulfur trifluoride (DAST) and subsequently deprotected to give phenol (71).
  • DAST diethylaminosulfur trifluoride
  • Compound (s-1) is synthesized according to the method described in JP-A-2011-136924. Compound (s-1) is reduced with a reducing agent such as sodium borohydride to obtain compound (s-2). This compound is halogenated with triphenylphosphine and carbon tetrahalogenate, and treated with a dehalogenating agent such as diazabicycloundecene (DBU) to obtain the target compound (1a).
  • a reducing agent such as sodium borohydride
  • DBU diazabicycloundecene
  • compound (1b) The synthesis scheme of compound (1b) is as described above.
  • Compound (s-4) is obtained by reacting compound (s-3) with aldehyde (17) in the presence of a Lewis acid such as boron trifluoride diethyl ether complex, and then hydrogenating the compound (s-3). This compound is reduced with a reducing agent such as lithium aluminum hydride to obtain compound (s-5).
  • Compound (1b) is obtained by halogenating this compound with triphenylphosphine and carbon tetrahalogenate and treating it with a dehalogenating agent such as diazabicycloundecene (DBU).
  • DBU diazabicycloundecene
  • the liquid crystal composition of the present invention contains at least one compound (1) as a component (a).
  • the composition may contain two or more compounds (1).
  • the component of the composition may be only compound (1).
  • the composition preferably contains at least one of the compound (1) in the range of 1% by weight to 99% by weight in order to exhibit good physical properties.
  • the preferable content of the compound (1) is in the range of 5% by weight to 60% by weight.
  • the preferable content of the compound (1) is 30% by weight or less.
  • This composition contains compound (1) as component (a).
  • the composition preferably further contains a liquid crystal compound selected from the components (b) to (e) shown in Table 1.
  • a liquid crystal compound selected from the components (b) to (e) shown in Table 1.
  • This composition may contain liquid crystalline compounds different from compounds (1) to (13) and (21) to (24). This composition does not have to contain such a liquid crystal compound.
  • Component (b) is a compound having two terminal groups such as alkyl.
  • Preferred examples of the component (b) include compounds (2-1) to (2-11), compounds (3-1) to (3-19), and compounds (4-1) to (4-7). be able to.
  • R 11 and R 12 are independently alkyls with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, and in these R 11 and R 12 , at least one -CH 2- It may be replaced with —O—, and at least one hydrogen may be replaced with fluorine.
  • Component (b) has a small dielectric anisotropy. Component (b) is close to neutral. Compound (2) has the effect of lowering the viscosity or adjusting the optical anisotropy. Compounds (3) and (4) have the effect of widening the temperature range of the nematic phase or adjusting the optical anisotropy by raising the upper limit temperature.
  • the content of the component (b) is preferably 30% by weight or more, more preferably 40% by weight or more, based on the weight of the liquid crystal composition. be.
  • the component (c) is a compound (5) to (13). These compounds have phenylene in which the lateral position is replaced by two halogens, such as 2,3-difluoro-1,4-phenylene.
  • Preferred examples of the component (c) include compounds (5-1) to (5-9), compounds (6-1) to (6-19), compounds (7-1) and (7-2), compounds ( 8-1) to (8-3), compounds (9-1) to (9-3), compounds (10-1) to (10-11), compounds (11-1) to (11-3), Compounds (12-1) to (12-3), and compound (13-1) can be mentioned.
  • R 13 and R 14 are independently alkyls with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, and in these R 13 and R 14 , at least one -CH 2- may be replaced by -O-, at least one hydrogen may be replaced by fluorine, R 15 is hydrogen, fluorine, alkenyl alkyl or 2 to 10 carbon atoms from 10 1 carbon atoms, In this R 15 , at least one -CH 2- may be replaced by -O-, and in this R 15 , at least one hydrogen may be replaced by fluorine.
  • Component (c) has a large negative dielectric anisotropy.
  • Ingredient (c) is used when preparing compositions for modes such as IPS, VA, PSA.
  • the content of the component (c) is increased, the dielectric anisotropy of the composition becomes negatively large, but the viscosity becomes large. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the content is preferably small.
  • the dielectric anisotropy is about ⁇ 5
  • the content is preferably 40% by weight or more in order to drive the voltage sufficiently.
