WO2019111892A1 - Compound, liquid crystal composition, and liquid crystal display element - Google Patents

Compound, liquid crystal composition, and liquid crystal display element Download PDF

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WO2019111892A1
WO2019111892A1 PCT/JP2018/044555 JP2018044555W WO2019111892A1 WO 2019111892 A1 WO2019111892 A1 WO 2019111892A1 JP 2018044555 W JP2018044555 W JP 2018044555W WO 2019111892 A1 WO2019111892 A1 WO 2019111892A1
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replaced
diyl
carbons
hydrogen
ring
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Japanese (ja)
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田中　裕之
匡一 矢野
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Jnc株式会社
Jnc石油化学株式会社
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Priority to JP2019558223A priority Critical patent/JP7238786B2/en
Publication of WO2019111892A1 publication Critical patent/WO2019111892A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—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
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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
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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
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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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—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
    • C09K19/38—Polymers
    • C—CHEMISTRY; METALLURGY
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C—CHEMISTRY; METALLURGY
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    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • 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 compound, a liquid crystal composition and a liquid crystal display device. More specifically, a compound having both a polar group such as -OH group and a plurality of polymerizable groups such as methacryloyloxy, a liquid crystal composition containing this compound and having positive or negative dielectric anisotropy, and this composition or The present invention relates to a liquid crystal display element including a part of the cured product.
  • the liquid crystal display elements are classified based on the operation mode of liquid crystal molecules: PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS ( It can be classified into modes such as in-plane switching (VA), vertical alignment (VA), fringe field switching (FFS), and field-induced photo-reactive alignment (FPA). Also, based on the driving method of the element, it can be classified into PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into thin film transistor (TFT), metal insulator metal (MIM), etc.
  • PC phase change
  • TN twisted nematic
  • STN super twisted nematic
  • ECB electrically controlled birefringence
  • OCB optical compensated bend
  • IPS It can be classified into modes such as in-plane switching (VA), vertical alignment (VA), fringe field switching (FFS),
  • TFTs can be classified into amorphous silicon and polycrystal silicon. The latter are classified into high temperature type and low temperature type according to the manufacturing process.
  • the classification based on light source can be classified into a reflection type using natural light, a transmission type using back light, and a semi-transmission type using both natural light and back light.
  • the liquid crystal composition having a nematic phase has appropriate properties. By improving the properties of this composition, an AM element having good properties can be obtained.
  • the relationship between the properties of the composition and the properties of the AM device is summarized in Table 1 below.
  • the characteristics of the composition are further described based on commercially available AM devices.
  • the temperature range of the nematic phase (the temperature range exhibiting the nematic phase) relates to the usable temperature range of the device.
  • the preferred upper temperature limit of the nematic phase is about 70 ° C. or higher, and the preferred lower temperature limit of the nematic phase is about -10 ° C. or lower.
  • the viscosity of the composition is related to the response time of the device. Short response times are preferred for displaying motion pictures on the device. Even shorter response times of 1 millisecond are desirable. Therefore, the viscosity of the composition is preferably low, and more preferably low even at low temperatures.
  • the optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large or small optical anisotropy, ie a suitable optical anisotropy, is required.
  • the product ( ⁇ n ⁇ d) of the optical anisotropy ( ⁇ n) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio.
  • the appropriate product value depends on the type of operating mode. This value is about 0.45 ⁇ m for devices of modes such as TN. This value is in the range of about 0.30 ⁇ m to about 0.40 ⁇ m in the VA mode device and in the range of about 0.20 ⁇ m to about 0.30 ⁇ m in the IPS mode or FFS mode device.
  • compositions with large optical anisotropy are preferred for small cell gap devices.
  • the large dielectric anisotropy in the composition contributes to low threshold voltage, low power consumption and high contrast ratio in the device. Therefore, positive or negative large dielectric anisotropy is preferred.
  • the large resistivity in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a large specific resistance at an initial stage not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable. After long time use, a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable.
  • the stability of the composition to ultraviolet light and heat is related to the lifetime of the device. When this stability is high, the lifetime of the device is long. Such characteristics are preferable for an AM element used for a liquid crystal projector, a liquid crystal television or the like.
  • a liquid crystal composition containing a polymer is used.
  • a composition to which a small amount of a polymerizable compound is added is injected into the device.
  • polymerizable compounds having a plurality of polymerizable groups are generally used.
  • the composition is irradiated with ultraviolet light.
  • the polymerizable compound polymerizes to form a polymer network in the composition.
  • the polymer can control the alignment of liquid crystal molecules, so that the response time of the device is shortened and the image sticking is improved.
  • Such an effect of the polymer can be expected in devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
  • a mode is proposed in which a polar compound is added to a liquid crystal composition to align liquid crystal molecules.
  • a composition to which a small amount of polar compound and a small amount of polymerizable compound are added is injected into the device.
  • the polymerizable compound polymerizable compounds having a plurality of polymerizable groups are generally used.
  • the liquid crystal molecules are oriented by the action of the polar compound.
  • the composition is irradiated with ultraviolet light.
  • the polymerizable compound is polymerized to stabilize the alignment of liquid crystal molecules.
  • the polar compound and the polymer make it possible to control the alignment of liquid crystal molecules, so that the response time of the device is shortened and the image sticking is improved.
  • the step of forming the alignment film is unnecessary. Since there is no alignment film, the interaction between the alignment film and the composition does not lower the electrical resistance of the device.
  • Such an effect by the combination of a polar compound and a polymer can be expected to an element having modes such as TN, ECB, OCB, IPS, VA, FFS, FPA.
  • Patent Document 1 describes a polymerizable compound (S-1) having a plurality of polar groups and a plurality of polymerizable groups.
  • One embodiment of the present invention is a compound having at least one of high chemical stability, high ability to align liquid crystal molecules, high polymerization reactivity by ultraviolet irradiation, and high solubility in a liquid crystal composition.
  • One embodiment of the present invention comprises this compound, and the high upper limit temperature of the nematic phase, the low lower limit temperature of the nematic phase, the low viscosity, the appropriate optical anisotropy, the positive or negative large dielectric anisotropy, the large
  • a liquid crystal composition satisfying at least one of properties such as specific resistance, high stability to ultraviolet light, high stability to heat, a large elastic constant, and a large voltage holding ratio when used in a liquid crystal display element.
  • One embodiment of the present invention is characterized by wide temperature range where the device can be used, short response time, high transmittance, large voltage holding ratio, low threshold voltage, large contrast ratio, long lifetime, good vertical orientation, etc.
  • a liquid crystal display device comprising at least one of
  • One embodiment of the present invention is a liquid crystal display device comprising a compound represented by the formula (1), a liquid crystal composition containing this compound, and a polymer obtained by polymerizing at least a part of this composition and / or this composition. About.
  • Ring A 1 and ring A 2 are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4 -Cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2 , 5-diyl, 1,3-dioxan
  • At least one of chemically high stability, high ability to align liquid crystal molecules, high polymerization reactivity by ultraviolet irradiation, and large voltage holding ratio when used in a liquid crystal display device It is possible to provide a compound having a high solubility in a liquid crystal composition. According to one embodiment of the present invention, comprising this compound, and high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, low viscosity, suitable optical anisotropy, positive or negative large dielectric anisotropy It is possible to provide a liquid crystal composition satisfying at least one of the properties such as large resistivity, high stability to ultraviolet light, high stability to heat, and a large elastic constant.
  • a wide temperature range in which the device can be used short response time, high transmittance, large voltage holding ratio, low threshold voltage, large contrast ratio, long lifetime, good vertical alignment, etc.
  • a liquid crystal display device having at least one of the following characteristics can be provided.
  • liquid crystal compound liquid crystal composition
  • liquid crystal display element liquid crystal display element
  • compound liquid crystal phase
  • element liquid crystal display element
  • Liquid crystalline compound is a compound having a liquid crystal phase such as a nematic phase or smectic phase, and has no liquid crystal phase, but controls physical properties of the composition such as upper limit temperature, lower limit temperature, viscosity, dielectric anisotropy, etc.
  • a generic term for compounds added for the purpose of This compound usually has a 6-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and the molecular structure is rod like.
  • the "polymerizable compound” is a compound to be added for the purpose of forming a polymer in the composition.
  • the liquid crystal compound having an alkenyl is not a polymerizable compound in that sense.
  • the “polar group” interacts non-covalently with a substrate surface such as glass (or metal oxide), etc., and the following —OH, —NH 2 , —OR 3 , —N (R 3 ) 2 , —COOH A group such as —SH or —Si (R 3 ) 3 .
  • the “polar compound” assists the alignment of liquid crystal molecules by interaction of polar groups with the substrate surface and the like.
  • “Liquid crystal display element” is a generic term for liquid crystal display panels and liquid crystal display modules.
  • the liquid crystal composition is usually prepared by mixing a plurality of liquid crystal compounds.
  • a polymerizable compound for the purpose of further adjusting the physical properties, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer, a dye, and an extinction
  • Additives such as foaming agents are added as needed.
  • the proportion (content) of the liquid crystal compound in the liquid crystal composition is represented by weight percentage (% by weight) based on the weight of the liquid crystal composition not including the additive, even when the additive is added.
  • the proportion (addition amount) of the additive in the liquid crystal composition is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition without the additive. That is, the proportions of the liquid crystal compound and the additive are calculated based on the total weight of the liquid crystal compound. Parts per million by weight (ppm) may be used.
  • the proportions of the polymerization initiator and the polymerization inhibitor in the liquid crystal composition are exceptionally expressed based on the weight of the polymerizable compound.
  • the “clearing point” is the transition temperature of the liquid crystal phase to the isotropic phase in the liquid crystal compound.
  • the “lower limit temperature of the liquid crystal phase” is a transition temperature of a solid-liquid crystal phase (eg, smectic phase, nematic phase) in a liquid crystal compound.
  • the “upper limit temperature of the nematic phase” is a transition temperature of the nematic phase-isotropic phase in the mixture of the liquid crystal compound and the base 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 expressions "increase dielectric anisotropy” and “large dielectric anisotropy” mean that the absolute value of the value increases or is large.
  • the voltage holding ratio is large means that the device has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit at the initial stage, and even after using the device for a long time, not only the room temperature but also the upper limit temperature. It means that it has a large voltage holding ratio even at temperatures close to.
  • the characteristics of the composition or element may be examined before and after the aging test (including the accelerated aging test).
  • the expression "high solubility in liquid crystal composition” means that the solubility is high in any of the composition containing the liquid crystal compound at normal temperature, but as the composition, in the following examples, It can be based on the composition used to assess solubility.
  • the compound represented by Formula (1) may be abbreviated as "compound (1).”
  • the compound (1) means one compound represented by the formula (1), a mixture of two compounds, or a mixture of three or more compounds. This rule also applies to at least one compound etc. selected from the group of compounds represented by formula (2). Symbols such as A 1 , B 1 and C 1 surrounded by a hexagon correspond to ring A 1 , ring B 1 and ring C 1 and the like, respectively.
  • the hexagon represents a six-membered ring such as a cyclohexane ring or a benzene ring or a fused ring such as a naphthalene ring.
  • any hydrogen on the ring may be replaced by a group such as -Sp 1 -P 1 .
  • the subscripts such as f, g, h etc indicate the number of substituted groups. When the subscript is 0, there is no such replacement.
  • the ring A and the ring C are independently X, Y or Z”, “separately” is used because the subject is plural. When the subject is "ring A”, “independent” is not used because the subject is singular.
  • the symbol of the terminal group R 11 is used for a plurality of compounds, but the groups represented by R 11 in these compounds may be the same or different.
  • R 11 of Compound (2) when R 11 of Compound (2) is ethyl, R 11 of compound (3) may be ethyl, it may be other groups, such as propyl.
  • This rule also applies to other symbols.
  • compound (8) when i is 2, two rings D 1 are present. Two groups represented by two rings D 1 in this compound may be identical or different. When i is greater than 2, it also applies to any two rings D 1 . This rule also applies to other symbols.
  • the expression "at least one 'A'” means that the number of 'A' is arbitrary.
  • the expression “at least one 'A' may be replaced by 'B'” is replaced by one 'A' by 'B' in the case of 'A' itself which is not replaced by 'B' In this case, the case where two or more 'A's are replaced by' B 'is included, and in these, the position of' A 'replaced by' B 'is arbitrary.
  • the rule that the substitution position is optional also applies to the expression "at least one 'A' has been replaced by 'B'".
  • At least one A may be replaced by B, C or D
  • B, C or D means that if A is not substituted then at least one A is replaced by C if at least one A is replaced by B And when at least one A is replaced by D, it is meant to include the case where more than one A is replaced by at least two of B, C, D.
  • R 11 and R 12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — is replaced by —O— Also, in these groups, the expression “at least one hydrogen may be replaced by fluorine” may be used. In this expression, “in these groups” may be interpreted literally. In this expression, “these groups” mean alkyl, alkenyl, alkoxy, alkenyloxy and the like. That is, “these groups” represent all of the groups described earlier than the term “in these groups”. This common sense interpretation applies to other terms as well.
  • Halogen means fluorine, chlorine, bromine or iodine. Preferred halogens are fluorine or chlorine. A further preferred halogen is fluorine.
  • the alkyl is linear or branched and does not include cyclic alkyl. Linear alkyls are generally preferred over branched alkyls. The same is true for end groups such as alkoxy and alkenyl.
  • the configuration of 1,4-cyclohexylene is preferably trans rather than cis in order to raise the upper limit temperature of the nematic phase.
  • 2-fluoro-1,4-phenylene means the following two divalent groups.
  • fluorine may be leftward (L) or rightward (R). This rule also applies to asymmetric asymmetric divalent groups generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl.
  • One embodiment of the present invention includes the following items and the like.
  • Item 1 The compound represented by Formula (1).
  • Ring A 1 and ring A 2 are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4 -Cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2 , 5-diyl, 1,3-dioxan
  • the compound according to Item 1, wherein OCF 2 —, —CH 2 O—, —OCH 2 —, or —CF CF—.
  • Ring A 1 and ring A 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, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, and in these rings, at least one hydrogen is fluorine, chlorine, carbon number 1 10 alkyl, alkenyl of 2 to 10 carbons, alkoxy of 1 to 9 carbons, or alkenyloxy of 2 to 9 carbons, and in these groups, at least one hydrogen is fluorine or chlorine
  • the compound according to Item 1 or 2 which may be replaced by
  • Item 4. The compound according to any one of Items 1 to 3, which is represented by any one of formulas (1-1) to (1-4).
  • R 1 is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 14 carbons, or alkenyloxy having 2 to 14 carbons, and in these groups, at least one hydrogen is , May be replaced by fluorine;
  • Ring A 1 , ring A 2 , ring A 3 and ring A 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, Tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl, in which ring at least one hydrogen is fluorine, alkyl having 1 to 10 carbons, 2 to 10 carbons Of C 1 to C 9 alkoxy or C 2 to C 9 alkenyloxy, and in these groups, at least one hydrogen may be replaced by fluorine;
  • Z 1 , Z 2 and Z 3 independently represent a single
  • Item 5 The compound according to any one of Items 1 to 4, which is represented by any one of Formulas (1-5) to (1-7).
  • R 1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkoxy having 1 to 9 carbons;
  • Ring A 1 , ring A 2 , ring A 3 and ring A 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, Tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl, in which ring at least one hydrogen is fluorine, alkyl having 1 to 5 carbons, 2 to 5 carbons Or alkenyl of 1 to 4 carbon atoms;
  • Sp 1 , Sp 2 , Sp 3 , and Sp 4 are
  • Item 6. The compound according to any one of items 1 to 5, represented by any one of formulas (1-8) to (1-16):
  • R 1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkoxy having 1 to 9 carbons;
  • Z 1 and Z 2 are independently a single bond or-(CH 2 ) 2- ;
  • Sp 1 , Sp 2 and Sp 3 are independently a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one —CH 2 — may be replaced by —O—;
  • Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons, or 1 to 4 carbons Is alkoxy;
  • Z 1 is a single bond
  • Sp 2 and Sp 3 are -CH 2-
  • Y 1 and Y 2 are hydrogen
  • Sp 1 is not -CH 2- .
  • Item 7. The compound according to any one of items 1 to 6, which is represented by any one of formulas (1-17) to (1-23).
  • R 1 is alkyl having 1 to 10 carbons; Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 are independently hydrogen, fluorine, methyl or ethyl; Sp 1 is a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one —CH 2 — may be replaced by —O—; In formula (1-18), When Y 1 and Y 2 are hydrogen, Sp 1 is not —CH 2 —.
  • Item 8 A liquid crystal composition containing at least one of the compounds according to any one of items 1 to 7.
  • Item 9 The liquid crystal composition according to item 8, containing at least one compound selected from the group of compounds represented by formulas (2) to (4).
  • R 11 and R 12 independently represent alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one of —CH 2 — is replaced by —O— Well, in these groups at least one hydrogen may be replaced by fluorine;
  • Ring B 1 , ring B 2 , ring B 3 and ring B 4 are each independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene, or pyrimidine-2,5-diyl;
  • Item 10 The liquid crystal composition according to item 8 or 9, containing at least one compound selected from the group of compounds represented by formulas (5) to (7).
  • R 13 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—, and in these groups, 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 ;
  • Ring C 1 , ring C 2 and ring C 3 are independently 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl Pyrimidine-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine;
  • Z 14, Z 15, and Z 16 are independently a
  • Item 11 The liquid crystal composition according to any one of items 8 to 10, containing at least one compound selected from the group of compounds represented by formula (8).
  • R 14 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—, and in these groups, At least one hydrogen may be replaced by fluorine;
  • X 12 is -C ⁇ N or -C ⁇ C-C ⁇ N;
  • Ring D 1 is 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or at least 1
  • Z 17 represents a single bond, -COO-, -OCO-, -CH 2 O-, -OCH 2- , -CF 2 O-, -OCF 2- , -CH 2 CH 2- , or -C ⁇ C- And L 13 and L
  • Item 12. The liquid crystal composition according to any one of items 8 to 11, containing at least one compound selected from the group of compounds represented by formulas (11) to (19).
  • R 15, R 16, and R 17 are independently alkenyl alkyl carbon atoms or 2 to 10 of 1 to 10 carbon atoms, in the alkyl and alkenyl, at least one of -CH 2 - by -O- Which may be replaced, in these groups at least one hydrogen may be replaced by fluorine, and R 17 may be hydrogen or fluorine;
  • Ring E 1 , ring E 2 , ring E 3 and ring E 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl Decahydronaphthalene-2,6-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine;
  • Ring E 5 and ring E 6 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl
  • Item 13 The liquid crystal composition according to any one of items 8 to 12, containing at least one polymerizable compound represented by formula (20) other than the compound represented by formula (1).
  • Ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl or pyridine -2-yl, in these rings, at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 1 carbon having at least one hydrogen replaced with halogen May be replaced by 12 alkyls; Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl
  • Item 14 The liquid crystal according to item 13, wherein P 11 , P 12 and P 13 are independently a group selected from the group of polymerizable groups represented by formula (P-1) to formula (P-5) Composition.
  • M 11 , M 12 and M 13 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen.
  • Item 15 Item 13 or 14, wherein the polymerizable compound represented by Formula (20) is at least one compound selected from the group of polymerizable compounds represented by Formula (20-1) to Formula (20-7) The liquid crystal composition as described in.
  • L 31 , L 32 , L 33 , L 34 , L 35 , L 36 , L 37 and L 38 are independently hydrogen, fluorine or methyl;
  • P 11 , P 12 and P 13 are independently a group selected from the group of polymerizable groups represented by Formula (P-1) to Formula (P-3).
  • M 11 , M 12 and M 13 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen.
  • Ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl or pyridine -2-yl, in these rings, at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 1 carbon having at least one hydrogen replaced with halogen May be replaced by 12 alkyls; Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl
  • Item 17 At least one selected from the group consisting of the liquid crystal composition according to any one of items 8 to 16, and at least a part of the liquid crystal composition according to any one of items 8 to 16 polymerized. Liquid crystal display element contained.
  • One embodiment of the present invention also includes the following items.
  • A At least two of additives such as a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer, a pigment, and an antifoamer
  • additives such as a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer, a pigment, and an antifoamer
  • B A polymerizable composition prepared by adding a polymerizable compound different from the compound (1) and the compound (20) to the liquid crystal composition described above.
  • C A polymerizable composition prepared by adding the compound (1) and the compound (20) to the liquid crystal composition described above.
  • D A liquid crystal composite prepared by polymerizing the polymerizable composition.
  • the compound (1) is characterized by having a mesogenic moiety composed of at least one ring, one polar group, and two or more polymerizable groups. Further, a spacer moiety (below Sp 1 ) bonded to a ring is branched to have a polymerizable group and a polar group on at least one side, and at least one polymerizable group on the other side, in particular, a polymerizable group characterized in that via a spacer part (below Sp 4) capped ethoxy group is attached to.
  • the compound (1) is useful because polar groups interact non-covalently with a substrate surface such as glass (or metal oxide).
  • One of the uses is an additive for a liquid crystal composition used in a liquid crystal display device, and in this use, the compound (1) is added for the purpose of controlling the alignment of liquid crystal molecules. It is preferable that such an additive is chemically stable under the condition sealed in a device, has a high ability to orient liquid crystal molecules, and has a high solubility in a liquid crystal composition, and that the additive When using for a liquid crystal display element, it is preferable that a liquid crystal display element with a large voltage holding ratio can be obtained.
  • the compound (1) fulfills such properties to a considerable extent, and the solubility in liquid crystal compositions is extremely high, which can not be achieved by the conventional compounds, and by using the compound (1), the conventional compounds A device excellent in orientation and long-term stability can be easily obtained as compared with the case of using.
  • the compound (1) will be described. Preferred examples of the symbols such as R 1 , A 1 and Sp 1 in compound (1) also apply to subformulas of compound (1), for example, formula (1-1) and the like.
  • the properties can be arbitrarily adjusted by appropriately combining the types of these groups.
  • the compound (1) may contain isotopes such as 2 H (deuterium) and 13 C in an amount larger than the natural abundance ratio because there is no significant difference in the properties of the compounds.
  • R 1 is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 14 carbons, or alkenyloxy having 2 to 14 carbons, and in these groups, at least one hydrogen May be replaced by fluorine. More preferable R 1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 9 carbons. Particularly preferred R 1 is alkyl having 1 to 10 carbons.
  • R 1 is alkyl having 1 to 15 carbons or alkoxy having 1 to 14 carbons tend to have high chemical stability.
  • Compounds in which R 1 is alkyl having 1 to 15 carbons, alkenyls having 2 to 15 carbons, or alkenyloxys having 2 to 14 carbons tend to have high solubility in liquid crystal compositions.
  • Compounds in which R 1 is alkyl having 1 to 15 carbon atoms tend to have high ability to align liquid crystal molecules.
  • Ring A 1 and ring A 2 are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4 -Cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2 , 5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl in which at least one hydrogen is fluorine, chlorine , Alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyloxy having 2 to 9 carbons. In these groups, at least
  • Preferred ring A 1 and ring A 2 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1, 3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl in which at least one hydrogen is fluorine, chlorine, 1 to 10 carbon atoms Alkyl, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyloxy having 2 to 9 carbons, and in these groups, at least one hydrogen is replaced by fluorine or chlorine It may be done.
  • More preferred ring A 1 and ring A 2 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl in which at least one hydrogen is fluorine, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons in these rings Or alkenyloxy having 2 to 9 carbon atoms, and in these groups, at least one hydrogen may be replaced by fluorine.
  • ring A 1 and ring A 2 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl in which at least one hydrogen is fluorine, alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons, or 1 to 4 carbons. It may be replaced by alkoxy.
  • Particularly preferable ring A 1 and ring A 2 are 1,4-cyclohexylene, 1,4-phenylene, 2-substituted, 3-substituted, or 2- and 3-substituted 1,4-phenylene, and the substituents Is preferably hydrogen, fluorine, alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons, or alkoxy having 1 to 4 carbons, and more preferably hydrogen, fluorine, methyl or ethyl .
  • Ring A 1 and ring A 2 are independently 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-phenylene, or at least one hydrogen is replaced by fluorine 1 , 4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with alkyl having 1 to 5 carbon atoms, decahydronaphthalene-2,6-diyl, or tetrahydropyran-2,5-diyl , Chemical stability tends to be high.
  • Ring A 1 and Ring A 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine, at least Compounds in which one hydrogen is 1,4-phenylene in which one hydrogen is replaced by alkyl having 1 to 5 carbons or 1,4-phenylene in which at least one hydrogen is replaced by alkenyl having 2 to 5 carbons have a liquid crystal composition There is a tendency for the solubility to be large.
  • Ring A 1 and Ring A 2 are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by alkyl having 1 to 2 carbon atoms; And the ability to align liquid crystal molecules tends to be high.
  • Ring A 1 and Ring A 2 are independently 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by alkyl having 1 to 5 carbon atoms, at least one hydrogen has 1 to 4 carbon atoms
  • Compounds that are alkoxy-substituted 1,4-phenylene, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl tend to be highly polymerizable by ultraviolet irradiation. It is in.
  • a is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 1, 2 or 3 and particularly preferably 1 or 2. It is.
  • Compounds in which a is 0 tend to have high solubility in liquid crystal compositions.
  • Compounds in which a is 3 or 4 tend to have high ability to align liquid crystal molecules.
  • Compounds in which a is 1 or 2 have high solubility in liquid crystal compositions, high ability to align liquid crystal molecules, and tend to have high polymerization reactivity due to ultraviolet irradiation.
  • a particularly preferred Z 1 which is a bond or-(CH 2 ) 2- is a single bond.
  • Sp 1 is a single bond or an alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one —CH 2 — may be replaced by —O—;
  • Sp 2 and Sp 3 are independently a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one —CH 2 — may be replaced by —O—, more preferably -CH 2- and Sp 4 is -CH 2- .
  • Sp 5 is alkylene having 2 to 10 carbons, and in this alkylene, at least one —CH 2 — may be replaced by —O—.
  • Preferred Sp 5 is alkylene having 2 to 7 carbon atoms, in which at least one —CH 2 — may be replaced by —O—.
  • Compounds in which Sp 5 is an alkylene having 2 to 7 carbon atoms have high chemical stability and tend to be more excellent in solubility in liquid crystal compositions.
  • Compounds in which Sp 5 is a group in which at least one —CH 2 — of C 2 to C 7 alkylene is replaced by —O— have a high solubility in liquid crystal compositions and tend to have high ability to align liquid crystal molecules. It is in.
  • Sp 5 is particularly preferably — (CH 2 ) 2 — from the viewpoint of being a compound which is more excellent due to the solubility in the liquid crystal composition.
  • M 1 , M 2 , M 3 and M 4 independently represent hydrogen, fluorine, chlorine, alkyl having 1 to 5 carbon atoms, or 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine
  • Preferred R 2 is hydrogen or alkyl having 1 to 5 carbons. More preferable R 2 is alkyl having 1 to 3 carbon atoms, from the viewpoint of being a compound which is more excellent in solubility in liquid crystal composition, high in chemical stability, and high in ability to align liquid crystal molecules, etc.
  • Preferred R 2 is methyl.
  • X 1 is —OH, —NH 2 , —OR 3 , —N (R 3 ) 2 , —COOH, —SH, or —Si (R 3 ) 3 .
  • preferable X 1 is —OH, —NH 2 or —SH, and particularly preferable X 1 is —OH.
  • Examples of preferable compound (1) are compounds (1-1) to (1-4) described in Item 4. Examples of more preferable compound (1) are compounds (1-5) to (1-7) described in item 5. Examples of further preferable compound (1) are compounds (1-8) to (1-16) described in Item 6. Examples of the most preferred compound (1) are compounds (1-17) to (1-23) described in Item 7.
  • Synthesis of Compound (1) A synthesis method of compound (1) will be described.
  • the compound (1) can be synthesized by appropriately combining the methods of synthetic organic chemistry.
  • the compounds that did not describe the synthesis method are “Organic Synthesis” (Organic Syntheses, John Wiley & Sons, Inc.), “Organic Reactions” (Organic Reactions, John Wiley & Sons, Inc.), “Comprehensive Organic” Synthesis can be carried out by the method described in the book such as “Comprehensive Organic Synthesis, Pergamon Press”, “New Experimental Chemistry Lecture” (Maruzen).
  • MSG 1 (or MSG 2 ) is a monovalent organic group having at least one ring.
  • the monovalent organic groups represented by a plurality of MSG 1 (or MSG 2 ) may be the same or different.
  • Compounds (1A) to (1G) correspond to compound (1) or an intermediate of compound (1).
  • ring A 1 and A 2 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-cyclohexenylene , 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl
  • Starting materials are commercially available with respect to rings such as 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, etc., or a synthetic method is well known .
  • Sp 4 is -CH 2-
  • Sp 5 is-(CH 2 ) 2-
  • M 1 , M 2 , M 3 and M 4 are hydrogen and X 1 is-
  • the compound (1-51) which is OH can be synthesized by the following method.
  • Compound (51) is reacted with formaldehyde in the presence of DABCO (1,4-diazabicyclo [2.2.2] octane) to give compound (52).
  • Compound (52) is reacted with trifluoromethanesulfonic anhydride (Tf 2 O) and triethylamine, and then reacted with ethylene glycol to give compound (53).
  • Tf 2 O trifluoromethanesulfonic anhydride
  • Compound (53) is reacted with 3,4-dihydro-2H-pyran in the presence of PPTS (pyridinium p-toluenesulfonate) to give compound (54).
  • Compound (54) is hydrolyzed with lithium hydroxide to give compound (55).
  • Diol (56) synthesized by a known method and compound (57) are reacted in the presence of triethylamine to obtain compound (58).
  • Compound (58) and Compound (55) are reacted in the presence of DCC and DMAP to obtain Compound (59), and then deprotected using PPTS to lead to Compound (1-51). it can.
  • Liquid Crystal Composition 3-1 Component Compound
  • the liquid crystal composition according to an embodiment of the present invention contains the compound (1) as a component A.
  • the compound (1) can control the alignment of liquid crystal molecules by noncovalent interaction with the substrate of the device. It is preferable that this composition contains the compound (1) as the component A, and further contains at least one liquid crystal compound selected from the following components B, C, D, and E.
  • Component B is selected from compounds (2) to (4).
  • Component C is selected from compounds (5) to (7) other than compounds (2) to (4).
  • Component D is a compound (8).
  • Component E is selected from compounds (11) to (19). This composition may contain other liquid crystal compounds different from the compounds (2) to (8) and (11) to (19).
  • compositions with appropriately selected components have high upper limit temperature, lower limit temperature, lower viscosity, suitable optical anisotropy (ie large optical anisotropy or small optical anisotropy), positive or negative large dielectric constant It has anisotropy, high specific resistance, stability to heat or ultraviolet light, and a suitable elastic constant (ie, a large elastic constant or a small elastic constant).
  • the compound (1) is added to the composition for the purpose of controlling the alignment of liquid crystal molecules.
  • the preferred ratio of the compound (1) to 100% by weight of the liquid crystal composition is 0.05% by weight or more from the viewpoint that liquid crystal molecules can be easily aligned, etc., and the display defect of the device can be further prevented. From the point of etc., it is preferable that it is 10 weight% or less. A more preferable ratio is in the range of 0.1% by weight to 7% by weight, and a further preferable ratio is in the range of 0.4% by weight to 5% by weight, and a particularly preferable ratio is 0.5% by weight to 5%. It is the range of weight%. These ratios also apply to the composition containing compound (20).
  • Component B is a compound in which the two end groups are alkyl or the like.
  • Component B has a small dielectric anisotropy.
  • Preferred examples of component B include compounds (2-1) to (2-11), compounds (3-1) to (3-19), and compounds (4-1) to (4-7). it can.
  • R 11 and R 12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl or alkenyl, at least one —CH 2 — is —O— In these groups, at least one hydrogen may be replaced by fluorine.
  • the component B is a compound close to neutrality because the absolute value of the dielectric anisotropy is small.
  • the compound (2) is mainly effective in reducing the viscosity or adjusting the optical anisotropy.
  • the compounds (3) and (4) are effective in extending the temperature range of the nematic phase or in adjusting the optical anisotropy by raising the upper limit temperature.
  • the content of Component B is preferably 30% by weight or more, more preferably 40% by weight or more, based on 100% by weight of the liquid crystal composition, and the upper limit thereof is not particularly limited, and is, for example, 99.95% by weight.
  • Component C is a compound having a fluorine, chlorine or fluorine-containing group at at least one end.
  • Component C has a large dielectric anisotropy.
  • Preferred examples of component C include compounds (5-1) to (5-16), compounds (6-1) to (6-116), and compounds (7-1) to (7-59). .
  • R 13 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O— In these groups, 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 C has a positive dielectric anisotropy and is very good in stability to heat, light and the like, and thus is suitably used when preparing a composition for modes such as IPS, FFS and OCB. .
  • the content of component C with respect to 100% by weight of the liquid crystal composition is suitably in the range of 1% by weight to 99% by weight, and preferably Is in the range of 10% by weight to 97% by weight, more preferably in the range of 40% by weight to 95% by weight.
  • component C is added to a composition having a negative dielectric anisotropy, the content of component C is preferably 30% by weight or less based on 100% by weight of the liquid crystal composition.
  • Component D is a compound (8) in which one terminal group is —C ⁇ N or —C ⁇ C—C ⁇ N.
  • Component D has a cyano group and thus has a larger dielectric anisotropy positively.
  • compounds (8-1) to (8-64) can be mentioned.
  • R 14 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O— In these groups, at least one hydrogen may be replaced by fluorine; -X 12 is -C ⁇ N or -C ⁇ C-C ⁇ N.
  • Component D is mainly used when preparing a composition for a mode such as TN since the dielectric anisotropy is positive and the value thereof is large. By adding this component D, the dielectric anisotropy of the composition can be increased. Component D has the effect of widening the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. Component D is also useful for adjusting the voltage-transmittance curve of the device.
  • the content of component D with respect to 100% by weight of the liquid crystal composition is suitably in the range of 1% by weight to 99% by weight, and preferably Is in the range of 10% by weight to 97% by weight, more preferably in the range of 40% by weight to 95% by weight.
  • the content of component D is preferably 30% by weight or less based on 100% by weight of the liquid crystal composition.
  • Component E is selected from compounds (11) to (19).
  • Component E has a large negative dielectric anisotropy. These compounds have phenylene in which lateral position is substituted by two halogens (fluorine or chlorine) like 2,3-difluoro-1,4-phenylene.
  • Preferred examples of component E include compounds (11-1) to (11-9), compounds (12-1) to (12-19), compounds (13-1) and (13-2), and compounds (14-). 1) to (14-3), compounds (15-1) to (15-3), compounds (16-1) to (16-11), compounds (17-1) to (17-3), compounds 18-1) to (18-3) and the compound (19-1) can be mentioned.
  • R 15, R 16, and R 17 are independently alkenyl alkyl carbon atoms or 2 to 10 of 1 to 10 carbon atoms, in the alkyl and alkenyl, at least one -CH 2 - May be replaced by —O—, in these groups at least one hydrogen may be replaced by fluorine and R 17 may be hydrogen or fluorine.
  • Component E has a large negative dielectric anisotropy.
  • Component E is suitably used when preparing a composition for modes such as IPS, VA, PSA and the like.
  • the dielectric anisotropy of the composition increases negatively, but the viscosity increases. Therefore, as long as the required value of the threshold voltage of the device is satisfied, the content is preferably as small as possible.
  • the content of component E with respect to 100% by weight of the liquid crystal composition is preferably 40% by weight or more in order to achieve sufficient voltage driving.
  • the compound (11) is a bicyclic compound, it has an effect of lowering the viscosity, adjusting the optical anisotropy or increasing the dielectric anisotropy.
  • Compounds (12) and (13) are tricyclic compounds, and compound (14) is a tetracyclic compound. Therefore, the effects of increasing the maximum temperature, optical anisotropy, or dielectric anisotropy are obtained. is there.
  • Compounds (15) to (19) have the effect of increasing the dielectric anisotropy.
  • the content of the component E is preferably 40% by weight or more, more preferably 50% by weight, relative to 100% by weight of the liquid crystal composition. % To 95% by weight.
  • the content of component E is preferably 30% by weight or less based on 100% by weight of the liquid crystal composition.
  • liquid crystal composition satisfying at least one of the properties such as specific resistance, high stability to ultraviolet light, high stability to heat, and a large elastic constant.
  • the liquid crystal composition is prepared by a known method. For example, there is a method in which the components are mixed and dissolved with one another by heating.
  • additives may be added to the composition.
  • additives include polymerizable compounds other than the compound (1), polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dyes, antifoaming agents, etc. It is. Such additives are well known to those skilled in the art and are described in the literature.
  • the polymerizable compound is added in order to form a polymer in the liquid crystal composition.
  • a polymer can be produced
  • the compound (1) is immobilized in the state where its polar group interacts non-covalently with the substrate surface of the glass (or metal oxide).
  • the ability to control the alignment of liquid crystal molecules is further improved, and an appropriate pretilt is obtained, so that the response time is shortened.
  • Preferred examples of the polymerizable compound are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes), and vinyl ketones. Further preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. Further preferred examples also include compounds having both acryloyloxy and methacryloyloxy.
  • a particularly preferred example of the polymerizable compound includes the compound (20).
  • the compound (20) is a compound different from the compound (1).
  • the compound (1) has a polar group. On the other hand, it is preferable that a compound (20) does not have a polar group.
  • ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine- 2-yl or pyridin-2-yl in which at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is halogen It may be substituted by substituted C 1 to C 12 alkyl.
  • Preferred ring F and ring I are cyclohexyl, cyclohexenyl, phenyl, fluorophenyl, difluorophenyl, 1-naphthyl or 2-naphthyl. Further preferred ring F and ring I are cyclohexyl, cyclohexenyl or phenyl. Particularly preferred ring F and ring I are phenyl.
  • ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene- 1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2, 6-diyl, naphthalene-2,7-diyl, phenanthrene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or Pyridine-2,5-diyl
  • Preferred ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3 -Diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl Naphthalene-2,6-diyl and naphthalene-2,7-diyl.
  • More preferable ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene or 2-fluoro-1,4-phenylene.
  • Particularly preferred ring G is 1,4-phenylene or 2-fluoro-1,4-phenylene.
  • the most preferred ring G is 1,4-phenylene.
  • Preferred Z 22 and Z 23 are a single bond, -CH 2 CH 2- , -CH 2 O-, -OCH 2- , -COO-, or -OCO-. Further preferred Z 22 and Z 23 are single bonds.
  • P 11 , P 12 and P 13 are independently a polymerizable group.
  • Preferred P 11 to P 13 are groups selected from the group of polymerizable groups represented by formulas (P-1) to (P-5). Further preferable P 11 to P 13 are groups represented by Formula (P-1), Formula (P-2), or Formula (P-3). Particularly preferable P 11 to P 13 are groups represented by formula (P-1).
  • the wavy lines in formulas (P-1) to (P-5) indicate the binding site.
  • M 11 , M 12 and M 13 independently represent hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is replaced by halogen Alkyl having 1 to 5 carbon atoms.
  • Preferred M 11 , M 12 and M 13 are hydrogen or methyl to increase the reactivity.