  • the compound (5) is a bicyclic compound, and therefore has the effects of lowering the viscosity, adjusting the optical anisotropy, or increasing the dielectric anisotropy.
  • the compounds (6) and (7) are tricyclic compounds and the compound (8) is a tetracyclic compound, they have the effect of increasing the upper limit temperature, increasing the optical anisotropy, or increasing the dielectric anisotropy. be.
  • Compounds (9) to (13) have the effect of increasing the dielectric anisotropy.
  • the content of the component (c) is preferably 40% by weight or more, more preferably 50% based on the weight of the liquid crystal composition. It ranges from% to 95% by weight.
  • the content of the component (c) is preferably 30% by weight or less.
  • Component (d) is a compound having a halogen or fluorine-containing group at the right end.
  • Preferred examples of the component (d) include compounds (21-1) to (21-16), compounds (22-1) to (22-116), and compounds (23-1) to (23-59). Can be done.
  • R 16 is alkenyl having 2 to 10 carbon alkyl or C 1 to 10 carbon atoms, in the R 16, at least one -CH 2 - may be replaced by -O-, at least One hydrogen may be replaced by fluorine.
  • X 11 is fluorine, chlorine, -OCF 3 , -OCHF 2 , -CF 3 , -CHF 2 , -CH 2 F, -OCF 2 CHF 2 , or -OCF 2 CHFCF 3 .
  • Component (d) has a positive dielectric anisotropy and very good stability against heat and light, and is therefore used when preparing a composition for modes such as IPS, FFS, and OCB.
  • the content of the component (d) is preferably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, more preferably from 40% by weight, based on the weight of the liquid crystal composition. It is in the range of 95% by weight.
  • the content of the component (d) is preferably 30% by weight or less.
  • Component (e) is compound (24) whose right terminal group is -C ⁇ N or -C ⁇ C-C ⁇ N.
  • Preferred examples of the component (e) include compounds (24-1) to (24-64).
  • R 17 is alkenyl having 2 to 10 carbon alkyl or C 1 to 10 carbon atoms, in the R 17, at least one -CH 2 - may be replaced by -O-, At least one hydrogen may be replaced with fluorine.
  • X 12 is -C ⁇ N or -C ⁇ C-C ⁇ N.
  • the component (e) has a positive dielectric anisotropy and a large value, and is therefore used when preparing a composition for a mode such as TN. By adding this component (e), the dielectric anisotropy of the composition can be increased.
  • the component (e) has the effect of widening the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy.
  • the component (e) is also useful for adjusting the voltage-transmittance curve of the device.
  • the content of the component (e) is preferably in the range of 1% by weight to 99% by weight, preferably 10% by weight, based on the weight of the liquid crystal composition. % To 97% by weight, more preferably 40% to 95% by weight.
  • the content of the component (e) is preferably 30% by weight or less.
  • Directionality ie, large optical anisotropy or small optical anisotropy
  • positive or negative large dielectric anisotropy large specific resistance
  • appropriate elastic constants ie, large elastic constants or small elastic constants
  • a liquid crystal composition satisfying at least one of the physical characteristics can be prepared.
  • Devices containing such compositions have a wide temperature range in which the device can be used, short response times, high voltage retention, low threshold voltage, high contrast ratio, low flicker rate, and long lifetime.
  • the flicker rate (%) can be expressed by (
  • An element having a flicker rate in the range of 0% to 1% is less likely to cause flicker on the display screen even if the element is used for a long time.
  • This flicker is related to image burn-in and is presumed to be caused by the potential difference between the positive and negative frames when driven by alternating current.
  • the composition containing the compound (1) is also useful for reducing the occurrence of flicker.
  • the liquid crystal composition is prepared by a known method. For example, the constituent compounds are mixed and dissolved by heating. Additives may be added to this composition depending on the application. Examples of additives are polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dyes, defoamers and the like. Such additives are well known to those of skill in the art and are described in the literature.
  • the composition contains a polymer.
  • the polymerizable compound is added for the purpose of forming a polymer in the composition.
  • a polymer is produced in the composition by irradiating ultraviolet rays with a voltage applied between the electrodes to polymerize the polymerizable compound.