  • Further preferred M 11 is hydrogen or methyl, and further preferred M 12 and M 13 are hydrogen.
  • Preferred Sp 11 , Sp 12 and Sp 13 are single bonds.
  • u is 0, 1 or 2.
  • Preferred u is 0 or 1.
  • f, g and h are independently 0, 1, 2, 3 or 4 and the sum of f, g and h is 1 or more.
  • Preferred f, g or h is 0, 1 or 2.
  • the preferred sum is 2, 3 or 4. More preferable sum is 2 or 3.
  • Preferred examples of the compound (20) are the compounds (20-1) to the compounds (20-7) described in item 15 and the following compounds (20-8) to (20-11). Further preferable examples are compound (20-1-1) to (20-1-5), compound (20-2-1) to (20-2-5), compound (20-4-1), compound ( 20-5-1), a compound (20-6-1), and a compound (20-7-1).
  • 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 alkyl having 1 to 5 carbons;
  • v and x are independently 0 or 1;
  • t and u are independently an integer of 1 to 10 And t + v and x + u are each at most 10;
  • L 31 to L 36 are independently hydrogen or fluorine, and
  • L 37 and L 38 are independently hydrogen, fluorine or methyl.
  • the polymerizable compound in the composition can be rapidly polymerized by using a polymerization initiator such as a radical photopolymerization initiator.
  • a polymerization initiator such as a radical photopolymerization initiator.
  • the amount of the remaining polymerizable compound can be reduced by optimizing the reaction conditions in the polymerization.
  • photo radical polymerization initiators include TPO, 1173, and 4265 from Darocure series of BASF, and 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, from Irgacure series. 1850 and 2959 can be mentioned.
  • photo radical polymerization initiators include 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyl Dimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate mixture, benzophenone / methyltriethanolamine mixture It is.
  • polymerization After adding a photo radical polymerization initiator to the liquid crystal composition, polymerization can be performed by irradiating ultraviolet light in a state where an electric field is applied. However, unreacted polymerization initiator or decomposition products of the polymerization initiator may cause display defects such as image sticking to the device. In order to prevent this, photopolymerization may be carried out without adding a polymerization initiator.
  • the preferred wavelength of the light to be irradiated is in the range of 150 nm to 500 nm. A further preferred wavelength is in the range of 250 nm to 450 nm, and the most preferred wavelength is 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. When the polymerization compound contains a polymerization inhibitor, it 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.
  • the optically active compound has an effect of preventing reverse twist by inducing a helical structure to liquid crystal molecules to give a necessary twist angle.
  • the helical pitch can be adjusted by adding an optically active compound.
  • Two or more optically active compounds may be added in order to adjust the temperature dependency of the helical pitch.
  • the optically active compounds the following compounds (Op-1) to (Op-18) can be mentioned.
  • ring J is 1,4-cyclohexylene or 1,4-phenylene
  • R 28 is alkyl having 1 to 10 carbons.
  • the symbol * represents an asymmetric carbon.
  • an antioxidant is effective to maintain a large voltage holding ratio of the device.
  • the following compounds (AO-1) and (AO-2); Irganox 415, Irganox 565, Irganox 1010, Irganox 1035, Irganox 3114, and Irganox 1098 (trade name; manufactured by BASF) can be mentioned.
  • UV absorber is effective to prevent the lowering of the upper limit temperature of the device.
  • Preferred examples of UV absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like, and specific examples thereof include the following compounds (AO-3) and (AO-4); Tinuvin 329, Tinuvin P, Tinuvin 326, Tinuvin 326, Tinuvin 213, Tinuvin 400, There may be mentioned Tinuvin 328, and Tinuvin 99-2 (trade name; BASF AG); and 1,4-diazabicyclo [2.2.2] octane (DABCO).
  • light stabilizers such as sterically hindered amines is preferred to maintain high voltage holding of the device.
  • the following compounds AO-5), (AO-6), and (AO-7); Tinuvin 144, Tinuvin 765, and Tinuvin 770 DF (trade name; BASF Corporation); LA-77Y and LA- 77G (trade name; ADEKA company) can be mentioned.
  • heat stabilizer is also effective for maintaining a large voltage holding ratio of the device, and a preferred example is Irgafos 168 (trade name; BASF Corporation).
  • a dichroic dye such as an azo dye or an anthraquinone dye is added to the composition.
  • Defoamers are effective to prevent foaming.
  • Preferred examples of the antifoaming agent are dimethyl silicone oil, methylphenyl silicone oil and the like.
  • R 40 is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, -COOR 41 , or -CH 2 CH 2 COOR 41 , wherein R 41 is 1 carbon To 20 alkyl.
  • R 42 is alkyl having 1 to 20 carbons.
  • R 43 is hydrogen, methyl or O.
  • ring G 1 is 1,4-cyclohexylene or 1,4-phenylene; in compound (AO-7)
  • ring G 2 is a group in which at least one hydrogen of 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene is replaced by fluorine; compounds (AO-5) and (AO-7) In the above, z is 1, 2 or 3.
  • the liquid crystal composition has an operation mode such as PC, TN, STN, OCB or PSA and can be suitably used for a liquid crystal display element driven by an active matrix system.
  • This composition has an operation mode such as PC, TN, STN, OCB, VA, IPS, etc., and can also be suitably used for a liquid crystal display element driven by a passive matrix system.
  • These elements can be applied to any of reflective, transmissive and semi-transmissive types.
  • the composition is also suitable for a nematic curvilinear aligned phase (NCAP) device, in which the composition is microencapsulated.
  • NCAP nematic curvilinear aligned phase
  • This composition can also be used for polymer dispersed liquid crystal display (PDLCD) and polymer network liquid crystal display (PNLCD).
  • PDLCD polymer dispersed liquid crystal display
  • PLCD polymer network liquid crystal display
  • the ratio of the polymerizable compound is preferably 10% by weight or less with respect to 100% by weight of the liquid crystal composition, and a more preferable ratio is 0.1% by weight to 2% %, And more preferably 0.2% to 1.0% by weight.
  • the element in the PSA mode can be driven by a driving method such as an active matrix method or a passive matrix method. Such an element can be applied to any of reflective, transmissive, and semi-transmissive types.
  • a polymer contained in the composition aligns liquid crystal molecules.
  • Polar compounds help the liquid crystal molecules to align. That is, a polar compound can be used instead of the alignment film.
  • An example of a method of manufacturing such a device is as follows. An element having two substrates called an array substrate and a color filter substrate is prepared. This substrate does not have an alignment film. At least one of the substrates has an electrode layer. A liquid crystal compound is mixed to prepare a liquid crystal composition. To this composition is added compound (1), and, if necessary, other polymerizable compounds and polar compounds. Additives may be further added as needed. The composition is injected into the device. Light is irradiated in a state where a voltage is applied to this element. UV light is preferred. The polymerizable compound is polymerized by light irradiation. By this polymerization, a composition containing a polymer is formed, and a device having a PSA mode is produced.
  • polar compounds are arranged on the substrate as the polar groups interact with the substrate surface.
  • This polar compound aligns the liquid crystal molecules.
  • the interaction with the substrate surface becomes stronger and can be oriented at a low concentration.
  • the alignment of liquid crystal molecules is further promoted by the action of an electric field.
  • the polymerizable compound is also oriented according to this orientation. In this state, since the polymerizable compound is polymerized by ultraviolet light, a polymer maintaining this orientation is formed. The effect of the polymer is to additionally stabilize the orientation of the liquid crystal molecules, thus reducing the response time of the device. Since image sticking is a malfunction of liquid crystal molecules, the effect of the polymer is to simultaneously improve the sticking.
  • the compound (1) Since the compound (1) is polymerizable, it is consumed by polymerization. The compound (1) is also consumed by copolymerizing with other polymerizable compounds. Accordingly, the compound (1) has a polar group but is consumed, so that a liquid crystal display device having a large voltage holding ratio can be obtained. In addition, since the effects of both the polar compound and the polymerizable compound can be achieved with one compound by using the polar compound having the polymerizability, the polymerizable compound having no polar group is not required. is there.
  • the present invention will be described in more detail by way of examples (including synthesis examples and usage examples). The invention is not limited by these examples.
  • the invention also includes mixtures prepared by mixing at least two of the compositions of the Use Examples.
  • Example 1 Examples of Compound (1) Unless otherwise stated, reactions were carried out under a nitrogen atmosphere. Compound (1) was synthesized by the procedure shown in Example 1 and the like. The compound synthesized was identified by a method such as NMR analysis. The properties of the compound (1), the liquid crystal compound, the composition and the device were measured by the following methods.
  • NMR analysis For measurement, DRX-500 manufactured by Bruker Biospin Ltd. was used. In the measurement of 1 H-NMR, the sample was dissolved in a deuterated solvent such as CDCl 3, and the measurement was performed at room temperature under conditions of 500 MHz and 16 integrations. Tetramethylsilane was used as an internal standard. In the measurement of 19 F-NMR, CFCl 3 was used as an internal standard, and the measurement was performed under the condition of 24 times of integration. In the description of nuclear magnetic resonance spectrum, s is singlet, d is doublet, t is triplet, q is quartet, quin is quintet, sext is sextet, m is multiplet, br is broad.
  • a GC-2010 gas chromatograph manufactured by Shimadzu Corporation was used for measurement.
  • capillary columns DB-1 (length 60 m, inner diameter 0.25 mm, film thickness 0.25 ⁇ m) manufactured by Agilent Technologies Inc. were used.
  • Helium (1 ml / min) was used as a carrier gas.
  • the temperature of the sample vaporization chamber was set to 300 ° C.
  • the temperature of the detector (FID) portion was set to 300 ° C.
  • the sample was dissolved in acetone to prepare a 1% by weight solution, and 1 ⁇ l of the resulting solution was injected into the sample vaporization chamber.
  • a recorder a GC Solution system manufactured by Shimadzu Corporation was used.
  • HPLC analysis For measurement, Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used.
  • the column used was YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle diameter 5 ⁇ m) manufactured by YMC.
  • the eluate was used by appropriately mixing acetonitrile and water.
  • a detector a UV detector, an RI detector, a CORONA detector, etc. were used suitably. When a UV detector was used, the detection wavelength was 254 nm.
  • the sample was dissolved in acetonitrile to prepare 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 spectroscopy For measurement, PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used. The detection wavelength was from 190 nm to 700 nm. The sample was dissolved in acetonitrile to prepare 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 (clearing point, melting point, polymerization initiation temperature, etc.), the compound itself was used as a sample.
  • Measurement method The measurement of the characteristics was performed by the following method. Many of these are described in the JEITA standard (JEITA ED-2521B) deliberated and enacted by the Japan Electronics and Information Technology Industries Association (JEITA), or a modified method thereof. there were. A thin film transistor (TFT) was not attached to the TN device used for the measurement.
  • JEITA Japan Electronics and Information Technology Industries Association
  • Phase structure The sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarization microscope (model: FP-52 hot stage manufactured by Mettler). While heating this sample at a rate of 3 ° C./min, the phase state and its change were observed with a polarization microscope to identify the type of phase.
  • a polarization microscope model: FP-52 hot stage manufactured by Mettler
  • Transition temperature (° C)
  • a scanning calorimeter manufactured by Perkin Elmer, a Diamond DSC system, or a high-sensitivity differential scanning calorimeter manufactured by Hitachi High-Tech Science Co., Ltd., X-DSC7000 was used.
  • the temperature of the sample was raised and lowered at a rate of 3 ° C./min, and the transition point was determined by extrapolating the start point of the endothermic peak or exothermic peak associated with the phase change of the sample.
  • the melting point of the compound and the polymerization initiation temperature were also measured using this apparatus.
  • 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 "the lower limit temperature of the liquid crystal phase”.
  • the temperature at which a compound transitions from liquid crystal phase to liquid may be abbreviated as the "clearing point”.
  • the crystal is designated C.
  • the smectic phase is represented by S and the nematic phase is represented by N.
  • a smectic A phase, a smectic B phase, a smectic C phase, or a smectic F phase can be distinguished among the smectic phases, they are represented as S A , S B , S C or S F , respectively.
  • the liquid (isotropic) was designated as I.
  • the transition temperature is expressed as, for example, "C 50.0 N 100.0 I". This indicates that the transition temperature from crystal to nematic phase is 50.0 ° C., and the transition temperature from nematic phase to liquid is 100.0 ° C.
  • T NI or NI Maximum temperature of nematic phase
  • the sample was placed on the hot plate of a melting point apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when part of the sample changed from the nematic phase to the isotropic liquid.
  • the upper limit temperature of the nematic phase may be abbreviated as "upper limit temperature”.
  • TNI When the sample is a mixture of compound (1) and mother liquid crystals, it is indicated by the symbol TNI .
  • TNI When the sample is a mixture of compound (1) and a compound such as component B, C or D, it is indicated by the symbol NI.
  • Viscosity Bulk viscosity; ;; measured at 20 ° C .; mPa ⁇ s
  • an E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used.
  • the measurement method of characteristics may be different between the sample with positive dielectric anisotropy and the sample with negative dielectric anisotropy.
  • the measuring methods when the dielectric anisotropy is positive are described in the items (8a) to (12a).
  • the terms (8b) to (12b) are described.
  • Viscosity Rotational viscosity; ⁇ 1; measured at 25 ° C .; mPa ⁇ s) Positive dielectric anisotropy: The measurement was according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). The sample was placed in a TN device having a twist angle of 0 degree and a distance between two glass substrates (cell gap) of 5 ⁇ m. A voltage was applied to this element in steps of 0.5 V in the range of 16 V to 19.5 V. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds).
  • the peak current and peak time of transient current generated by this application were measured. These measurements and M.
  • the rotational viscosity was obtained from the paper of Imai et al., Calculation formula (8) on page 40. The value of dielectric anisotropy required for this calculation was determined by the method described below using the device for which this rotational viscosity was measured.
  • Viscosity Rotational viscosity; ⁇ 1; measured at 25 ° C .; mPa ⁇ s
  • Negative dielectric anisotropy Measurement was according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 20 ⁇ m. A voltage was applied to the device stepwise in steps of 1 volt in the range of 39 to 50 volts. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds).
  • the dielectric constants ( ⁇ and ⁇ ) were measured as follows. 1) Measurement of dielectric constant ( ⁇ ): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a well-cleaned glass substrate. The glass substrate was rotated by a spinner and then heated at 150 ° C. for 1 hour. A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 4 ⁇ m, and this device was sealed with an adhesive cured with ultraviolet light.
  • Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant ( ⁇ ) in the major axis direction of liquid crystal molecules was measured.
  • 2) Measurement of dielectric constant ( ⁇ ) A polyimide solution was applied to a well-cleaned glass substrate. After firing the glass substrate, the obtained alignment film was rubbed. The sample was placed in a TN device in which the distance between two glass substrates (cell gap) was 9 ⁇ m and the twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant ( ⁇ ) in the minor axis direction of liquid crystal molecules was measured.
  • Threshold voltage (Vth; measured at 25 ° C .; V) Positive dielectric anisotropy: For measurement, an LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. The sample was placed in a normally white mode TN device in which the distance between two glass substrates (cell gap) is 0.45 / ⁇ n ( ⁇ m) and the twist angle is 80 degrees. The voltage (32 Hz, rectangular wave) applied to this element was gradually increased by 0.02 V from 0 V to 10 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The threshold voltage was represented by the voltage at 90% transmittance.
  • Threshold voltage (Vth; measured at 25 ° C .; V) Negative dielectric anisotropy: For measurement, an LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. A sample is placed in a normally black mode VA device in which the distance between two glass substrates (cell gap) is 4 ⁇ m and the rubbing direction is antiparallel, and an adhesive for curing this device with ultraviolet light is used. Used and sealed. The voltage (60 Hz, rectangular wave) applied to this element was gradually increased by 0.02 V from 0 V to 20 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The threshold voltage was represented by the voltage at 10% transmittance.
  • the rise time ( ⁇ r: millisecond) is the time taken for the transmittance to change from 90% to 10%.
  • the fall time ( ⁇ f: milliseconds) is the time taken to change from 10% transmission to 90% transmission.
  • the response time is represented by the sum of the rise time and the fall time obtained in this manner.
  • a rectangular wave 60 Hz, 10 V, 0.5 seconds was applied to this element.
  • the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. It was considered that the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum.
  • the response time is represented by the time (fall time; milliseconds) taken to change from 90% transmittance to 10% transmittance.
  • Raw materials Solmix (registered trademark) A-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (IPA) (1.1%), and is sold by Nippon Alcohol Sales Co., Ltd. obtained.
  • Step 2 Compound (T-2) (6.18 g), 3,4-dihydro-2H-pyran (3.57 g), pyridinium p-toluenesulfonate (PPTS) (0.970 g), and dichloromethane (60. 6). 0 ml) was charged into the reactor and stirred at room temperature for 12 hours. The reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate.
  • PPTS pyridinium p-toluenesulfonate
  • Step 3 Compound (T-3) (9.15 g), THF (45.0 ml), and water (45.0 ml) were charged into a reactor and cooled to 0 ° C. Lithium hydroxide monohydrate (3.14 g) was added there, and it stirred for 7 hours, returning to room temperature. The reaction mixture was poured into water, 6N hydrochloric acid (15 ml) was slowly added to acidify, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to give compound (T-4) (5.07 g; 59%).
  • Step 4 Compound (T-5) (124 g), triethylamine (52.4 g), and THF (3100 ml) synthesized according to the method described in WO 2014/097952 were charged into a reactor and cooled to 0 ° C. .
  • the compound (T-6) (50.0 g) was slowly dropped there, and stirred at 50 ° C. for 3 hours.
  • the reaction mixture was poured into brine and the aqueous layer was extracted with t-butyl methyl ether.
  • the obtained organic layer was washed successively with water and brine, and dried over anhydrous magnesium sulfate.
  • Step 3 Lithium aluminum hydride (2.46 g) and THF (200 ml) were charged to the reactor and cooled to 0 ° C. A solution of compound (T-12) (34.8 g) in THF (150 ml) was slowly added thereto, and the mixture was stirred for 3 hours while returning to room temperature. The reaction mixture was poured into water, insolubles were filtered off, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by recrystallization from heptane to give compound (T-13) (18.3 g; 61%).
  • TsCl p-toluenesulfon
  • Step 8 Compound (T-19) (6.67 g; 88%) was obtained in the same manner as in the fifth step of Synthesis Example 1 using compound (T-18) (5.00 g) as a starting material.
  • Step 9 Using compound (T-19) (6.67 g) as a starting material, and according to the same method as step 6 of Synthesis Example 1, compound (1-2-6) (4.32 g; 75%) was obtained.
  • Step 3 Compound (T-22) (137 g), triphenylphosphine (115 g), and dichloromethane (850 ml) were charged into a reactor, and cooled to 0 ° C. Thereto, a solution of carbon tetrabromide (145 g) in THF (500 ml) was slowly added, and stirred for 12 hours while returning to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (heptane) to give compound (T-23) (132 g; 82%).
  • Step 4 Compound (T-23) (132 g), triphenylphosphine (94.1 g), and toluene (2500 ml) were placed in a reactor, and heating to reflux was carried out at 110 ° C. for 15 hours. The reaction mixture was cooled to 0 ° C., and the precipitated crystals were collected by filtration to give compound (T-24) (178 g; 82%).
  • Step 5 Compound (T-24) (178 g) and THF (900 ml) were placed in a reactor and cooled to -30.degree. To this was added potassium t-butoxide (29.9 g), and the mixture was stirred at -30 ° C for 1 hour. Next, a solution of compound (T-25) (38.4 g) in THF (900 ml) was slowly added dropwise, and stirred for 12 hours while returning to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate.
  • Step 6 Using compound (T-26) (78.1 g) as a starting material, compound (T-27) (78.0 g; 99%) was obtained in the same manner as in the second step of Synthesis Example 2.
  • Step 7 The compound (T-27) (74.6 g), p-toluenesulfonic acid monohydrate (PTSA), toluene (800 ml) and methanol (800 ml) were placed in a reactor and stirred at room temperature for 12 hours did.
  • the reaction mixture was poured into saturated aqueous sodium hydrogen carbonate solution, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate.
  • the solution was concentrated under reduced pressure to give compound (T-28) (59.0 g, yield 87%).
  • Step 8 Compound (T-29) (6.44 g; 43%) was obtained in the same manner as in the seventh step of Synthesis Example 2 using compound (T-28) (12.9 g) as a starting material.
  • Step 9 Using compound (T-29) (22.0 g) as a starting material, compound (T-30) (24.6 g; 78%) was obtained in the same manner as in the fifth step of Synthesis Example 1.
  • Step 10 Compound (1-3-4) (19.5 g; 90%) was obtained by the same method as in Step 6 of Synthesis Example 1 using compound (T-30) (24.6 g) as a starting material.
  • compound (T-30) (24.6 g)
  • Step 3 Compound (T-33) (9.75 g; 54%) was obtained in the same manner as in the third step of Synthesis Example 1 using compound (T-32) (19.2 g) as a starting material.
  • Step 4 Using compound (T-18) (5.00 g) and compound (T-33) (4.72 g) as starting materials, compound (T-34) in the same manner as in the fifth step of Synthesis Example 1. Obtained (7.32 g; 90%).
  • Step 5 Using compound (T-34) (7.32 g) as a starting material, and according to a procedure similar to the sixth step of Synthesis Example 1, compound (1-2-16) (4.56 g; 71%) is obtained.
  • Step 3 Compound (T-37) (13.0 g; 91%) was obtained in the same manner as in the third step of Synthesis Example 1 using compound (T-36) (15.0 g) as a starting material.
  • Step 4 Using the compound (T-18) (5.00 g) and the compound (T-37) (4.23 g) as starting materials, the compound (T-38) is prepared in the same manner as in the fifth step of Synthesis Example 1. (6.84 g; 82%) were obtained.
  • Step 5 Using compound (T-38) (6.84 g) as a starting material, and according to a method similar to the sixth step of Synthesis Example 1, compound (1-2-17) (2.33 g; 39%) is obtained.
  • Comparative Example 1 As a comparison compound, the following compound (S-1) described in WO 2017/047177 was synthesized based on the description of the publication, and the characteristics thereof were measured.
  • composition (i) The proportions of the components of composition (i) are indicated in% by weight.
  • the compound (1-2-2), the compound (1-2-6), the compound (1-3-4), the compound (1-2-16), and the compound (I) per 100% by weight of the composition (i) 1-2-17), or a comparison compound (S-1) was added at a ratio of 0.1 wt% to 1.0 wt% shown in Table A to prepare a sample.
  • the sample was allowed to stand at 25 ° C. for 7 days and then visually observed.
  • the compound (1-2-2), the compound (1-2-6), the compound (1-3-4), the compound (1-2-16), and the compound (1-2-2) 17) maintained the nematic phase even when added to the mother liquid crystal (composition (i)) at 1.0% by weight, whereas the comparative compound (S-1) maintained 0.2% by weight for crystals. It precipitated.
  • These compounds are similar compounds in that they have a plurality of polymerizable groups, but their compatibility with the mother liquid crystals is largely different.
  • the compound (1-2-2), the compound (1-2-6), the compound (1-3-4), the compound, while the comparative compound (S-1) has a plurality of hydroxyl groups as a polar group.
  • the compound (1) can be said to be an excellent compound having a plurality of polymerizable groups and having practical compatibility.
  • Example 1 1-BB-3 (2-8) 5% 1-BB-5 (2-8) 8% 2-BTB-1 (2-10) 2% 3-HHB-1 (3-1) 6% 3-HHB-3 (3-1) 14% 3-HHB-O1 (3-1) 5% 3-HHB-F (6-1) 4% 2-HHB (F) -F (6-2) 7% 3-HHB (F) -F (6-2) 8% 5-HHB (F) -F (6-2) 8% 3-HHB (F, F) -F (6-3) 5% 3-HHEB-F (6-10) 4% 5-HHEB-F (6-10) 5% 2-HB-C (8-1) 5% 3-HB-C (8-1) 14%
  • the following compound (1-2-2) was added at a ratio of 1% by weight to 100% by weight of a composition containing these components.
  • the following compound (1-2-6) was added in a proportion of 0.5% by weight to 100% by weight of the composition containing these components.
  • the following compound (1-3-4) was added in a proportion of 2% by weight to 100% by weight of the composition containing these components.
  • the following compound (1-3-21) was added in a proportion of 5% by weight to 100% by weight of the composition containing these components.
  • V-HBB-2 (3-4) 12% 1O1-HBBH-4 (4-1) 5% 1O1-HBBH-5 (4-1) 4% 3-HHB (F, F) -F (6-3) 9% 3-H2HB (F, F) -F (6-15) 9% 4-H2HB (F, F) -F (6-15) 9% 5-H2HB (F, F) -F (6-15) 8% 3-HBB (F, F) -F (6-24) 11% 5-HBB (F, F) -F (6-24) 18% 3-H2BB (F, F) -F (6-27) 9% 5-HBBB (F, F) -F (7-6) 2% 3-HH2BB (F, F) -F (7-15) 2% 5-HHEBB-F (7-17) 2%
  • the following compound (1-3-66) was added at a ratio of 1.5% by weight to 100% by weight of a composition containing these components.
  • the following compound (1-3-62) was added in a proportion of 2% by weight to 100% by weight of the composition containing these components.
  • the following compound (1-3-88) was added at a ratio of 0.8% by weight to 100% by weight of a composition containing these components.
  • the following compound (1-2-2) was added in a proportion of 3% by weight to 100% by weight of the composition containing these components.
  • the following compound (1-2-6) was added in a proportion of 4% by weight to 100% by weight of the composition containing these components.
  • the following compound (1-3-4) was added in a proportion of 5% by weight to 100% by weight of the composition containing these components.
  • the following compound (1-3-21) was added at a ratio of 1.5% by weight to 100% by weight of a composition containing these components.
  • the liquid crystal composition containing the compound (1) can be used for display elements such as a liquid crystal projector and a liquid crystal television.

Abstract

The present invention relates to a compound, a liquid crystal composition, and a liquid crystal display element. The compound is represented by formula (1). R1 is hydrogen or alkyl that may be substituted; rings A1 and A2 are each cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclohexenylene, phenylene, naphthalenediyl, decahydronaphthalenediyl, tetrahydronaphthalenediyl, tetrahydropyrandiyl, dioxanediyl, pyrimidinediyl, or pyridinediyl that may be substituted; "a" is 0 to 4; Z1 is a single bond or alkylene that may be substituted; Sp1 to Sp5 are each a single bond or alkylene that may be substituted; M1 to M4 are each H, F, Cl, or alkyl that may be substituted; R2 is hydrogen or C1-C5 alkyl that may be substituted; and X1 is -OH, -NH2, -OR3, -N(R3)2, -COOH, -SH, or -Si(R3)3.

Description

化合物、液晶組成物、および液晶表示素子Compound, liquid crystal composition, and liquid crystal display device
　本発明は、化合物、液晶組成物および液晶表示素子に関する。さらに詳しくは、－ＯＨ基などの極性基と複数のメタクリロイルオキシなどの重合性基とを併せ持つ化合物、この化合物を含み、誘電率異方性が正または負の液晶組成物、およびこの組成物またはその一部の硬化物を含む液晶表示素子に関する。 The present invention relates to a compound, a liquid crystal composition and a liquid crystal display device. More specifically, a compound having both a polar group such as -OH group and a plurality of polymerizable groups such as methacryloyloxy, a liquid crystal composition containing this compound and having positive or negative dielectric anisotropy, and this composition or The present invention relates to a liquid crystal display element including a part of the cured product.
　液晶表示素子を液晶分子の動作モードに基づいて分類すると、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）などのモードに分類できる。また、素子の駆動方式に基づくと、ＰＭ（passive matrix）とＡＭ（active matrix）に分類できる。ＰＭは、スタティック（static）、マルチプレックス（multiplex）などに分類され、ＡＭは、ＴＦＴ（thin film transistor）、ＭＩＭ（metal insulator metal）などに分類される。さらに、ＴＦＴは非晶質シリコン（amorphous silicon）および多結晶シリコン（polycrystal silicon）に分類できる。後者は製造工程によって高温型と低温型とに分類される。光源に基づいた分類すると、自然光を利用する反射型、バックライトを利用する透過型、そして自然光とバックライトの両方を利用する半透過型に分類できる。 The liquid crystal display elements are classified based on the operation mode of liquid crystal molecules: PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS ( It can be classified into modes such as in-plane switching (VA), vertical alignment (VA), fringe field switching (FFS), and field-induced photo-reactive alignment (FPA). Also, based on the driving method of the element, it can be classified into PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into thin film transistor (TFT), metal insulator metal (MIM), etc. In addition, TFTs can be classified into amorphous silicon and polycrystal silicon. The latter are classified into high temperature type and low temperature type according to the manufacturing process. The classification based on light source can be classified into a reflection type using natural light, a transmission type using back light, and a semi-transmission type using both natural light and back light.
　ネマチック相を有する液晶組成物は、適切な特性を有する。この組成物の特性を向上させることによって、良好な特性を有するＡＭ素子を得ることができる。前記組成物の特性とＡＭ素子の特性との関連を下記の表１にまとめる。 The liquid crystal composition having a nematic phase has appropriate properties. By improving the properties of this composition, an AM element having good properties can be obtained. The relationship between the properties of the composition and the properties of the AM device is summarized in Table 1 below.
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
　前記組成物の特性を市販されているＡＭ素子に基づいてさらに説明する。ネマチック相の温度範囲（ネマチック相を呈する温度範囲）は、素子の使用できる温度範囲に関連する。ネマチック相の好ましい上限温度は約７０℃以上であり、そしてネマチック相の好ましい下限温度は約－１０℃以下である。
　前記組成物の粘度は素子の応答時間に関連する。素子で動画を表示するためには短い応答時間が好ましい。１ミリ秒でもより短い応答時間が望ましい。したがって、前記組成物の粘度は低いことが好ましく、さらに、低温でも低いとより好ましい。 The characteristics of the composition are further described based on commercially available AM devices. The temperature range of the nematic phase (the temperature range exhibiting the nematic phase) relates to the usable temperature range of the device. The preferred upper temperature limit of the nematic phase is about 70 ° C. or higher, and the preferred lower temperature limit of the nematic phase is about -10 ° C. or lower.
The viscosity of the composition is related to the response time of the device. Short response times are preferred for displaying motion pictures on the device. Even shorter response times of 1 millisecond are desirable. Therefore, the viscosity of the composition is preferably low, and more preferably low even at low temperatures.
　前記組成物の光学異方性は、素子のコントラスト比に関連する。素子のモードに応じて、大きな光学異方性または小さな光学異方性、すなわち適切な光学異方性が必要である。組成物の光学異方性（Δｎ）と素子のセルギャップ（ｄ）との積（Δｎ×ｄ）は、コントラスト比を最大にするように設計される。適切な積の値は動作モードの種類に依存する。この値は、ＴＮなどのモードの素子では約０．４５μｍである。この値は、ＶＡモードの素子では約０．３０μｍから約０．４０μｍの範囲であり、ＩＰＳモードまたはＦＦＳモードの素子では約０．２０μｍから約０．３０μｍの範囲である。これらの場合、小さなセルギャップの素子には大きな光学異方性を有する組成物が好ましい。
　前記組成物における大きな誘電率異方性は、素子における低いしきい値電圧、小さな消費電力と大きなコントラスト比に寄与する。したがって、正または負に大きな誘電率異方性が好ましい。組成物における大きな比抵抗は、素子における大きな電圧保持率と大きなコントラスト比とに寄与する。したがって、初期段階において室温だけでなくネマチック相の上限温度に近い温度でも大きな比抵抗を有する組成物が好ましい。長時間使用した後、室温だけでなくネマチック相の上限温度に近い温度でも大きな比抵抗を有する組成物が好ましい。
　紫外線および熱に対する組成物の安定性は、素子の寿命に関連する。この安定性が高いとき、素子の寿命は長い。このような特性は、液晶プロジェクター、液晶テレビなどに用いるＡＭ素子に好ましい。 The optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large or small optical anisotropy, ie a suitable optical anisotropy, is required. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate product value depends on the type of operating mode. This value is about 0.45 μm for devices of modes such as TN. This value is in the range of about 0.30 μm to about 0.40 μm in the VA mode device and in the range of about 0.20 μm to about 0.30 μm in the IPS mode or FFS mode device. In these cases, compositions with large optical anisotropy are preferred for small cell gap devices.
The large dielectric anisotropy in the composition contributes to low threshold voltage, low power consumption and high contrast ratio in the device. Therefore, positive or negative large dielectric anisotropy is preferred. The large resistivity in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a large specific resistance at an initial stage not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable. After long time use, a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable.
The stability of the composition to ultraviolet light and heat is related to the lifetime of the device. When this stability is high, the lifetime of the device is long. Such characteristics are preferable for an AM element used for a liquid crystal projector, a liquid crystal television or the like.
　高分子支持配向（ＰＳＡ；polymer sustained alignment）型の液晶表示素子では、重合体を含有する液晶組成物が用いられる。まず、少量の重合性化合物を添加した組成物を素子に注入する。ここでは、複数の重合性基を有する重合性化合物が一般的に使用される。次に、この素子を挟持する基板の間に電圧を印加しながら、組成物に紫外線を照射する。重合性化合物は重合して、組成物中に重合体の網目構造を生成する。この組成物を用いると、重合体によって液晶分子の配向を制御することが可能になるので、素子の応答時間が短縮され、画像の焼き付きが改善される。重合体のこのような効果は、ＴＮ、ＥＣＢ、ＯＣＢ、ＩＰＳ、ＶＡ、ＦＦＳ、ＦＰＡなどのモードを有する素子に期待できる。 In a liquid crystal display device of the polymer supported alignment (PSA) type, a liquid crystal composition containing a polymer is used. First, a composition to which a small amount of a polymerizable compound is added is injected into the device. Here, polymerizable compounds having a plurality of polymerizable groups are generally used. Next, while applying a voltage between the substrates sandwiching the element, the composition is irradiated with ultraviolet light. The polymerizable compound polymerizes to form a polymer network in the composition. When this composition is used, the polymer can control the alignment of liquid crystal molecules, so that the response time of the device is shortened and the image sticking is improved. Such an effect of the polymer can be expected in devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
　汎用の液晶表示素子において、液晶分子の垂直配向は、ポリイミド配向膜によって達成される。一方、配向膜を有さない液晶表示素子として、極性化合物を液晶組成物に添加し、液晶分子を配向させるモードが提案されている。まず、少量の極性化合物および少量の重合性化合物を添加した組成物を素子に注入する。該重合性化合物としては、複数の重合性基を有する重合性化合物が一般的に使用される。ここで、極性化合物の作用によって液晶分子が配向される。次に、この素子を挟持する基板の間に電圧を印加しながら、組成物に紫外線を照射する。ここで、重合性化合物が重合し、液晶分子の配向を安定化させる。この組成物を用いると、極性化合物および重合体によって液晶分子の配向を制御することが可能になるので、素子の応答時間が短縮され、画像の焼き付きが改善される。さらに、配向膜を有さない素子では、配向膜を形成する工程が不要である。配向膜がないので、配向膜と組成物との相互作用によって、素子の電気抵抗が低下することはない。極性化合物と重合体の組合せによるこのような効果は、ＴＮ、ＥＣＢ、ＯＣＢ、ＩＰＳ、ＶＡ、ＦＦＳ、ＦＰＡなどのモードを有する素子に期待できる。 In a general-purpose liquid crystal display device, vertical alignment of liquid crystal molecules is achieved by a polyimide alignment film. On the other hand, as a liquid crystal display device having no alignment film, a mode is proposed in which a polar compound is added to a liquid crystal composition to align liquid crystal molecules. First, a composition to which a small amount of polar compound and a small amount of polymerizable compound are added is injected into the device. As the polymerizable compound, polymerizable compounds having a plurality of polymerizable groups are generally used. Here, the liquid crystal molecules are oriented by the action of the polar compound. Next, while applying a voltage between the substrates sandwiching the element, the composition is irradiated with ultraviolet light. Here, the polymerizable compound is polymerized to stabilize the alignment of liquid crystal molecules. With this composition, the polar compound and the polymer make it possible to control the alignment of liquid crystal molecules, so that the response time of the device is shortened and the image sticking is improved. Furthermore, in the element having no alignment film, the step of forming the alignment film is unnecessary. Since there is no alignment film, the interaction between the alignment film and the composition does not lower the electrical resistance of the device. Such an effect by the combination of a polar compound and a polymer can be expected to an element having modes such as TN, ECB, OCB, IPS, VA, FFS, FPA.