  • Preferred examples of the polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxylane, oxetane), and vinyl ketone. More preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. More preferred examples also include compounds having both acryloyloxy and methacryloyloxy.
  • R 25 to R 31 are independently hydrogen or methyl;
  • R 32 , R 33 , and R 34 are independently hydrogen or alkyl having 1 to 5 carbon atoms, R 32 , At least one of R 33 , and R 34 is an alkyl having 1 to 5 carbon atoms;
  • v, w, and x are 0 or 1 independently;
  • u and y are independently 1 to 10 It is an integer.
  • L 21 to L 26 are independently hydrogen or fluorine;
  • L 27 and L 28 are independently hydrogen, fluorine, or methyl.
  • the polymerizable compound can be rapidly polymerized by adding a polymerization initiator. By optimizing the reaction conditions, the amount of residual polymerizable compound can be reduced.
  • photoradical polymerization initiators are TPO, 1173, and 4265 from BASF's DaroCure series and 184,369,500,651,784,819,907,1300,1700,1800,1850 from the Irgacure series. , And 2959.
  • photoradical polymerization initiators include 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystylyl) -5-trichloromethyl-1,3,4-oxadiazole, 9-Phenylaclysine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyl Dimethylketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2,4-diethylxanthone / p-dimethylaminomethyl benzoate mixture, benzophenone / methyltriethanolamine mixture Is.
  • polymerization After adding a photoradical polymerization initiator to the liquid crystal composition, polymerization can be carried out by irradiating ultraviolet rays with an electric field applied. However, unreacted polymerization initiators or degradation products of the polymerization initiators may cause display defects such as image burn-in on the device. In order to prevent this, photopolymerization may be carried out without adding a polymerization initiator.
  • the preferred wavelength of the emitted light is in the range of 150 nm to 500 nm. More preferred wavelengths are in the range of 250 nm to 450 nm, and most preferred wavelengths are in the range of 300 nm to 400 nm.
  • a polymerization inhibitor When storing the polymerizable compound, a polymerization inhibitor may be added to prevent polymerization.
  • the polymerizable compound is usually added to the composition without removing the polymerization inhibitor.
  • polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine and the like.
  • the optically active compound has the effect of preventing reverse twisting by inducing a helical structure in the liquid crystal molecule to give a necessary twist angle.
  • the spiral pitch can be adjusted by adding an optically active compound.
  • Two or more optically active compounds may be added for the purpose of adjusting the temperature dependence of the spiral pitch.
  • Preferred examples of the optically active compound include the following compounds (Op-1) to (Op-18).
  • ring J is 1,4-cyclohexylene or 1,4-phenylene
  • R 28 is an alkyl having 1 to 10 carbon atoms. * Marks represent asymmetric carbon.
  • Antioxidants are effective in maintaining a large voltage retention rate.
  • Preferred examples of the antioxidant include the following compounds (AO-1) and (AO-2); Irganox415, Irganox565, Irganox1010, Irganox1035, Irganox3114, and Irganox1098 (trade name: BASF).
  • the ultraviolet absorber is effective for preventing a decrease in the upper limit temperature.
  • UV absorber is benzophenone derivatives, benzoate derivatives, triazole derivatives and the like, and specific examples thereof include the following compounds (AO-3) and (AO-4); Tinuvin 328, and Tinuvin 99-2 (trade name; BASF); and 1,4-diazabicyclo [2.2.2] octane (DABCO) can be mentioned.
  • a light stabilizer such as amine with steric hindrance is preferable in order to maintain a large voltage holding ratio.
  • Preferred examples of light stabilizers are the following compounds (AO-5), (AO-6), (AO-7), (AO-8), and (AO-9); Product name; BASF); LA-52, LA-57, LA-77Y, and LA-77G (trade name: ADEKA) can be mentioned.
  • a heat stabilizer is also effective for maintaining a large voltage holding ratio, and Irgafos 168 (trade name; BASF) can be mentioned as a preferable example.
  • Dichroic dyes such as azo dyes, anthraquinone dyes, etc. are added to the composition to accommodate devices in GH (guest host) mode. Defoamers are effective in preventing foaming.
  • Preferred examples of the defoaming agent are dimethyl silicone oil, methyl phenyl silicone oil and the like.