　これまでに、配向膜を有さない液晶表示素子において、極性化合物の作用と重合性化合物の作用を兼ね備えた化合物として、重合性を有する極性化合物が合成されてきた（例えば、特許文献１および２）。特許文献１には、複数の極性基と複数の重合性基を有する重合性化合物（Ｓ－１）が記載されている。 So far, in liquid crystal display devices having no alignment film, a polar compound having a polymerizability has been synthesized as a compound having both the action of the polar compound and the action of the polymerizable compound (for example, Patent Documents 1 and 2) ). Patent Document 1 describes a polymerizable compound (S-1) having a plurality of polar groups and a plurality of polymerizable groups.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
国際公開第２０１７／０４７１７７号International Publication No. 2017/047177 国際公開第２０１６／１２９４９０号International Publication No. 2016/129490
　本発明の一実施形態は、化学的に高い安定性、液晶分子を配向させる高い能力、紫外線照射による高い重合反応性の少なくとも１つを有し、そして液晶組成物への高い溶解度を有する化合物を提供する。本発明の一実施形態は、この化合物を含み、そしてネマチック相の高い上限温度、ネマチック相の低い下限温度、低粘度、適切な光学異方性、正または負に大きな誘電率異方性、大きな比抵抗、紫外線に対する高い安定性、熱に対する高い安定性、大きな弾性定数、液晶表示素子に用いた場合の大きな電圧保持率などの特性の少なくとも１つを充足する液晶組成物を提供する。本発明の一実施形態は、素子を使用できる広い温度範囲、短い応答時間、高い透過率、大きな電圧保持率、低いしきい値電圧、大きなコントラスト比、長い寿命、良好な垂直配向性などの特性の少なくとも１つを有する液晶表示素子を提供する。 One embodiment of the present invention is a compound having at least one of high chemical stability, high ability to align liquid crystal molecules, high polymerization reactivity by ultraviolet irradiation, and high solubility in a liquid crystal composition. provide. One embodiment of the present invention comprises this compound, and the high upper limit temperature of the nematic phase, the low lower limit temperature of the nematic phase, the low viscosity, the appropriate optical anisotropy, the positive or negative large dielectric anisotropy, the large Provided is a liquid crystal composition satisfying at least one of properties such as specific resistance, high stability to ultraviolet light, high stability to heat, a large elastic constant, and a large voltage holding ratio when used in a liquid crystal display element. One embodiment of the present invention is characterized by wide temperature range where the device can be used, short response time, high transmittance, large voltage holding ratio, low threshold voltage, large contrast ratio, long lifetime, good vertical orientation, etc. A liquid crystal display device comprising at least one of
　本発明の一実施形態は、式（１）で表される化合物、この化合物を含む液晶組成物、およびこの組成物および／またはこの組成物の少なくとも一部が重合した重合物を含む液晶表示素子に関する。 One embodiment of the present invention is a liquid crystal display device comprising a compound represented by the formula (1), a liquid crystal composition containing this compound, and a polymer obtained by polymerizing at least a part of this composition and / or this composition. About.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　式（１）において、
　Ｒ1は、水素または炭素数１から１５のアルキルであり、このアルキルにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－または－Ｓ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
　環Ａ1および環Ａ2は独立して、１，２－シクロプロピレン、１，３－シクロブチレン、１，３－シクロペンチレン、１，４－シクロヘキシレン、１，４－シクロヘプチレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－２，６－ジイル、デカヒドロナフタレン－２，６－ジイル、１，２，３，４－テトラヒドロナフタレン－２，６－ジイル、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、またはピリジン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１０のアルキル、炭素数２から１０のアルケニル、炭素数１から９のアルコキシ、または炭素数２から９のアルケニルオキシで置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
　ａは、０、１、２、３、または４であり；
　Ｚ1は、単結合または炭素数１から６のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
　Ｓｐ1、Ｓｐ2、Ｓｐ3、およびＳｐ4は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
　Ｓｐ5は、炭素数２から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよく；
　Ｍ1、Ｍ2、Ｍ3、およびＭ4は独立して、水素、フッ素、塩素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルであり；
　Ｒ2は、水素または炭素数１から５のアルキルであり、このアルキルにおいて、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
　Ｘ1は、－ＯＨ、－ＮＨ2、－ＯＲ3、－Ｎ（Ｒ3）2、－ＣＯＯＨ、－ＳＨ、または－Ｓｉ（Ｒ3）3であり；
－ＯＲ3、－Ｎ（Ｒ3）2、および－Ｓｉ（Ｒ3）3において、
　Ｒ3は水素または炭素数１から１０のアルキルであり、このアルキルにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
　ａが１であり、環Ａ1が１，４－シクロヘキシレンであり、環Ａ2が１，４－フェニレンであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｓｐ5が－（ＣＨ2）2－であり、Ｒ2がメチルであり、Ｘ1が－ＯＨであるときは、Ｓｐ1は、－ＣＨ2－ではなく；
　ａが１であり、環Ａ1が１，４－フェニレンであり、環Ａ2がナフタレン－２，６－ジイルであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｓｐ5が－（ＣＨ2）2－であり、Ｒ2がメチルであり、Ｘ1が－ＯＨであるときは、Ｓｐ1は、－ＣＨ2－ではなく；
　ａが３であり、４つの環がＲ1側からそれぞれ、１，４－フェニレン、２－エチル－１，４－フェニレン、１，４－シクロヘキシレン、および１，４－シクロヘキシレンであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｓｐ5が－（ＣＨ2）2－であり、Ｒ2がメチルであり、Ｘ1が－ＯＨであるときは、Ｓｐ1は、－ＣＨ2－ではない。 In equation (1),
R 1 is hydrogen or alkyl having 1 to 15 carbons, and in this alkyl, at least one —CH 2 — may be replaced by —O— or —S—, and at least one — (CH 2) ) 2 -may be replaced by -CH = CH- or -C≡C-, and in these groups at least one hydrogen may be replaced by fluorine or chlorine;
Ring A 1 and ring A 2 are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4 -Cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2 , 5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl in which at least one hydrogen is fluorine, chlorine , Alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyloxy having 2 to 9 carbons. Or in these groups at least one hydrogen may be replaced by fluorine or chlorine;
a is 0, 1, 2, 3 or 4;
Z 1 represents a single bond or an alkylene having 1 to 6 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —CO—, —COO—, —OCO—, or —OCOO— And at least one — (CH 2 ) 2 — may be replaced by —CH = CH— or —C≡C—, and in these groups at least one hydrogen is fluorine or May be replaced by chlorine;
Sp 1 , Sp 2 , Sp 3 and Sp 4 are each independently a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —CO— And -COO-, -OCO-, or -OCOO-, and at least one-(CH 2 ) 2 -may be replaced with -CH = CH- or -C≡C-, In these groups, at least one hydrogen may be replaced by fluorine or chlorine;
Sp 5 is alkylene having 2 to 10 carbons, and in this alkylene, at least one —CH 2 — may be replaced by —O—;
M 1 , M 2 , M 3 and M 4 independently represent hydrogen, fluorine, chlorine, alkyl having 1 to 5 carbon atoms, or 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine Alkyl;
R 2 is hydrogen or alkyl having 1 to 5 carbon atoms, and in this alkyl, at least one — (CH 2 ) 2 — may be replaced by —CH = CH— or —C≡C—, In these groups, at least one hydrogen may be replaced by fluorine or chlorine;
X 1 is —OH, —NH 2 , —OR 3 , —N (R 3 ) 2 , —COOH, —SH, or —Si (R 3 ) 3 ;
In -OR 3 , -N (R 3 ) 2 , and -Si (R 3 ) 3 ,
R 3 is hydrogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one —CH 2 — may be replaced by —O—, and at least one — (CH 2 ) 2 — is -CH = CH- may be replaced, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine;
a is 1, ring A 1 is 1,4-cyclohexylene, ring A 2 is 1,4-phenylene, Z 1 is a single bond, Sp 2 , Sp 3 , and Sp 4 are When CH 2- , Sp 5 is-(CH 2 ) 2- , R 2 is methyl and X 1 is -OH, then Sp 1 is not -CH 2- ;
a is 1, ring A 1 is 1,4-phenylene, ring A 2 is naphthalene-2,6-diyl, Z 1 is a single bond, Sp 2 , Sp 3 , and Sp 4 are When -CH 2- , Sp 5 is-(CH 2 ) 2- , R 2 is methyl and X 1 is -OH, then Sp 1 is not -CH 2- ;
a is 3, and 4 rings from the R 1 side are respectively 1,4-phenylene, 2-ethyl-1,4-phenylene, 1,4-cyclohexylene, and 1,4-cyclohexylene; 1 is a single bond, Sp 2 , Sp 3 and Sp 4 are -CH 2- , Sp 5 is-(CH 2 ) 2- , R 2 is methyl and X 1 is -OH Sometimes, Sp 1 is not -CH 2- .
　本発明の一実施形態によれば、化学的に高い安定性、液晶分子を配向させる高い能力、紫外線照射による高い重合反応性、液晶表示素子に用いた場合の大きな電圧保持率の少なくとも１つを有し、そして液晶組成物への高い溶解度を有する化合物を提供できる。本発明の一実施形態によれば、この化合物を含み、そしてネマチック相の高い上限温度、ネマチック相の低い下限温度、低粘度、適切な光学異方性、正または負に大きな誘電率異方性、大きな比抵抗、紫外線に対する高い安定性、熱に対する高い安定性、大きな弾性定数などの特性の少なくとも１つを充足する液晶組成物を提供できる。本発明の一実施形態によれば、素子を使用できる広い温度範囲、短い応答時間、高い透過率、大きな電圧保持率、低いしきい値電圧、大きなコントラスト比、長い寿命、良好な垂直配向性などの特性の少なくとも１つを有する液晶表示素子を提供できる。 According to one embodiment of the present invention, at least one of chemically high stability, high ability to align liquid crystal molecules, high polymerization reactivity by ultraviolet irradiation, and large voltage holding ratio when used in a liquid crystal display device It is possible to provide a compound having a high solubility in a liquid crystal composition. According to one embodiment of the present invention, comprising this compound, and high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, low viscosity, suitable optical anisotropy, positive or negative large dielectric anisotropy It is possible to provide a liquid crystal composition satisfying at least one of the properties such as large resistivity, high stability to ultraviolet light, high stability to heat, and a large elastic constant. According to one embodiment of the present invention, a wide temperature range in which the device can be used, short response time, high transmittance, large voltage holding ratio, low threshold voltage, large contrast ratio, long lifetime, good vertical alignment, etc. A liquid crystal display device having at least one of the following characteristics can be provided.
　この明細書における用語の使い方は、次のとおりである。「液晶性化合物」、「液晶組成物」、および「液晶表示素子」の用語をそれぞれ「化合物」、「組成物」、および「素子」と略すことがある。
　「液晶性化合物」は、ネマチック相、スメクチック相などの液晶相を有する化合物、および液晶相を有さないが、上限温度、下限温度、粘度、誘電率異方性などの組成物の物性を調節する目的で添加する化合物の総称である。この化合物は、通常、１，４－シクロヘキシレンや１，４－フェニレンなどの六員環を有し、その分子構造は棒状（rod like）である。
　「重合性化合物」は、組成物中に重合体を生成させる目的で添加する化合物である。アルケニルを有する液晶性化合物は、その意味では重合性化合物ではない。
　「極性基」は、ガラス（または金属酸化物）等の基板表面などと非共有結合的に相互作用する、下記－ＯＨ、－ＮＨ2、－ＯＲ3、－Ｎ（Ｒ3）2、－ＣＯＯＨ、－ＳＨ、または－Ｓｉ（Ｒ3）3などの基である。
　「極性化合物」は、極性基が基板表面などと相互作用することによって液晶分子が配列するのを援助する。
　「液晶表示素子」は液晶表示パネルおよび液晶表示モジュールなどの総称である。 The usage of the terms in this specification is as follows. The terms "liquid crystal compound", "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "compound", "composition" and "element", respectively.
"Liquid crystalline compound" is a compound having a liquid crystal phase such as a nematic phase or smectic phase, and has no liquid crystal phase, but controls physical properties of the composition such as upper limit temperature, lower limit temperature, viscosity, dielectric anisotropy, etc. Is a generic term for compounds added for the purpose of This compound usually has a 6-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and the molecular structure is rod like.
The "polymerizable compound" is a compound to be added for the purpose of forming a polymer in the composition. The liquid crystal compound having an alkenyl is not a polymerizable compound in that sense.
The “polar group” interacts non-covalently with a substrate surface such as glass (or metal oxide), etc., and the following —OH, —NH 2 , —OR 3 , —N (R 3 ) 2 , —COOH A group such as —SH or —Si (R 3 ) 3 .
The “polar compound” assists the alignment of liquid crystal molecules by interaction of polar groups with the substrate surface and the like.
"Liquid crystal display element" is a generic term for liquid crystal display panels and liquid crystal display modules.
　液晶組成物は、通常、複数の液晶性化合物を混合することによって調製される。この組成物には、物性をさらに調整する目的で、重合性化合物、重合開始剤、重合禁止剤、光学活性化合物、酸化防止剤、紫外線吸収剤、光安定剤、熱安定剤、色素、および消泡剤などの添加物が必要に応じて添加される。液晶組成物中の液晶性化合物の割合（含有量）は、添加物を添加した場合であっても、添加物を含まない液晶組成物の重量に基づいた重量百分率（重量％）で表す。液晶組成物中の添加物の割合（添加量）は、添加物を含まない液晶組成物の重量に基づいた重量百分率（重量％）で表す。すなわち、液晶性化合物や添加物の割合は、液晶性化合物の全重量に基づいて算出される。重量百万分率（ｐｐｍ）が用いられることもある。液晶組成物中の重合開始剤および重合禁止剤の割合は、例外的に重合性化合物の重量に基づいて表す。 The liquid crystal composition is usually prepared by mixing a plurality of liquid crystal compounds. In this composition, for the purpose of further adjusting the physical properties, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer, a dye, and an extinction Additives such as foaming agents are added as needed. The proportion (content) of the liquid crystal compound in the liquid crystal composition is represented by weight percentage (% by weight) based on the weight of the liquid crystal composition not including the additive, even when the additive is added. The proportion (addition amount) of the additive in the liquid crystal composition is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition without the additive. That is, the proportions of the liquid crystal compound and the additive are calculated based on the total weight of the liquid crystal compound. Parts per million by weight (ppm) may be used. The proportions of the polymerization initiator and the polymerization inhibitor in the liquid crystal composition are exceptionally expressed based on the weight of the polymerizable compound.
　「透明点」は、液晶性化合物における液晶相－等方相の転移温度である。「液晶相の下限温度」は、液晶性化合物における固体－液晶相（スメクチック相、ネマチック相など）の転移温度である。「ネマチック相の上限温度」は、液晶性化合物と母液晶との混合物または液晶組成物におけるネマチック相－等方相の転移温度であり、「上限温度」と略すことがある。「ネマチック相の下限温度」を「下限温度」と略すことがある。「誘電率異方性を上げる」や「大きな誘電率異方性」との表現は、その値の絶対値が増加するまたは大きいことを意味する。「電圧保持率が大きい」とは、素子が初期段階において室温だけでなく上限温度に近い温度でも大きな電圧保持率を有し、そして素子を長時間使用した後においても、室温だけでなく上限温度に近い温度でも大きな電圧保持率を有することを意味する。組成物や素子では、経時変化試験（加速劣化試験を含む）の前後で特性が検討されることがある。「液晶組成物への溶解度が高い」との表現は、常温での液晶性化合物を含む組成物のいずれにも対しても溶解度が高いことを意味するが、該組成物として、下記実施例で溶解性を評価するのに用いた組成物を規準とすることができる。 The “clearing point” is the transition temperature of the liquid crystal phase to the isotropic phase in the liquid crystal compound. The “lower limit temperature of the liquid crystal phase” is a transition temperature of a solid-liquid crystal phase (eg, smectic phase, nematic phase) in a liquid crystal compound. The “upper limit temperature of the nematic phase” is a transition temperature of the nematic phase-isotropic phase in the mixture of the liquid crystal compound and the base 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 expressions "increase dielectric anisotropy" and "large dielectric anisotropy" mean that the absolute value of the value increases or is large. "The voltage holding ratio is large" means that the device has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit at the initial stage, and even after using the device for a long time, not only the room temperature but also the upper limit temperature. It means that it has a large voltage holding ratio even at temperatures close to. The characteristics of the composition or element may be examined before and after the aging test (including the accelerated aging test). The expression "high solubility in liquid crystal composition" means that the solubility is high in any of the composition containing the liquid crystal compound at normal temperature, but as the composition, in the following examples, It can be based on the composition used to assess solubility.
　式（１）で表される化合物を「化合物（１）」と略すことがある。化合物（１）は、式（１）で表される１つの化合物、２つの化合物の混合物、または３つ以上の化合物の混合物を意味する。このルールは、式（２）で表される化合物の群から選択される少なくとも１つの化合物などにも適用される。
　六角形で囲んだＡ1、Ｂ1、Ｃ1などの記号はそれぞれ環Ａ1、環Ｂ1、環Ｃ1などに対応する。六角形は、シクロヘキサン環やベンゼン環などの六員環またはナフタレン環などの縮合環を表す。この六角形の一辺を横切る直線は、環上の任意の水素が－Ｓｐ1－Ｐ1などの基で置き換えられてもよいことを表す。
　ｆ、ｇ、ｈなどの添え字は、置き換えられた基の数を示す。添え字が０のとき、そのような置き換えはない。
　「環Ａおよび環Ｃは独立して、Ｘ、Ｙ、またはＺである」との表現では、主語が複数であるから、「独立して」を用いる。主語が「環Ａは」であるときは、主語が単数であるから「独立して」を用いない。 The compound represented by Formula (1) may be abbreviated as "compound (1)." The compound (1) means one compound represented by the formula (1), a mixture of two compounds, or a mixture of three or more compounds. This rule also applies to at least one compound etc. selected from the group of compounds represented by formula (2).
Symbols such as A 1 , B 1 and C 1 surrounded by a hexagon correspond to ring A 1 , ring B 1 and ring C 1 and the like, respectively. The hexagon represents a six-membered ring such as a cyclohexane ring or a benzene ring or a fused ring such as a naphthalene ring. A straight line across one side of this hexagon indicates that any hydrogen on the ring may be replaced by a group such as -Sp 1 -P 1 .
The subscripts such as f, g, h etc indicate the number of substituted groups. When the subscript is 0, there is no such replacement.
In the expression “the ring A and the ring C are independently X, Y or Z”, “separately” is used because the subject is plural. When the subject is "ring A", "independent" is not used because the subject is singular.
　化学式において、末端基Ｒ11の記号を複数の化合物に用いているが、これらの化合物におけるＲ11が表す基はそれぞれ同一であってもよく、または異なってもよい。例えば、化合物（２）のＲ11がエチルである場合、化合物（３）のＲ11はエチルであってもよく、プロピルなどの他の基であってもよい。このルールは、他の記号にも適用される。化合物（８）において、ｉが２のとき、２つの環Ｄ1が存在する。この化合物において２つの環Ｄ1が表す２つの基は、同一であってもよく、または異なってもよい。ｉが２より大きいとき、任意の２つの環Ｄ1にも適用される。このルールは、他の記号にも適用される。 In the chemical formulas, the symbol of the terminal group R 11 is used for a plurality of compounds, but the groups represented by R 11 in these compounds may be the same or different. For example, when R 11 of Compound (2) is ethyl, R 11 of compound (3) may be ethyl, it may be other groups, such as propyl. This rule also applies to other symbols. In compound (8), when i is 2, two rings D 1 are present. Two groups represented by two rings D 1 in this compound may be identical or different. When i is greater than 2, it also applies to any two rings D 1 . This rule also applies to other symbols.
　「少なくとも１つの‘Ａ’」との表現は、‘Ａ’の数は任意であることを意味する。「少なくとも１つの‘Ａ’は、‘Ｂ’で置き換えられてもよい」との表現は、‘Ｂ’で置き換えられない‘Ａ’そのものの場合、１つの‘Ａ’が‘Ｂ’で置き換えられた場合、２つ以上の‘Ａ’が‘Ｂ’で置き換えられた場合を含み、これらにおいて、‘Ｂ’で置き換えられる‘Ａ’の位置は任意である。置換位置が任意であるとのルールは、「少なくとも１つの‘Ａ’が、‘Ｂ’で置き換えられた」との表現にも適用される。「少なくとも１つのＡが、Ｂ、Ｃ、またはＤで置き換えられてもよい」という表現は、Ａが置換されない場合、少なくとも１つのＡがＢで置き換えられた場合、少なくとも１つのＡがＣで置き換えられた場合、および少なくとも１つのＡがＤで置き換えられた場合、さらに複数のＡがＢ、Ｃ、Ｄの少なくとも２つで置き換えられた場合を含むことを意味する。少なくとも１つの－ＣＨ2－（または、－ＣＨ2ＣＨ2－）が－Ｏ－（または、－ＣＨ＝ＣＨ－）で置き換えられてもよいアルキルには、例えば、アルキル、アルケニル、アルコキシ、アルコキシアルキル、アルコキシアルケニル、アルケニルオキシアルキルが含まれる。なお、連続する２つの－ＣＨ2－が－Ｏ－で置き換えられて、－Ｏ－Ｏ－のようになることは好ましくない。アルキルなどにおいて、メチル部分（－ＣＨ2－Ｈ）の－ＣＨ2－が－Ｏ－で置き換えられて－Ｏ－Ｈになることも好ましくない。 The expression "at least one 'A'" means that the number of 'A' is arbitrary. The expression “at least one 'A' may be replaced by 'B'” is replaced by one 'A' by 'B' in the case of 'A' itself which is not replaced by 'B' In this case, the case where two or more 'A's are replaced by' B 'is included, and in these, the position of' A 'replaced by' B 'is arbitrary. The rule that the substitution position is optional also applies to the expression "at least one 'A' has been replaced by 'B'". The expression "at least one A may be replaced by B, C or D" means that if A is not substituted then at least one A is replaced by C if at least one A is replaced by B And when at least one A is replaced by D, it is meant to include the case where more than one A is replaced by at least two of B, C, D. Examples of alkyl in which at least one —CH 2 — (or —CH 2 CH 2 —) may be replaced by —O— (or —CH = CH—) include, for example, alkyl, alkenyl, alkoxy, alkoxyalkyl And alkoxyalkenyl and alkenyloxyalkyl. In addition, it is not preferable that two successive -CH 2 -be replaced by -O- to be -O-O-. Alkyl such as in, -CH 2 methyl moiety (-CH 2 -H) - by is replaced by -O- is not preferred also be the -O-H.