  • R 40 is an alkyl having 1 to 20 carbon atoms, an alkoxy having 1 to 20 carbon atoms, -COOR 41 , or-(CH 2 ) 2- COOR 41 , where R 41 is carbon. Alkoxy of numbers 1 to 20.
  • R 42 is an alkyl having 1 to 20 carbon atoms.
  • R 43 is hydrogen, methyl or O ⁇ (oxygen radical);
  • ring G 1 is 1,4-cyclohexylene or 1,4-phenylene;
  • ring G 2 is 1,4-cyclohexylene, 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen has been replaced with fluorine; compound (AO-5),.
  • z is 1, 2, or 3.
  • the liquid crystal composition has an operation mode such as PC, TN, STN, OCB, PSA, and can be used for a liquid crystal display element driven by an active matrix method.
  • This composition has an operation mode such as PC, TN, STN, OCB, VA, and IPS, and can also be used for a liquid crystal display element driven by a passive matrix method.
  • These elements can be applied to any type of reflective type, transmissive type, and semitransparent type.
  • This composition is also suitable for NCAP (nematic curvilinear aligned phase) devices, where the composition is microencapsulated.
  • This composition can also be used in a polymer-dispersed liquid crystal display element (PDLCD) and a polymer network liquid crystal display element (PNLCD).
  • PDLCD polymer-dispersed liquid crystal display element
  • PLCD polymer network liquid crystal display element
  • a large amount of the polymerizable compound is added.
  • a liquid crystal display element in PSA mode is produced.
  • the preferred proportion is in the range of 0.1% by weight to 2% by weight.
  • a more preferable ratio is in the range of 0.2% by weight to 1.0% by weight.
  • the PSA mode element can be driven by a drive system such as an active matrix system or a passive matrix system. Such an element can be applied to any type of reflective type, transmissive type, and semitransparent type.
  • NMR analysis DRX-500 manufactured by Bruker Biospin Co., Ltd. was used for the measurement. 1 In the 1 H-NMR measurement, the sample was dissolved in a deuterated solvent such as CDCl 3 and measured at room temperature, 500 MHz, and the number of integrations was 16 times. Tetramethylsilane was used as an internal standard. 19 In the F-NMR measurement, CFCl 3 was used as an internal standard, and the number of integrations was 24. In the description of the nuclear magnetic resonance spectrum, s means singlet, d means doublet, t means triplet, q means quartet, quin means quintet, sext means sextet, m means multiplet, and br means broad.
  • a GC-2010 type gas chromatograph manufactured by Shimadzu Corporation was used for the measurement.
  • a capillary column DB-1 (length 60 m, inner diameter 0.25 mm, film thickness 0.25 ⁇ m) manufactured by Agilent Technologies Inc. was used.
  • Helium (1 mL / min) was used as the carrier gas.
  • the temperature of the sample vaporization chamber was set to 300 ° C., and the temperature of the detector (FID) was set to 300 ° C.
  • the sample was dissolved in acetone to prepare a 1% by weight solution, and 1 ⁇ L of the obtained solution was injected into the sample vaporization chamber.
  • a GC Solution system manufactured by Shimadzu Corporation was used as the recorder.
  • Gas chromatograph mass spectrometry A QP-2010 Ultra type gas chromatograph mass spectrometer manufactured by Shimadzu Corporation was used for the measurement.
  • a capillary column DB-1 (length 60 m, inner diameter 0.25 mm, film thickness 0.25 ⁇ m) manufactured by Agilent Technologies Inc. was used.
  • Helium (1 mL / min) was used as the carrier gas.
  • the temperature of the sample vaporization chamber was set to 300 ° C.
  • the temperature of the ion source was set to 200 ° C.
  • the ionization voltage was set to 70 eV
  • the emission current was set to 150 uA.
  • the sample was dissolved in acetone to prepare a 1% by weight solution, and 1 ⁇ L of the obtained solution was injected into the sample vaporization chamber.
  • a GCMS solution system manufactured by Shimadzu Corporation was used as the recorder.
  • HPLC analysis Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used for the measurement.
  • YMC-Pack ODS-A length 150 mm, inner diameter 4.6 mm, particle diameter 5 ⁇ m
  • the eluate used was an appropriate mixture of acetonitrile and water.
  • the detector a UV detector, an RI detector, a CORONA detector and the like were appropriately used. When a UV detector was used, the detection wavelength was 254 nm.
  • the sample was prepared to dissolve in acetonitrile to form a 0.1% by weight solution, and 1 ⁇ L of this solution was introduced into the sample chamber.
  • C-R7Aplus manufactured by Shimadzu Corporation was used.
  • Ultraviolet-visible spectroscopic analysis For the measurement, PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used. The detection wavelength was 190 nm to 700 nm. The sample was prepared by dissolving it in acetonitrile to form a solution of 0.01 mmol / L, and placed in a quartz cell (optical path length 1 cm) for measurement.
  • Measurement sample When measuring the phase structure and transition temperature (transparency point, melting point, polymerization start temperature, etc.), the compound itself was used as a sample. When measuring physical properties such as the upper limit temperature, viscosity, optical anisotropy, and dielectric anisotropy of the nematic phase, a mixture of the compound and the mother liquid crystal was used as a sample.
  • the ratio of the compound to the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% by weight.
  • the physical properties of the sample were measured at the rate at which the crystals (or smectic phase) did not precipitate at 25 ° C.
  • the ratio of the compound to the mother liquid crystal display is 15% by weight: 85% by weight.
  • the dielectric anisotropy of the compound was zero or positive
  • the following mother liquid crystal display (A) was used.
  • the ratio of each component was expressed in% by weight.
  • the dielectric anisotropy of the compound was zero or negative
  • the following mother liquid crystal display (B) was used.
  • the ratio of each component was expressed in% by weight.
  • Mother liquid crystal (C) A mother liquid crystal (C) containing the following fluorine-based compounds as components was also used. The ratio of the components of the mother liquid crystal display (C) was expressed in% by weight.
  • the ratio of the compound and the mother liquid crystal display (C) was 20% by weight: 80% by weight.
  • the ratio of the compound to the mother liquid crystal (C) is 15% by weight: 85% by weight, 10% by weight: 90% by weight, 5% by weight.
  • the changes were made in the order of: 95% by weight, 1% by weight: 99% by weight, and the physical characteristics of the sample were measured at a rate at which crystals (or smectic phase) did not precipitate at 25 ° C.
  • the ratio of the compound to the mother liquid crystal display (C) is 20% by weight: 80% by weight.
  • Measurement method The physical properties were measured by the following method. Many of these are described in the JEITA standard (JEITA ED-2521B), which is deliberated and enacted by the Japan Electronics and Information Technology Industries Association (JEITA). A modified method was also used. A thin film transistor (TFT) was not attached to the TN element used for the measurement.
  • Phase structure A sample was placed on a hot plate (FP-52 type hot stage manufactured by METTLER CORPORATION) of a melting point measuring device equipped with a polarizing microscope. The phase state and its change were observed with a polarizing microscope while heating this sample at a rate of 3 ° C./min to identify the type of phase.
  • FP-52 type hot stage manufactured by METTLER CORPORATION
  • Transition temperature (° C.): A scanning calorimeter manufactured by PerkinElmer, a Diamond DSC system, or a high-sensitivity differential scanning calorimeter manufactured by SII Nanotechnology, X-DSC7000 was used for the measurement. The temperature of the sample was raised and lowered at a rate of 3 ° C./min, and the start point of the endothermic peak or the exothermic peak accompanying the phase change of the sample was determined by extrapolation to determine the transition temperature. The melting point of the compound and the polymerization initiation temperature were also measured using this device.
  • the temperature at which a compound transitions from a solid to a liquid crystal phase such as a smectic phase or a nematic phase may be abbreviated as "lower limit temperature of the liquid crystal phase”.
  • the temperature at which a compound transitions from the liquid crystal phase to a liquid may be abbreviated as "transparency point”.
  • the crystal was represented as C.
  • the smectic phase was represented as S and the nematic phase was represented as N.
  • the liquid (isotropic) was represented as I.
  • the transition temperature is expressed as, for example, "C 50.0 N 100.0 I". This indicates that the transition temperature from the crystal to the nematic phase is 50.0 ° C. and the transition temperature from the nematic phase to the liquid is 100.0 ° C.