　「Ｒ11およびＲ12は独立して、炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの－ＣＨ2－は－Ｏ－で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよい」との表現が使われることがある。この表現において、「これらの基において」は、文言どおりに解釈してよい。この表現では、「これらの基」は、アルキル、アルケニル、アルコキシ、アルケニルオキシなどを意味する。すなわち、「これらの基」は、「これらの基において」の用語よりも前に記載された基の総てを表す。この常識的な解釈は、他の用語にも適用される。 “R 11 and R 12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — is replaced by —O— Also, in these groups, the expression "at least one hydrogen may be replaced by fluorine" may be used. In this expression, "in these groups" may be interpreted literally. In this expression, "these groups" mean alkyl, alkenyl, alkoxy, alkenyloxy and the like. That is, "these groups" represent all of the groups described earlier than the term "in these groups". This common sense interpretation applies to other terms as well.
　ハロゲンは、フッ素、塩素、臭素、またはヨウ素を意味する。好ましいハロゲンは、フッ素または塩素である。さらに好ましいハロゲンはフッ素である。液晶性化合物において、アルキルは、直鎖状または分岐状であり、環状アルキルを含まない。直鎖状アルキルは、一般的に分岐状アルキルよりも好ましい。これらのことは、アルコキシ、アルケニルなどの末端基についても同様である。１，４－シクロヘキシレンに関する立体配置は、ネマチック相の上限温度を上げるために、シスよりもトランスが好ましい。２－フルオロ－１，４－フェニレンは、下記の２つの二価基を意味する。化学式において、フッ素は左向き（Ｌ）であってもよいし、右向き（Ｒ）であってもよい。このルールは、テトラヒドロピラン－２，５－ジイルなどの環から水素を２つ除くことによって生成した左右非対称な二価基にも適用される。 Halogen means fluorine, chlorine, bromine or iodine. Preferred halogens are fluorine or chlorine. A further preferred halogen is fluorine. In the liquid crystal compound, the alkyl is linear or branched and does not include cyclic alkyl. Linear alkyls are generally preferred over branched alkyls. The same is true for end groups such as alkoxy and alkenyl. The configuration of 1,4-cyclohexylene is preferably trans rather than cis in order to raise the upper limit temperature of the nematic phase. 2-fluoro-1,4-phenylene means the following two divalent groups. In the chemical formula, fluorine may be leftward (L) or rightward (R). This rule also applies to asymmetric asymmetric divalent groups generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　本発明の一実施形態は、下記の項などを包含する。 One embodiment of the present invention includes the following items and the like.
項１．
　式（１）で表される化合物。
Figure JPOXMLDOC01-appb-C000019
 Item 1.
The compound represented by Formula (1).
Figure JPOXMLDOC01-appb-C000019
　式（１）において、
　Ｒ1は、水素または炭素数１から１５のアルキルであり、このアルキルにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－または－Ｓ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
　環Ａ1および環Ａ2は独立して、１，２－シクロプロピレン、１，３－シクロブチレン、１，３－シクロペンチレン、１，４－シクロヘキシレン、１，４－シクロヘプチレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－２，６－ジイル、デカヒドロナフタレン－２，６－ジイル、１，２，３，４－テトラヒドロナフタレン－２，６－ジイル、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、またはピリジン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１０のアルキル、炭素数２から１０のアルケニル、炭素数１から９のアルコキシ、または炭素数２から９のアルケニルオキシで置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
　ａは、０、１、２、３、または４であり；
　Ｚ1は、単結合または炭素数１から６のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
　Ｓｐ1、Ｓｐ2、Ｓｐ3、およびＳｐ4は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
　Ｓｐ5は、炭素数２から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよく；
　Ｍ1、Ｍ2、Ｍ3、およびＭ4は独立して、水素、フッ素、塩素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルであり；
　Ｒ2は、水素または炭素数１から５のアルキルであり、このアルキルにおいて、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
　Ｘ1は、－ＯＨ、－ＮＨ2、－ＯＲ3、－Ｎ（Ｒ3）2、－ＣＯＯＨ、－ＳＨ、または－Ｓｉ（Ｒ3）3であり；
－ＯＲ3、－Ｎ（Ｒ3）2、および－Ｓｉ（Ｒ3）3において、
　Ｒ3は水素または炭素数１から１０のアルキルであり、このアルキルにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
　ａが１であり、環Ａ1が１，４－シクロヘキシレンであり、環Ａ2が１，４－フェニレンであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｓｐ5が－（ＣＨ2）2－であり、Ｒ2がメチルであり、Ｘ1が－ＯＨであるときは、Ｓｐ1は、－ＣＨ2－ではなく；
　ａが１であり、環Ａ1が１，４－フェニレンであり、環Ａ2がナフタレン－２，６－ジイルであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｓｐ5が－（ＣＨ2）2－であり、Ｒ2がメチルであり、Ｘ1が－ＯＨであるときは、Ｓｐ1は、－ＣＨ2－ではなく；
　ａが３であり、４つの環がＲ1側からそれぞれ、１，４－フェニレン、２－エチル－１，４－フェニレン、１，４－シクロヘキシレン、および１，４－シクロヘキシレンであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｓｐ5が－（ＣＨ2）2－であり、Ｒ2がメチルであり、Ｘ1が－ＯＨであるときは、Ｓｐ1は、－ＣＨ2－ではない。 In equation (1),
R 1 is hydrogen or alkyl having 1 to 15 carbons, and in this alkyl, at least one —CH 2 — may be replaced by —O— or —S—, and at least one — (CH 2) ) 2 -may be replaced by -CH = CH- or -C≡C-, and in these groups at least one hydrogen may be replaced by fluorine or chlorine;
Ring A 1 and ring A 2 are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4 -Cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2 , 5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl in which at least one hydrogen is fluorine, chlorine , Alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyloxy having 2 to 9 carbons. Or in these groups at least one hydrogen may be replaced by fluorine or chlorine;
a is 0, 1, 2, 3 or 4;
Z 1 represents a single bond or an alkylene having 1 to 6 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —CO—, —COO—, —OCO—, or —OCOO— And at least one — (CH 2 ) 2 — may be replaced by —CH = CH— or —C≡C—, and in these groups at least one hydrogen is fluorine or May be replaced by chlorine;
Sp 1 , Sp 2 , Sp 3 and Sp 4 are each independently a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —CO— And -COO-, -OCO-, or -OCOO-, and at least one-(CH 2 ) 2 -may be replaced with -CH = CH- or -C≡C-, In these groups, at least one hydrogen may be replaced by fluorine or chlorine;
Sp 5 is alkylene having 2 to 10 carbons, and in this alkylene, at least one —CH 2 — may be replaced by —O—;
M 1 , M 2 , M 3 and M 4 independently represent hydrogen, fluorine, chlorine, alkyl having 1 to 5 carbon atoms, or 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine Alkyl;
R 2 is hydrogen or alkyl having 1 to 5 carbon atoms, and in this alkyl, at least one — (CH 2 ) 2 — may be replaced by —CH = CH— or —C≡C—, In these groups, at least one hydrogen may be replaced by fluorine or chlorine;
X 1 is —OH, —NH 2 , —OR 3 , —N (R 3 ) 2 , —COOH, —SH, or —Si (R 3 ) 3 ;
In -OR 3 , -N (R 3 ) 2 , and -Si (R 3 ) 3 ,
R 3 is hydrogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one —CH 2 — may be replaced by —O—, and at least one — (CH 2 ) 2 — is -CH = CH- may be replaced, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine;
a is 1, ring A 1 is 1,4-cyclohexylene, ring A 2 is 1,4-phenylene, Z 1 is a single bond, Sp 2 , Sp 3 , and Sp 4 are When CH 2- , Sp 5 is-(CH 2 ) 2- , R 2 is methyl and X 1 is -OH, then Sp 1 is not -CH 2- ;
a is 1, ring A 1 is 1,4-phenylene, ring A 2 is naphthalene-2,6-diyl, Z 1 is a single bond, Sp 2 , Sp 3 , and Sp 4 are When -CH 2- , Sp 5 is-(CH 2 ) 2- , R 2 is methyl and X 1 is -OH, then Sp 1 is not -CH 2- ;
a is 3, and 4 rings from the R 1 side are respectively 1,4-phenylene, 2-ethyl-1,4-phenylene, 1,4-cyclohexylene, and 1,4-cyclohexylene; 1 is a single bond, Sp 2 , Sp 3 and Sp 4 are -CH 2- , Sp 5 is-(CH 2 ) 2- , R 2 is methyl and X 1 is -OH Sometimes, Sp 1 is not -CH 2- .
項２．
　式（１）において、
　Ｚ1が、単結合、－（ＣＨ2）2－、－（ＣＨ2）4－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＦ2Ｏ－、－ＯＣＦ2－、－ＣＨ2Ｏ－、－ＯＣＨ2－、または－ＣＦ＝ＣＦ－である、項１に記載の化合物。 Item 2.
In equation (1),
Z 1 is a single bond, - (CH 2) 2 - , - (CH 2) 4 -, - CH = CH -, - C≡C -, - COO -, - OCO -, - CF 2 O -, - The compound according to Item 1, wherein OCF 2 —, —CH 2 O—, —OCH 2 —, or —CF = CF—.
項３．
　式（１）において、
　環Ａ1および環Ａ2が独立して、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－２，６－ジイル、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、またはピリジン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１０のアルキル、炭素数２から１０のアルケニル、炭素数１から９のアルコキシ、または炭素数２から９のアルケニルオキシで置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい、項１または２に記載の化合物。 Item 3.
In equation (1),
Ring A 1 and ring A 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, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, and in these rings, at least one hydrogen is fluorine, chlorine, carbon number 1 10 alkyl, alkenyl of 2 to 10 carbons, alkoxy of 1 to 9 carbons, or alkenyloxy of 2 to 9 carbons, and in these groups, at least one hydrogen is fluorine or chlorine The compound according to Item 1 or 2, which may be replaced by
項４．
　式（１－１）から式（１－４）のいずれか１つで表される、項１から３のいずれか１項に記載の化合物。
Figure JPOXMLDOC01-appb-C000020
 Item 4.
Item 4. The compound according to any one of Items 1 to 3, which is represented by any one of formulas (1-1) to (1-4).
Figure JPOXMLDOC01-appb-C000020
　式（１－１）から式（１－４）において、
　Ｒ1は、炭素数１～１５のアルキル、炭素数２～１５のアルケニル、炭素数１～１４のアルコキシ、または炭素数２～１４のアルケニルオキシであり、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；
　環Ａ1、環Ａ2、環Ａ3、および環Ａ4は独立して、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－２，６－ジイル、テトラヒドロピラン－２，５－ジイル、または１，３－ジオキサン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、炭素数１から１０のアルキル、炭素数２から１０のアルケニル、炭素数１から９のアルコキシ、または炭素数２から９のアルケニルオキシで置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；
　Ｚ1、Ｚ2、およびＺ3は独立して、単結合、－（ＣＨ2）2－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＦ2Ｏ－、－ＯＣＦ2－、－ＣＨ2Ｏ－、－ＯＣＨ2－、または－ＣＦ＝ＣＦ－であり；
　Ｓｐ1、Ｓｐ2、Ｓｐ3、およびＳｐ4は独立して、単結合または炭素数１から７のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；
　Ｓｐ5は、炭素数２から７のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよく；
　Ｍ1、Ｍ2、Ｍ3、およびＭ4は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素で置き換えられた炭素数１から５のアルキルであり；
　Ｒ2は、水素または炭素数１から５のアルキルであり；
　Ｘ1は、－ＯＨ、－ＮＨ2、または－ＳＨであり；
式（１－２）において、
　環Ａ1が１，４－シクロヘキシレンであり、環Ａ2が１，４－フェニレンであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｓｐ5が－（ＣＨ2）2－であり、Ｒ2がメチルであり、Ｘ1が－ＯＨであるときは、Ｓｐ1は、－ＣＨ2－ではなく；式（１－２）において、
　環Ａ1が１，４－フェニレンであり、環Ａ2がナフタレン－２，６－ジイルであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｓｐ5が－（ＣＨ2）2－であり、Ｒ2がメチルであり、Ｘ1が－ＯＨであるときは、Ｓｐ1は、－ＣＨ2－ではなく；
式（１－４）において、
　環Ａ1が１，４－フェニレンであり、環Ａ2が２－エチル－１，４－フェニレンであり、環Ａ3および環Ａ4が共に１，４－シクロヘキシレンであり、Ｚ1、Ｚ2、およびＺ3が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｓｐ5が－（ＣＨ2）2－であり、Ｒ2がメチルであり、Ｘ1が－ＯＨであるときは、Ｓｐ1は、－ＣＨ2－ではない。 In formulas (1-1) to (1-4),
R 1 is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 14 carbons, or alkenyloxy having 2 to 14 carbons, and in these groups, at least one hydrogen is , May be replaced by fluorine;
Ring A 1 , ring A 2 , ring A 3 and ring A 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, Tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl, in which ring at least one hydrogen is fluorine, alkyl having 1 to 10 carbons, 2 to 10 carbons Of C 1 to C 9 alkoxy or C 2 to C 9 alkenyloxy, and in these groups, at least one hydrogen may be replaced by fluorine;
Z 1 , Z 2 and Z 3 independently represent a single bond,-(CH 2 ) 2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CF 2 O- , -OCF 2- , -CH 2 O-, -OCH 2- , or -CF = CF-;
Sp 1 , Sp 2 , Sp 3 and Sp 4 independently represent a single bond or an alkylene having 1 to 7 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —COO— Or -OCO-, and at least one-(CH 2 ) 2 -may be replaced by -CH = CH-, and in these groups, at least one hydrogen is replaced by fluorine May be
Sp 5 is alkylene having 2 to 7 carbon atoms, and in this alkylene, at least one —CH 2 — may be replaced by —O—;
M 1 , M 2 , M 3 and M 4 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine;
R 2 is hydrogen or alkyl having 1 to 5 carbons;
X 1 is -OH, -NH 2 , or -SH;
In equation (1-2),
Ring A 1 is 1,4-cyclohexylene, Ring A 2 is 1,4-phenylene, Z 1 is a single bond, Sp 2 , Sp 3 and Sp 4 are —CH 2 — When Sp 5 is — (CH 2 ) 2 —, R 2 is methyl and X 1 is —OH, Sp 1 is not —CH 2 —; in formula (1-2)
Ring A 1 is 1,4-phenylene, ring A 2 is naphthalene-2,6-diyl, Z 1 is a single bond, Sp 2 , Sp 3 , and Sp 4 are —CH 2 — , Sp 5 is-(CH 2 ) 2- , R 2 is methyl and X 1 is -OH, then Sp 1 is not -CH 2- ;
In formula (1-4),
Ring A 1 is 1,4-phenylene, ring A 2 is 2-ethyl-1,4-phenylene, ring A 3 and ring A 4 are both 1,4-cyclohexylene, Z 1 , Z 2 and Z 3 are a single bond, Sp 2 , Sp 3 and Sp 4 are -CH 2- , Sp 5 is-(CH 2 ) 2- and R 2 is methyl, X 1 When is -OH, Sp 1 is not -CH 2- .
項５．
　式（１－５）から式（１－７）のいずれか１つで表される、項１から４のいずれか１項に記載の化合物。
Figure JPOXMLDOC01-appb-C000021
 Item 5.
The compound according to any one of Items 1 to 4, which is represented by any one of Formulas (1-5) to (1-7).
Figure JPOXMLDOC01-appb-C000021
　式（１－５）から式（１－７）において、
　Ｒ1は、炭素数１～１０のアルキル、炭素数２～１０のアルケニル、または炭素数１～９のアルコキシであり；
　環Ａ1、環Ａ2、環Ａ3、および環Ａ4は独立して、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－２，６－ジイル、テトラヒドロピラン－２，５－ジイル、または１，３－ジオキサン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、炭素数１から５のアルキル、炭素数２から５のアルケニル、または炭素数１から４のアルコキシで置き換えられてもよく；
　Ｚ1、Ｚ2、およびＺ3は独立して、単結合、－（ＣＨ2）2－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＨ2Ｏ－、または－ＯＣＨ2－であり；
　Ｓｐ1、Ｓｐ2、Ｓｐ3、およびＳｐ4は独立して、単結合または炭素数１から５のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－で置き換えられてもよく；
　Ｒ2は、炭素数１から３のアルキルであり；
式（１－５）において、
　環Ａ1が１，４－シクロヘキシレンであり、環Ａ2が１，４－フェニレンであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｒ2がメチルであるときは、Ｓｐ1は、－ＣＨ2－ではなく；
式（１－５）において、
　環Ａ1が１，４－フェニレンであり、環Ａ2がナフタレン－２，６－ジイルであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｒ2がメチルであるときは、Ｓｐ1は、－ＣＨ2－ではなく；
式（１－７）において、
　環Ａ1が１，４－フェニレンであり、環Ａ2が２－エチル－１，４－フェニレンであり、環Ａ3および環Ａ4が共に１，４－シクロヘキシレンであり、Ｚ1、Ｚ2、およびＺ3が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｒ2がメチルであるときは、Ｓｐ1は、－ＣＨ2－ではない。 In formulas (1-5) to (1-7),
R 1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkoxy having 1 to 9 carbons;
Ring A 1 , ring A 2 , ring A 3 and ring A 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, Tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl, in which ring at least one hydrogen is fluorine, alkyl having 1 to 5 carbons, 2 to 5 carbons Or alkenyl of 1 to 4 carbon atoms;
Z 1 , Z 2 and Z 3 are independently a single bond,-(CH 2 ) 2- , -CH = CH-, -C≡C-, -CH 2 O-, or -OCH 2- ;
Sp 1 , Sp 2 , Sp 3 , and Sp 4 are independently a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one —CH 2 — is replaced by —O— It may be, at least one - (CH 2) 2 - may be replaced by -CH = CH-;
R 2 is alkyl having 1 to 3 carbons;
In formula (1-5),
Ring A 1 is 1,4-cyclohexylene, Ring A 2 is 1,4-phenylene, Z 1 is a single bond, Sp 2 , Sp 3 and Sp 4 are —CH 2 — When R 2 is methyl, then Sp 1 is not -CH 2- ;
In formula (1-5),
Ring A 1 is 1,4-phenylene, ring A 2 is naphthalene-2,6-diyl, Z 1 is a single bond, Sp 2 , Sp 3 , and Sp 4 are —CH 2 — , When R 2 is methyl, Sp 1 is not -CH 2- ;
In equation (1-7),
Ring A 1 is 1,4-phenylene, ring A 2 is 2-ethyl-1,4-phenylene, ring A 3 and ring A 4 are both 1,4-cyclohexylene, Z 1 , Z When 2 and Z 3 are a single bond, Sp 2 , Sp 3 and Sp 4 are -CH 2- and R 2 is methyl, Sp 1 is not -CH 2- .
項６．
　式（１－８）から式（１－１６）のいずれか１つで表される、項１から５のいずれか１項に記載の化合物。
Figure JPOXMLDOC01-appb-C000022
 Item 6.
Item 6. The compound according to any one of items 1 to 5, represented by any one of formulas (1-8) to (1-16):
Figure JPOXMLDOC01-appb-C000022
　式（１－８）から式（１－１６）において、
　Ｒ1は、炭素数１～１０のアルキル、炭素数２～１０のアルケニル、または炭素数１～９のアルコキシであり；
　Ｚ1およびＺ2は独立して、単結合または－（ＣＨ2）2－であり；
　Ｓｐ1、Ｓｐ2、およびＳｐ3は独立して、単結合または炭素数１から５のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよく；
　Ｙ1、Ｙ2、Ｙ3、Ｙ4、Ｙ5、およびＹ6は独立して、水素、フッ素、炭素数１から５のアルキル、炭素数２から５のアルケニル、または炭素数１から４のアルコキシであり；
式（１－９）において、
　Ｚ1が単結合であり、Ｓｐ2、およびＳｐ3が－ＣＨ2－であり、Ｙ1およびＹ2が水素であるときは、Ｓｐ1は、－ＣＨ2－ではない。 In formulas (1-8) to (1-16),
R 1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkoxy having 1 to 9 carbons;
Z 1 and Z 2 are independently a single bond or-(CH 2 ) 2- ;
Sp 1 , Sp 2 and Sp 3 are independently a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one —CH 2 — may be replaced by —O—;
Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons, or 1 to 4 carbons Is alkoxy;
In formula (1-9),
When Z 1 is a single bond, Sp 2 and Sp 3 are -CH 2- , and Y 1 and Y 2 are hydrogen, Sp 1 is not -CH 2- .
項７．
　式（１－１７）から式（１－２３）のいずれか１つで表される、項１から６のいずれか１項に記載の化合物。
Figure JPOXMLDOC01-appb-C000023
 Item 7.
7. The compound according to any one of items 1 to 6, which is represented by any one of formulas (1-17) to (1-23).
Figure JPOXMLDOC01-appb-C000023
　式（１－１７）から式（１－２３）において、
　Ｒ1は、炭素数１～１０のアルキルであり；
　Ｙ1、Ｙ2、Ｙ3、Ｙ4、Ｙ5、およびＹ6は独立して、水素、フッ素、メチル、またはエチルであり、
　Ｓｐ1は単結合または炭素数１から５のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよく；
式（１－１８）において、
　Ｙ1およびＹ2が水素であるときは、Ｓｐ1は、－ＣＨ2－ではない。 In formulas (1-17) to (1-23),
R 1 is alkyl having 1 to 10 carbons;
Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 are independently hydrogen, fluorine, methyl or ethyl;
Sp 1 is a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one —CH 2 — may be replaced by —O—;
In formula (1-18),
When Y 1 and Y 2 are hydrogen, Sp 1 is not —CH 2 —.
項８．
　項１から７のいずれか１項に記載の化合物の少なくとも１つを含有する液晶組成物。 Item 8.
Item 8. A liquid crystal composition containing at least one of the compounds according to any one of items 1 to 7.
項９．
　式（２）から（４）で表される化合物の群から選択された少なくとも１つの化合物を含有する、項８に記載の液晶組成物。
Figure JPOXMLDOC01-appb-C000024
 Item 9.
Item 9. The liquid crystal composition according to item 8, containing at least one compound selected from the group of compounds represented by formulas (2) to (4).
Figure JPOXMLDOC01-appb-C000024
　式（２）から（４）において、
　Ｒ11およびＲ12は独立して、炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの－ＣＨ2－は－Ｏ－で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく；
　環Ｂ1、環Ｂ2、環Ｂ3、および環Ｂ4は独立して、１，４－シクロヘキシレン、１，４－フェニレン、２－フルオロ－１，４－フェニレン、２，５－ジフルオロ－１，４－フェニレン、またはピリミジン－２，５－ジイルであり；
　Ｚ11、Ｚ12、およびＺ13は独立して、単結合、－ＣＯＯ－、－ＣＨ2ＣＨ2－、－ＣＨ＝ＣＨ－、または－Ｃ≡Ｃ－である。 In equations (2) to (4),
R 11 and R 12 independently represent alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one of —CH 2 — is replaced by —O— Well, in these groups at least one hydrogen may be replaced by fluorine;
Ring B 1 , ring B 2 , ring B 3 and ring B 4 are each independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene, or pyrimidine-2,5-diyl;
Z 11 , Z 12 and Z 13 are independently a single bond, -COO-, -CH 2 CH 2- , -CH = CH-, or -C≡C-.
項１０．
　式（５）から（７）で表される化合物の群から選択された少なくとも１つの化合物を含有する、項８または９に記載の液晶組成物。
Figure JPOXMLDOC01-appb-C000025
 Item 10.
Item 10. The liquid crystal composition according to item 8 or 9, containing at least one compound selected from the group of compounds represented by formulas (5) to (7).
Figure JPOXMLDOC01-appb-C000025
　式（５）から（７）において、
　Ｒ13は炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの－ＣＨ2－は－Ｏ－で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく；
　Ｘ11は、フッ素、塩素、－ＯＣＦ3、－ＯＣＨＦ2、－ＣＦ3、－ＣＨＦ2、－ＣＨ2Ｆ、－ＯＣＦ2ＣＨＦ2、または－ＯＣＦ2ＣＨＦＣＦ3であり；
　環Ｃ1、環Ｃ2、および環Ｃ3は独立して、１，４－シクロヘキシレン、１，４－フェニレン、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、または少なくとも１つの水素がフッ素で置き換えられた１，４－フェニレンであり；
　Ｚ14、Ｚ15、およびＺ16は独立して、単結合、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ2Ｏ－、－ＯＣＨ2－、－ＣＦ2Ｏ－、－ＯＣＦ2－、－ＣＨ2ＣＨ2－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、または－（ＣＨ2）4－であり；
　Ｌ11およびＬ12は独立して、水素またはフッ素である。 In equations (5) to (7),
R 13 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—, and in these groups, 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 ;
Ring C 1 , ring C 2 and ring C 3 are independently 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl Pyrimidine-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine;
Z 14, Z 15, and Z 16 are independently a single bond, -COO -, - OCO -, - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 -, - CH 2 CH 2 -, - CH = CH -, - C≡C-, or - (CH 2) 4 - a and;
L 11 and L 12 are independently hydrogen or fluorine.
項１１．
　式（８）で表される化合物の群から選択された少なくとも１つの化合物を含有する、項８から１０のいずれか１項に記載の液晶組成物。
Figure JPOXMLDOC01-appb-C000026
 Item 11.
Item 11. The liquid crystal composition according to any one of items 8 to 10, containing at least one compound selected from the group of compounds represented by formula (8).
Figure JPOXMLDOC01-appb-C000026
　式（８）において、
　Ｒ14は炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの－ＣＨ2－は－Ｏ－で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく；
　Ｘ12は－Ｃ≡Ｎまたは－Ｃ≡Ｃ－Ｃ≡Ｎであり；
　環Ｄ1は、１，４－シクロヘキシレン、１，４－フェニレン、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、または少なくとも１つの水素がフッ素で置き換えられた１，４－フェニレンであり；
　Ｚ17は、単結合、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ2Ｏ－、－ＯＣＨ2－、－ＣＦ2Ｏ－、－ＯＣＦ2－、－ＣＨ2ＣＨ2－、または－Ｃ≡Ｃ－であり；
　Ｌ13およびＬ14は独立して、水素またはフッ素であり；
　ｉは、１、２、３、または４である。 In equation (8),
R 14 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—, and in these groups, At least one hydrogen may be replaced by fluorine;
X 12 is -C≡N or -C≡C-C≡N;
Ring D 1 is 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or at least 1 Four hydrogens are substituted with fluorine and 1,4-phenylene;
Z 17 represents a single bond, -COO-, -OCO-, -CH 2 O-, -OCH 2- , -CF 2 O-, -OCF 2- , -CH 2 CH 2- , or -C≡C- And
L 13 and L 14 are independently hydrogen or fluorine;
i is 1, 2, 3 or 4;
項１２．
　式（１１）から（１９）で表される化合物の群から選択された少なくとも１つの化合物を含有する、項８から１１のいずれか１項に記載の液晶組成物。
Figure JPOXMLDOC01-appb-C000027
 Item 12.
Item 12. The liquid crystal composition according to any one of items 8 to 11, containing at least one compound selected from the group of compounds represented by formulas (11) to (19).
Figure JPOXMLDOC01-appb-C000027
　式（１１）から（１９）において、
　Ｒ15、Ｒ16、およびＲ17は独立して、炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの－ＣＨ2－は－Ｏ－で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく、そしてＲ17は、水素またはフッ素であってもよく；
　環Ｅ1、環Ｅ2、環Ｅ3、および環Ｅ4は独立して、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、テトラヒドロピラン－２，５－ジイル、デカヒドロナフタレン－２，６－ジイル、または少なくとも１つの水素がフッ素で置き換えられた１，４－フェニレンであり；
　環Ｅ5および環Ｅ6は独立して、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、テトラヒドロピラン－２，５－ジイル、またはデカヒドロナフタレン－２，６－ジイルであり；
　Ｚ18、Ｚ19、Ｚ20、およびＺ21は独立して、単結合、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ2Ｏ－、－ＯＣＨ2－、－ＣＦ2Ｏ－、－ＯＣＦ2－、－ＣＨ2ＣＨ2－、－ＣＦ2ＯＣＨ2ＣＨ2－、または－ＯＣＦ2ＣＨ2ＣＨ2－であり；
　Ｌ15およびＬ16は独立して、フッ素または塩素であり；
　Ｓ11は、水素またはメチルであり；
　Ｘは、－ＣＨＦ－または－ＣＦ2－であり；
　ｊ、ｋ、ｍ、ｎ、ｐ、ｑ、ｒ、およびｓは独立して、０または１であり、ｋ、ｍ、ｎ、およびｐの和は、１または２であり、ｑ、ｒ、およびｓの和は、０、１、２、または３であり、
　ｔは、１、２、または３である。 In equations (11) to (19),
R 15, R 16, and R 17 are independently alkenyl alkyl carbon atoms or 2 to 10 of 1 to 10 carbon atoms, in the alkyl and alkenyl, at least one of -CH 2 - by -O- Which may be replaced, in these groups at least one hydrogen may be replaced by fluorine, and R 17 may be hydrogen or fluorine;
Ring E 1 , ring E 2 , ring E 3 and ring E 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl Decahydronaphthalene-2,6-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine;
Ring E 5 and ring E 6 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6 -Is diil;
Z 18, Z 19, Z 20 , and Z 21 are independently a single bond, -COO -, - OCO -, - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 -, -CH 2 CH 2- , -CF 2 OCH 2 CH 2- , or -OCF 2 CH 2 CH 2- ;
L 15 and L 16 are independently fluorine or chlorine;
S 11 is hydrogen or methyl;
X is -CHF- or -CF 2- ;
j, k, m, n, p, q, r, and s are independently 0 or 1, and the sum of k, m, n, and p is 1 or 2, q, r, and The sum of s is 0, 1, 2 or 3 and
t is 1, 2 or 3.
項１３．
　式（１）で表される化合物以外の、式（２０）で表される少なくとも１つの重合性化合物を含有する、項８から１２のいずれか１項に記載の液晶組成物。
Figure JPOXMLDOC01-appb-C000028
 Item 13.
Item 13. The liquid crystal composition according to any one of items 8 to 12, containing at least one polymerizable compound represented by formula (20) other than the compound represented by formula (1).
Figure JPOXMLDOC01-appb-C000028
　式（２０）において、
　環Ｆおよび環Ｉは独立して、シクロヘキシル、シクロヘキセニル、フェニル、１－ナフチル、２－ナフチル、テトラヒドロピラン－２－イル、１，３－ジオキサン－２－イル、ピリミジン－２－イル、またはピリジン－２－イルであり、これらの環において、少なくとも１つの水素は、ハロゲン、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；
　環Ｇは、１，４－シクロへキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－１，２－ジイル、ナフタレン－１，３－ジイル、ナフタレン－１，４－ジイル、ナフタレン－１，５－ジイル、ナフタレン－１，６－ジイル、ナフタレン－１，７－ジイル、ナフタレン－１，８－ジイル、ナフタレン－２，３－ジイル、ナフタレン－２，６－ジイル、ナフタレン－２，７－ジイル、フェナントレン－２，７－ジイル、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、またはピリジン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、ハロゲン、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；
　Ｚ22およびＺ23は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ2ＣＨ2－は、－ＣＨ＝ＣＨ－、－Ｃ（ＣＨ3）＝ＣＨ－、－ＣＨ＝Ｃ（ＣＨ3）－、または－Ｃ（ＣＨ3）＝Ｃ（ＣＨ3）－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
　Ｐ11、Ｐ12、およびＰ13は独立して、重合性基であり；
　Ｓｐ11、Ｓｐ12、およびＳｐ13は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ2ＣＨ2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
　ｕは、０、１、または２であり；
　ｆ、ｇ、およびｈは独立して、０、１、２、３、または４であり、そしてｆ、ｇ、およびｈの和は、１以上である。 In equation (20),
Ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl or pyridine -2-yl, in these rings, at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 1 carbon having at least one hydrogen replaced with halogen May be replaced by 12 alkyls;
Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene- 2,7-diyl, phenanthrene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5- In these rings, at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one of Element may be replaced by alkyl having 1 carbon is replaced by a halogen 12;
Z 22 and Z 23 are independently a single bond or alkylene having 1 to 10 carbons, and in this alkylene, at least one —CH 2 — is —O—, —CO—, —COO—, or — OCO- may be replaced, and at least one -CH 2 CH 2 -is -CH = CH-, -C (CH 3 ) = CH-, -CH = C (CH 3 )-, or -C ( CH 3 ) = C (CH 3 ) — may be replaced and in these groups at least one hydrogen may be replaced by fluorine or chlorine;
P 11 , P 12 and P 13 are independently polymerizable groups;
Sp 11 , Sp 12 and Sp 13 independently represent a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —COO—, —OCO At least one of —CH 2 CH 2 — may be replaced by —CH = CH— or —C≡C—, and at least one of these groups may be replaced by Hydrogen may be replaced by fluorine or chlorine;
u is 0, 1 or 2;
f, g and h are independently 0, 1, 2, 3 or 4 and the sum of f, g and h is 1 or more.
項１４．
　式（２０）において、
　Ｐ11、Ｐ12、およびＰ13が独立して、式（Ｐ－１）から式（Ｐ－５）で表される重合性基の群から選択された基である、項１３に記載の液晶組成物。
Figure JPOXMLDOC01-appb-C000029
 Item 14.
In equation (20),
14. The liquid crystal according to item 13, wherein P 11 , P 12 and P 13 are independently a group selected from the group of polymerizable groups represented by formula (P-1) to formula (P-5) Composition.
Figure JPOXMLDOC01-appb-C000029
　式（Ｐ－１）から式（Ｐ－５）において、
　Ｍ11、Ｍ12、およびＭ13は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から５のアルキルである。 In formulas (P-1) to (P-5),
M 11 , M 12 and M 13 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen.
項１５．
　式（２０）で表される重合性化合物が、式（２０－１）から式（２０－７）で表される重合性化合物の群から選択された少なくとも１つの化合物である、項１３または１４に記載の液晶組成物。
Figure JPOXMLDOC01-appb-C000030
 Item 15.
Item 13 or 14, wherein the polymerizable compound represented by Formula (20) is at least one compound selected from the group of polymerizable compounds represented by Formula (20-1) to Formula (20-7) The liquid crystal composition as described in.
Figure JPOXMLDOC01-appb-C000030
　式（２０－１）から式（２０－７）において、
　Ｌ31、Ｌ32、Ｌ33、Ｌ34、Ｌ35、Ｌ36、Ｌ37、およびＬ38は独立して、水素、フッ素、またはメチルであり；
　Ｓｐ11、Ｓｐ12、およびＳｐ13は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ2ＣＨ2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
　Ｐ11、Ｐ12、およびＰ13は独立して、式（Ｐ－１）から式（Ｐ－３）で表される重合性基の群から選択された基である。
Figure JPOXMLDOC01-appb-C000031
 In formulas (20-1) to (20-7),
L 31 , L 32 , L 33 , L 34 , L 35 , L 36 , L 37 and L 38 are independently hydrogen, fluorine or methyl;
Sp 11 , Sp 12 and Sp 13 independently represent a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —COO—, —OCO At least one of —CH 2 CH 2 — may be replaced by —CH = CH— or —C≡C—, and at least one of these groups may be replaced by Hydrogen may be replaced by fluorine or chlorine;
P 11 , P 12 and P 13 are independently a group selected from the group of polymerizable groups represented by Formula (P-1) to Formula (P-3).
Figure JPOXMLDOC01-appb-C000031
　式（Ｐ－１）から式（Ｐ－３）において、
　Ｍ11、Ｍ12、およびＭ13は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から５のアルキルである。 In formulas (P-1) to (P-3),
M 11 , M 12 and M 13 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen.
項１６．
　式（１）および式（２０）で表される化合物とは異なる重合性化合物、重合開始剤、重合禁止剤、光学活性化合物、酸化防止剤、紫外線吸収剤、光安定剤、熱安定剤、色素、ならびに消泡剤の群から選択された少なくとも１つを含有する、項８から１５のいずれか１項に記載の液晶組成物。
Figure JPOXMLDOC01-appb-C000032
 Item 16.
Polymerizable compounds different from the compounds represented by the formulas (1) and (20), polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dyes Item 16. The liquid crystal composition according to any one of items 8 to 15, containing at least one selected from the group of antifoam agents.
Figure JPOXMLDOC01-appb-C000032
　式（２０）において、
　環Ｆおよび環Ｉは独立して、シクロヘキシル、シクロヘキセニル、フェニル、１－ナフチル、２－ナフチル、テトラヒドロピラン－２－イル、１，３－ジオキサン－２－イル、ピリミジン－２－イル、またはピリジン－２－イルであり、これらの環において、少なくとも１つの水素は、ハロゲン、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；
　環Ｇは、１，４－シクロへキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－１，２－ジイル、ナフタレン－１，３－ジイル、ナフタレン－１，４－ジイル、ナフタレン－１，５－ジイル、ナフタレン－１，６－ジイル、ナフタレン－１，７－ジイル、ナフタレン－１，８－ジイル、ナフタレン－２，３－ジイル、ナフタレン－２，６－ジイル、ナフタレン－２，７－ジイル、フェナントレン－２，７－ジイル、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、またはピリジン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、ハロゲン、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；
　Ｚ22およびＺ23は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ2ＣＨ2－は、－ＣＨ＝ＣＨ－、－Ｃ（ＣＨ3）＝ＣＨ－、－ＣＨ＝Ｃ（ＣＨ3）－、または－Ｃ（ＣＨ3）＝Ｃ（ＣＨ3）－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
　Ｐ11、Ｐ12、およびＰ13は独立して、重合性基であり；
　Ｓｐ11、Ｓｐ12、およびＳｐ13は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ2ＣＨ2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
　ｕは、０、１、または２であり；
　ｆ、ｇ、およびｈは独立して、０、１、２、３、または４であり、そしてｆ、ｇ、およびｈの和は、１以上である。 In equation (20),
Ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl or pyridine -2-yl, in these rings, at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 1 carbon having at least one hydrogen replaced with halogen May be replaced by 12 alkyls;
Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene- 2,7-diyl, phenanthrene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5- In these rings, at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one of Element may be replaced by alkyl having 1 carbon is replaced by a halogen 12;
Z 22 and Z 23 are independently a single bond or alkylene having 1 to 10 carbons, and in this alkylene, at least one —CH 2 — is —O—, —CO—, —COO—, or — OCO- may be replaced, and at least one -CH 2 CH 2 -is -CH = CH-, -C (CH 3 ) = CH-, -CH = C (CH 3 )-, or -C ( CH 3 ) = C (CH 3 ) — may be replaced and in these groups at least one hydrogen may be replaced by fluorine or chlorine;
P 11 , P 12 and P 13 are independently polymerizable groups;
Sp 11 , Sp 12 and Sp 13 independently represent a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —COO—, —OCO At least one of —CH 2 CH 2 — may be replaced by —CH = CH— or —C≡C—, and at least one of these groups may be replaced by Hydrogen may be replaced by fluorine or chlorine;
u is 0, 1 or 2;
f, g and h are independently 0, 1, 2, 3 or 4 and the sum of f, g and h is 1 or more.