  • Upper limit temperature of nematic phase ( TNI or NI; ° C.): A sample was placed on a hot plate of a melting point measuring device equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature at which a part of the sample changed from the nematic phase to the isotropic liquid was measured. When the sample was a mixture of compound (1) and the mother liquid crystal display, it was indicated by the TNI symbol. When the sample was a mixture of compound (1) and a compound selected from compounds (2) to (15), it was indicated by the symbol NI.
  • the upper limit temperature of the nematic phase may be abbreviated as "upper limit temperature".
  • T C Minimum Temperature of a Nematic Phase
  • Viscosity (bulk viscosity; ⁇ ; measured at 20 ° C.; mPa ⁇ s): An E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used for the measurement.
  • VHR-1 Voltage retention rate (VHR-1; measured at 25 ° C.;%):
  • the TN element used for the measurement had a polyimide alignment film, and the distance (cell gap) between the two glass substrates was 5 ⁇ m. .. This device was sealed with an adhesive that cures with ultraviolet light after the sample was placed. A pulse voltage (60 microseconds at 5 V) was applied to this device to charge it. The decaying voltage was measured with a high-speed voltmeter for 16.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit period was determined. Area B was the area when there was no attenuation. The voltage holding ratio is expressed as a percentage of the area A with respect to the area B.
  • VHR-2 Voltage retention rate (10) Voltage retention rate (VHR-2; measured at 80 ° C.;%): The voltage retention rate was measured by the above method except that the measurement was performed at 80 ° C. instead of 25 ° C. The results obtained are indicated by the symbol VHR-2.
  • Flicker rate (measured at 25 ° C.;%): A multimedia display tester 3298F manufactured by Yokogawa Electric Corporation was used for the measurement.
  • the light source was an LED.
  • the sample was placed in an FFS element in a normally black mode in which the distance (cell gap) between the two glass substrates was 3.5 ⁇ m and the rubbing direction was antiparallel. This element was sealed with an UV curable adhesive.
  • a voltage was applied to this device, and the voltage at which the amount of light transmitted through the device was maximized was measured. While applying this voltage to the element, the sensor unit was brought close to the element and the displayed flicker rate was read.
  • the method of measuring physical properties may differ between a sample with a positive dielectric anisotropy and a sample with a negative dielectric anisotropy.
  • the measuring method when the dielectric anisotropy is positive is described in measurement (12a) to measurement (16a).
  • the dielectric anisotropy was negative, it was described in measurement (12b) to measurement (16b).
  • Viscosity Rotational viscosity; ⁇ 1; measured at 25 ° C; mPa ⁇ s; sample with positive dielectric anisotropy: Measurement was performed by M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, The method described in 37 (1995) was followed. The sample was placed in a TN device having a twist angle of 0 degrees and a distance (cell gap) between the two glass substrates of 5 ⁇ m. A stepwise application of 16 V to 19.5 V was applied to this device in 0.5 V increments. After no application for 0.2 seconds, application was repeated under the conditions of only one square wave (rectangular pulse; 0.2 seconds) and no application (2 seconds).
  • Viscosity Rotational viscosity; ⁇ 1; measured at 25 ° C; mPa ⁇ s; sample with negative dielectric anisotropy: Measurement was performed by M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, The method described in 37 (1995) was followed. The sample was placed in a VA element having a distance (cell gap) between two glass substrates of 20 ⁇ m. A stepwise application of 39 V to 50 V was applied to this device in 1 V increments. After no application for 0.2 seconds, application was repeated under the conditions of only one square wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured.
  • a sample was placed in a VA element in which the distance (cell gap) between the two glass substrates was 4 ⁇ m, and this element was sealed with an adhesive that cures with ultraviolet rays.
  • a sine wave (0.5 V, 1 kHz) was applied to this element, and after 2 seconds, the dielectric constant ( ⁇ ) of the liquid crystal molecule in the long axis direction was measured.
  • the sample was placed in a TN element in which the distance (cell gap) between the two glass substrates was 9 ⁇ m and the twist angle was 80 degrees.
  • a sine wave (0.5 V, 1 kHz) was applied to this element, and after 2 seconds, the permittivity ( ⁇ ) of the liquid crystal molecule in the minor axis direction was measured.
  • Threshold voltage (Vth; measured at 25 ° C.; V; sample with positive dielectric anisotropy): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement.
  • the light source was a halogen lamp.
  • the sample was placed in a normally white mode TN element in which the distance (cell gap) between the two glass substrates was 0.45 / ⁇ n ( ⁇ m) and the twist angle was 80 degrees.
  • the voltage (32 Hz, square wave) applied to this device was gradually increased by 0.02 V from 0 V to 10 V.
  • the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured.
  • a voltage-transmittance curve was created in which the transmittance was 100% when the amount of light was maximum and the transmittance was 0% when the amount of light was minimum.
  • the threshold voltage is expressed as the voltage when the transmittance reaches 90%.
  • Threshold voltage (Vth; measured at 25 ° C.; V; sample with negative dielectric anisotropy): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement.
  • the light source was a halogen lamp.
  • a sample is placed in a VA element in normally black mode where the distance (cell gap) between the two glass substrates is 4 ⁇ m and the rubbing direction is anti-parallel, and an adhesive that cures this element with ultraviolet rays is applied. Sealed using.
  • the voltage (60 Hz, square wave) applied to this device was gradually increased by 0.02 V from 0 V to 20 V.
  • the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured.
  • a voltage-transmittance curve was created in which the transmittance was 100% when the amount of light was maximum and the transmittance was 0% when the amount of light was minimum.
  • the threshold voltage is expressed as the voltage when the transmittance reaches 10%.
  • the rise time ( ⁇ r: rise time; millisecond) is the time required for the transmittance to change from 90% to 10%.
  • the fall time ( ⁇ f: fall time; millisecond) is the time required for the transmittance to change from 10% to 90%.
  • the response time was expressed as the sum of the rise time and the fall time obtained in this way.
  • a square wave (60 Hz, 10 V, 0.5 seconds) was applied to this device.
  • the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. It was considered that the transmittance was 100% when the amount of light was maximum, and the transmittance was 0% when the amount of light was minimum.
  • the response time was expressed as the time required for the transmittance to change from 90% to 10% (fall time; fall time; millisecond).
  • Second step Synthesis of compound (t-9)
  • Commercially available compound (t-7) (12.5 g, 65.5 mmol), 1-bromobutane (9.86 g, 72.0 mmol), potassium carbonate (11.8 g, 85.1 mmol) was dissolved in N, N-dimethylformamide (125 mL) and stirred at 80 ° C. for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, poured into water, and extracted with toluene three times. The combined organic layers were washed with a 2N-NaOH aqueous solution and water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by short silica gel chromatography (heptane) to give compound (t-9) (14.2 g, 57.5 mmol) as a light brown liquid.
  • Phase transition temperature C 142.5 I.
  • the physical property value could not be measured because 3% was not dissolved.
  • Second step Synthesis of compound (t-16) Compound (t-15) (18.0 g, 72.8 mmol), benzylamine (9.37 g, 87.4 mmol), t-butoxysodium (10.5 g, 109 mmol) ) Is dissolved in toluene (252 mL), degassed under reduced pressure, and palladium (0) bis (dibenzylideneacetone) (0.838 g), 2- (di-t-butylphosphino) biphenyl (0.870 g, 2. 91 mmol) was added, and the mixture was heated and stirred at 60 ° C.
  • the dielectric anisotropy of compound (a-5) and comparative compound (Ref-1) was compared as follows.
  • the comparative compound (Ref-1) is compound (1-2-5) described in paragraph [0143] of WO 2015/129412.
  • the synthesis was carried out according to the method of paragraphs [0143] to [0154] of International Publication No. 2015/129412.
  • the dielectric anisotropy ( ⁇ ) of the compound (a-5) obtained by the synthesis of the compound (3) and the comparative compound (Ref-1) was compared. It was found that the dielectric anisotropy of compound (a-5) was much larger in the negative. Therefore, it can be concluded that compound (1) is superior to similar compounds.
  • the present invention will be described in more detail by way of examples.
  • the present invention is not limited by the examples, as the examples are typical.
  • the present invention includes, in addition to the composition of Examples, a mixture of the composition of Example 1 and the composition of Example 2.
  • the present invention also includes a mixture prepared by mixing at least two of the compositions of Examples.
  • the compounds in the use cases are represented by symbols based on the definitions in Table 2 below.
  • Table 2 the configuration for 1,4-cyclohexylene is trans.
  • the number in parentheses after the symbol represents the chemical formula to which the compound belongs.
  • the symbol (-) means a liquid crystal compound different from the compounds (1) to (15).
  • the proportion (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additives.
  • liquid crystal compound of the present invention has good physical characteristics. Liquid crystal compositions containing this compound can be widely used in liquid crystal display elements such as personal computers and televisions.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

Composé représenté par la formule (1). R1 et R2 représentent chacun un alkyle en C1-C15 ou similaire ; Ra représente un atome d'hydrogène ou similaire ; un cycle A1 et un cycle A2 représentent chacun le 1,4-cyclohexylène, le 1,4-phénylène ou similaire ; un cycle N1 et un cycle N2 représentent chacun le 1,2-cyclopropylène, le 1,3-cyclopentylène, ou similaire ; Z1, Z2, Z3 et Z4 représentent chacun une liaison simple ou similaire ; L1, L2, L3, L4, L5 et L6 représentent chacun un atome de fluor ou similaire ; et l et o représentent chacun 0 ou 1 et m et n représentent chacun 0, 1 ou 2.
PCT/JP2021/012218 2020-03-25 2021-03-24 Composé, composition de cristaux liquides et élément d'affichage à cristaux liquides WO2021193708A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4943973A (fr) * 1972-07-24 1974-04-25
WO2008096791A1 (fr) * 2007-02-07 2008-08-14 Astellas Pharma Inc. Dérivé d'acylguanidine
WO2010133278A1 (fr) * 2009-05-22 2010-11-25 Merck Patent Gmbh Affichage à cristaux liquides
WO2017084231A1 (fr) * 2015-11-17 2017-05-26 江苏师范大学 Série de composés carbazole contenant du fluor, leur procédé de préparation et utilisation
WO2018031410A2 (fr) * 2016-08-04 2018-02-15 Nitto Denko Corporation Composition de cristaux liquides hétérocycliques, élément à cristaux liquides dispersés dans un polymère en mode inverse, et dispositif à intensité sélectivement variable associé
WO2018088386A1 (fr) * 2016-11-10 2018-05-17 Dic株式会社 Élément d'affichage à cristaux liquides

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4943973A (fr) * 1972-07-24 1974-04-25
WO2008096791A1 (fr) * 2007-02-07 2008-08-14 Astellas Pharma Inc. Dérivé d'acylguanidine
WO2010133278A1 (fr) * 2009-05-22 2010-11-25 Merck Patent Gmbh Affichage à cristaux liquides
WO2017084231A1 (fr) * 2015-11-17 2017-05-26 江苏师范大学 Série de composés carbazole contenant du fluor, leur procédé de préparation et utilisation
WO2018031410A2 (fr) * 2016-08-04 2018-02-15 Nitto Denko Corporation Composition de cristaux liquides hétérocycliques, élément à cristaux liquides dispersés dans un polymère en mode inverse, et dispositif à intensité sélectivement variable associé
WO2018088386A1 (fr) * 2016-11-10 2018-05-17 Dic株式会社 Élément d'affichage à cristaux liquides

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Title
KUETHE, J. T ET AL.: "Suzuki-Miyaura cross- coupling of 2-nitroarenediazonrnm tetrafluoroborates: synthesis of unsymmetrical 2- nitrobiphenyls and highly functionalized carbazoles", ADVANCED SYNTHESIS & CATALYSIS, vol. 350, no. 10, 2008, pages 1577 - 1586, XP002542896, DOI: 10.1002/adsc.200800162 *
RIDDELL NICOLE, JIN UN-HO, SAFE STEPHEN, CHENG YATING, CHITTIM BROCK, KONSTANTINOV ALEX, PARETTE ROBERT, PENA-ABAURREA MIREN, REIN: "Characterization and Biological Potency of Mono-to Tetra-Halogenated Carbazoles", ENVIRONMENTAL SCIENCE & TECHNOLOGY, vol. 49, no. 17, 2015, pages 10658 - 10666, XP055861215, DOI: 10.1021/acs.est.5b02751 *

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