項１７．
　項８から１６のいずれか１項に記載の液晶組成物、および項８から１６のいずれか１項に記載の液晶組成物の少なくとも一部が重合したものからなる群より選択された少なくとも１つ含有する液晶表示素子。 Item 17.
Item 18. At least one selected from the group consisting of the liquid crystal composition according to any one of items 8 to 16, and at least a part of the liquid crystal composition according to any one of items 8 to 16 polymerized. Liquid crystal display element contained.
　本発明の一実施形態は、次の項も含む。
　（ａ）重合性化合物、重合開始剤、重合禁止剤、光学活性化合物、酸化防止剤、紫外線吸収剤、光安定剤、熱安定剤、色素、消泡剤などの添加物の少なくとも２つをさらに含有する前記の液晶組成物。
　（ｂ）前記の液晶組成物に化合物（１）および化合物（２０）とは異なる重合性化合物を添加することによって調製した重合性組成物。
　（ｃ）前記の液晶組成物に化合物（１）と化合物（２０）とを添加することによって調製した重合性組成物。
　（ｄ）前記重合性組成物を重合させることによって調製した液晶複合体。
　（ｅ）この液晶複合体を含有する高分子支持配向型の素子。
　（ｆ）前記の液晶組成物に化合物（１）と化合物（２０）と、化合物（１）および化合物（２０）とは異なる重合性化合物とを添加することによって調製した重合性組成物を使用することによって作成した高分子支持配向型の素子。 One embodiment of the present invention also includes the following items.
(A) At least two of additives such as a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer, a pigment, and an antifoamer The above liquid crystal composition containing.
(B) A polymerizable composition prepared by adding a polymerizable compound different from the compound (1) and the compound (20) to the liquid crystal composition described above.
(C) A polymerizable composition prepared by adding the compound (1) and the compound (20) to the liquid crystal composition described above.
(D) A liquid crystal composite prepared by polymerizing the polymerizable composition.
(E) A polymer supported alignment type device containing this liquid crystal complex.
(F) A polymerizable composition prepared by adding the compound (1), the compound (20), and a polymerizable compound different from the compound (1) and the compound (20) to the liquid crystal composition described above is used A polymer-supported oriented device made by
　以下、化合物（１）の態様、化合物（１）の合成、液晶組成物、および液晶表示素子について順に説明する。 Hereinafter, the aspect of compound (1), the synthesis of compound (1), the liquid crystal composition, and the liquid crystal display device will be described in order.
１．化合物（１）の態様
　本発明の一実施形態に係る化合物（１）は、少なくとも１つの環より構成されるメソゲン部位、１つの極性基、および２つ以上の重合性基を有することを特徴とし、さらに、環に結合したスペーサー部位（下記Ｓｐ1）が分岐して、少なくとも一方に重合性基と極性基を有し、他方に少なくとも重合性基を有することを特徴とし、特に、重合性基にスペーサー部位（下記Ｓｐ4）を介して末端置換エトキシ基等が結合していることを特徴とする。化合物（１）は、極性基がガラス（または金属酸化物）等の基板表面と非共有結合的に相互作用するので有用である。用途の一つは、液晶表示素子に使われる液晶組成物用の添加剤であり、この用途において、化合物（１）は液晶分子の配向を制御する目的で添加される。このような添加剤は、素子に密閉された条件下では化学的に安定であり、液晶分子を配向させる能力が高く、そして液晶組成物への溶解度が大きいことが好ましく、また、該添加剤を液晶表示素子に用いた場合、電圧保持率が大きい液晶表示素子を得ることができることが好ましい。化合物（１）は、このような特性をかなりの程度で充足し、従来の化合物では達成できなかった、液晶組成物への溶解度が極めて大きく、該化合物（１）を用いることで、従来の化合物を用いた場合に比べ、配向性および長期安定性に優れる素子を容易に得ることができる。 1. Aspect of Compound (1) The compound (1) according to one embodiment of the present invention is characterized by having a mesogenic moiety composed of at least one ring, one polar group, and two or more polymerizable groups. Further, a spacer moiety (below Sp 1 ) bonded to a ring is branched to have a polymerizable group and a polar group on at least one side, and at least one polymerizable group on the other side, in particular, a polymerizable group characterized in that via a spacer part (below Sp 4) capped ethoxy group is attached to. The compound (1) is useful because polar groups interact non-covalently with a substrate surface such as glass (or metal oxide). One of the uses is an additive for a liquid crystal composition used in a liquid crystal display device, and in this use, the compound (1) is added for the purpose of controlling the alignment of liquid crystal molecules. It is preferable that such an additive is chemically stable under the condition sealed in a device, has a high ability to orient liquid crystal molecules, and has a high solubility in a liquid crystal composition, and that the additive When using for a liquid crystal display element, it is preferable that a liquid crystal display element with a large voltage holding ratio can be obtained. The compound (1) fulfills such properties to a considerable extent, and the solubility in liquid crystal compositions is extremely high, which can not be achieved by the conventional compounds, and by using the compound (1), the conventional compounds A device excellent in orientation and long-term stability can be easily obtained as compared with the case of using.
　化合物（１）の好ましい例について説明をする。化合物（１）におけるＲ1、Ａ1、Ｓｐ1などの記号の好ましい例は、化合物（１）の下位式、例えば式（１－１）などにも適用される。化合物（１）において、これらの基の種類を適切に組み合わせることによって、特性を任意に調整することが可能である。化合物の特性に大きな差異がないので、化合物（１）は、2Ｈ（重水素）、13Ｃなどの同位体を天然存在比の量より多く含んでもよい。 Preferred examples of the compound (1) will be described. Preferred examples of the symbols such as R 1 , A 1 and Sp 1 in compound (1) also apply to subformulas of compound (1), for example, formula (1-1) and the like. In the compound (1), the properties can be arbitrarily adjusted by appropriately combining the types of these groups. The compound (1) may contain isotopes such as 2 H (deuterium) and 13 C in an amount larger than the natural abundance ratio because there is no significant difference in the properties of the compounds.
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
　Ｒ1は、水素または炭素数１から１５のアルキルであり、このアルキルにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－または－Ｓ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。 R 1 is hydrogen or alkyl having 1 to 15 carbons, and in this alkyl, at least one —CH 2 — may be replaced by —O— or —S—, and at least one — (CH 2) ) 2 -may be replaced by —CH = CH— or —C≡C—, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine.
　好ましいＲ1は、炭素数１から１５のアルキル、炭素数２から１５のアルケニル、炭素数１から１４のアルコキシ、または炭素数２から１４のアルケニルオキシであり、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよい。
　さらに好ましいＲ1は、炭素数１から１０のアルキル、炭素数２から１０のアルケニルまたは炭素数１から９のアルコキシである。
　特に好ましいＲ1は、炭素数１から１０のアルキルである。 Desirable R 1 is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 14 carbons, or alkenyloxy having 2 to 14 carbons, and in these groups, at least one hydrogen May be replaced by fluorine.
More preferable R 1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 9 carbons.
Particularly preferred R 1 is alkyl having 1 to 10 carbons.
　Ｒ1が炭素数１から１５のアルキルまたは炭素数１から１４のアルコキシである化合物は、化学的安定性が高い傾向にある。Ｒ1が炭素数１から１５のアルキル、炭素数２から１５のアルケニル、または炭素数２から１４のアルケニルオキシである化合物は、液晶組成物への溶解度が大きい傾向にある。Ｒ1が炭素数１～１５のアルキルである化合物は、液晶分子を配向させる能力が高い傾向にある。 Compounds in which R 1 is alkyl having 1 to 15 carbons or alkoxy having 1 to 14 carbons tend to have high chemical stability. Compounds in which R 1 is alkyl having 1 to 15 carbons, alkenyls having 2 to 15 carbons, or alkenyloxys having 2 to 14 carbons tend to have high solubility in liquid crystal compositions. Compounds in which R 1 is alkyl having 1 to 15 carbon atoms tend to have high ability to align liquid crystal molecules.
　環Ａ1および環Ａ2は独立して、１，２－シクロプロピレン、１，３－シクロブチレン、１，３－シクロペンチレン、１，４－シクロヘキシレン、１，４－シクロヘプチレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－２，６－ジイル、デカヒドロナフタレン－２，６－ジイル、１，２，３，４－テトラヒドロナフタレン－２，６－ジイル、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、またはピリジン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１０のアルキル、炭素数２から１０のアルケニル、炭素数１から９のアルコキシ、または炭素数２から９のアルケニルオキシで置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。 Ring A 1 and ring A 2 are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4 -Cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2 , 5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl in which at least one hydrogen is fluorine, chlorine , Alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyloxy having 2 to 9 carbons. In these groups, at least one hydrogen may be replaced by fluorine or chlorine.
　好ましい環Ａ1および環Ａ2は、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－２，６－ジイル、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、またはピリジン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１０のアルキル、炭素数２から１０のアルケニル、炭素数１から９のアルコキシ、または炭素数２から９のアルケニルオキシで置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。 Preferred ring A 1 and ring A 2 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1, 3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl in which at least one hydrogen is fluorine, chlorine, 1 to 10 carbon atoms Alkyl, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyloxy having 2 to 9 carbons, and in these groups, at least one hydrogen is replaced by fluorine or chlorine It may be done.
　より好ましい環Ａ1および環Ａ2は、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－２，６－ジイル、テトラヒドロピラン－２，５－ジイル、または１，３－ジオキサン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、炭素数１から１０のアルキル、炭素数２から１０のアルケニル、炭素数１から９のアルコキシ、または炭素数２から９のアルケニルオキシで置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよい。 More preferred ring A 1 and ring A 2 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl in which at least one hydrogen is fluorine, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons in these rings Or alkenyloxy having 2 to 9 carbon atoms, and in these groups, at least one hydrogen may be replaced by fluorine.
　さらに好ましい環Ａ1および環Ａ2は、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－２，６－ジイル、テトラヒドロピラン－２，５－ジイル、または１，３－ジオキサン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、炭素数１から５のアルキル、炭素数２から５のアルケニル、または炭素数１から４のアルコキシで置き換えられてもよい。 Further preferred ring A 1 and ring A 2 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl in which at least one hydrogen is fluorine, alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons, or 1 to 4 carbons. It may be replaced by alkoxy.
　特に好ましい環Ａ1および環Ａ2は、１，４－シクロヘキシレン、１，４－フェニレン、２位置換、３位置換、または２位および３位置換１，４－フェニレンであり、該置換基としては、好ましくは、水素、フッ素、炭素数１から５のアルキル、炭素数２から５のアルケニル、または炭素数１から４のアルコキシであり、より好ましくは水素、フッ素、メチル、またはエチルである。 Particularly preferable ring A 1 and ring A 2 are 1,4-cyclohexylene, 1,4-phenylene, 2-substituted, 3-substituted, or 2- and 3-substituted 1,4-phenylene, and the substituents Is preferably hydrogen, fluorine, alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons, or alkoxy having 1 to 4 carbons, and more preferably hydrogen, fluorine, methyl or ethyl .
　環Ａ1および環Ａ2が独立して、１，３－シクロペンチレン、１，４－シクロヘキシレン、１，４－シクロヘプチレン、１，４－フェニレン、少なくとも１つの水素がフッ素で置き換えられた１，４－フェニレン、少なくとも１つの水素が炭素数１から５のアルキルで置き換えられた１，４－フェニレン、デカヒドロナフタレン－２，６－ジイル、またはテトラヒドロピラン－２，５－ジイルである化合物は、化学的安定性が高い傾向にある。環Ａ1および環Ａ2が独立して、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、少なくとも１つの水素がフッ素で置き換えられた１，４－フェニレン、少なくとも１つの水素が炭素数１から５のアルキルで置き換えられた１，４－フェニレン、または少なくとも１つの水素が炭素数２から５のアルケニルで置き換えられた１，４－フェニレンである化合物は、液晶組成物への溶解度が大きい傾向にある。環Ａ1および環Ａ2が独立して、１，４－シクロヘキシレン、１，４－フェニレン、少なくとも１つの水素が炭素数１から２のアルキルで置き換えられた１，４－フェニレンである化合物は、液晶分子を配向させる能力が高い傾向にある。環Ａ1および環Ａ2が独立して、１，４－フェニレン、少なくとも１つの水素が炭素数１から５のアルキルで置き換えられた１，４－フェニレン、少なくとも１つの水素が炭素数１から４のアルコキシで置き換えられた１，４－フェニレン、ナフタレン－２，６－ジイル、ピリミジン－２，５－ジイル、またはピリジン－２，５－ジイルである化合物は、紫外線照射による重合反応性が高い傾向にある。 Ring A 1 and ring A 2 are independently 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-phenylene, or at least one hydrogen is replaced by fluorine 1 , 4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with alkyl having 1 to 5 carbon atoms, decahydronaphthalene-2,6-diyl, or tetrahydropyran-2,5-diyl , Chemical stability tends to be high. Ring A 1 and Ring A 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine, at least Compounds in which one hydrogen is 1,4-phenylene in which one hydrogen is replaced by alkyl having 1 to 5 carbons or 1,4-phenylene in which at least one hydrogen is replaced by alkenyl having 2 to 5 carbons have a liquid crystal composition There is a tendency for the solubility to be large. Compounds in which Ring A 1 and Ring A 2 are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by alkyl having 1 to 2 carbon atoms; And the ability to align liquid crystal molecules tends to be high. Ring A 1 and Ring A 2 are independently 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by alkyl having 1 to 5 carbon atoms, at least one hydrogen has 1 to 4 carbon atoms Compounds that are alkoxy-substituted 1,4-phenylene, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl tend to be highly polymerizable by ultraviolet irradiation. It is in.
　ａは、０、１、２、３、または４であり、好ましくは、０、１、２、または３であり、より好ましくは、１、２、または３であり、特に好ましくは、１または２である。 a is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 1, 2 or 3 and particularly preferably 1 or 2. It is.
　ａが０である化合物は、液晶組成物への溶解度が大きい傾向にある。ａが３または４である化合物は、液晶分子を配向させる能力が高い傾向にある。ａが１または２である化合物は、液晶組成物への溶解度が大きく、液晶分子を配向させる能力が高く、紫外線照射による重合反応性が高い傾向にある。 Compounds in which a is 0 tend to have high solubility in liquid crystal compositions. Compounds in which a is 3 or 4 tend to have high ability to align liquid crystal molecules. Compounds in which a is 1 or 2 have high solubility in liquid crystal compositions, high ability to align liquid crystal molecules, and tend to have high polymerization reactivity due to ultraviolet irradiation.
　Ｚ1は、単結合または炭素数１から６のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。 Z 1 represents a single bond or an alkylene having 1 to 6 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —CO—, —COO—, —OCO—, or —OCOO— And at least one — (CH 2 ) 2 — may be replaced by —CH = CH— or —C≡C—, and in these groups at least one hydrogen is fluorine or It may be replaced by chlorine.
　好ましいＺ1は、単結合、－（ＣＨ2）2－、－（ＣＨ2）4－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＦ2Ｏ－、－ＯＣＦ2－、－ＣＨ2Ｏ－、－ＯＣＨ2－、または－ＣＦ＝ＣＦ－である。
　より好ましいＺ1は、単結合、－（ＣＨ2）2－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＦ2Ｏ－、－ＯＣＦ2－、－ＣＨ2Ｏ－、－ＯＣＨ2－、または－ＣＦ＝ＣＦ－である。
　さらに好ましいＺ1は、単結合、－（ＣＨ2）2－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＨ2Ｏ－、または－ＯＣＨ2－であり、より好ましいＺ1は、単結合または－（ＣＨ2）2－であり、特に好ましいＺ1は、単結合である。 Preferred Z 1 is a single bond, — (CH 2 ) 2 —, — (CH 2 ) 4 —, —CH = CH—, —C≡C—, —COO—, —OCO—, —CF 2 O—, -OCF 2 -, - CH 2 O -, - OCH 2 -, or -CF = CF-.
More preferable Z 1 is a single bond,-(CH 2 ) 2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CF 2 O-, -OCF 2- , -CH 2 O-, -OCH 2- , or -CF = CF-.
Further preferred Z 1 is a single bond, - (CH 2) 2 - , - CH = CH -, - C≡C -, - CH 2 O-, or -OCH 2 - is a more preferred Z 1 is a single A particularly preferred Z 1 which is a bond or-(CH 2 ) 2- is a single bond.
　Ｚ1が単結合である化合物は、化学的安定性が高い傾向にある。Ｚ1が単結合、－（ＣＨ2）2－、－ＣＦ2Ｏ－、または－ＯＣＦ2－である化合物は、液晶組成物への溶解度が大きい傾向にある。Ｚ1が単結合または－（ＣＨ2）2－である化合物は、液晶分子を配向させる能力が高い傾向にある。Ｚ1が単結合、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ2Ｏ－、－ＯＣＨ2－である化合物は、紫外線照射による重合反応性が高い傾向にある。 Compounds in which Z 1 is a single bond tend to have high chemical stability. Compounds in which Z 1 is a single bond, — (CH 2 ) 2 —, —CF 2 O—, or —OCF 2 — tend to have high solubility in liquid crystal compositions. Compounds in which Z 1 is a single bond or — (CH 2 ) 2 — tend to have high ability to align liquid crystal molecules. Compounds in which Z 1 is a single bond, —CH = CH—, —C≡C—, —COO—, —OCO—, —CH 2 O—, or —OCH 2 — tend to have high polymerization reactivity due to ultraviolet irradiation. It is in.
　Ｓｐ1、Ｓｐ2、Ｓｐ3、およびＳｐ4は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。 Sp 1 , Sp 2 , Sp 3 and Sp 4 are each independently a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —CO— And -COO-, -OCO-, or -OCOO-, and at least one-(CH 2 ) 2 -may be replaced with -CH = CH- or -C≡C-, In these groups, at least one hydrogen may be replaced by fluorine or chlorine.
　好ましいＳｐ1、Ｓｐ2、Ｓｐ3、およびＳｐ4は独立して、単結合または炭素数１から７のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよい。 Preferred Sp 1 , Sp 2 , Sp 3 and Sp 4 are independently a single bond or alkylene having 1 to 7 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —COO -Or -OCO-, and at least one-(CH 2 ) 2 -may be replaced by -CH = CH-, and in these groups, at least one hydrogen is fluorine It may be replaced.
　Ｓｐ1、Ｓｐ2、Ｓｐ3、およびＳｐ4が独立して、単結合または炭素数１から７のアルキレンである化合物は、化学的安定性が高い傾向にある。Ｓｐ1、Ｓｐ2、Ｓｐ3、およびＳｐ4が独立して、炭素数１から７のアルキレン、または炭素数１から７のアルキレンの少なくとも１つの－ＣＨ2－が－Ｏ－で置き換えられた基である化合物は、液晶組成物への溶解度が大きい傾向にある。 Compounds in which Sp 1 , Sp 2 , Sp 3 and Sp 4 are independently a single bond or an alkylene having 1 to 7 carbon atoms tend to have high chemical stability. A group in which Sp 1 , Sp 2 , Sp 3 and Sp 4 are independently an alkylene having 1 to 7 carbon atoms, or at least one —CH 2 — of an alkylene having 1 to 7 carbon atoms is replaced by —O— The compounds that are the tend to have high solubility in liquid crystal compositions.
　より好ましいＳｐ1、Ｓｐ2、Ｓｐ3、およびＳｐ4は独立して、単結合または炭素数１から５のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－で置き換えられてもよい。 More preferable Sp 1 , Sp 2 , Sp 3 and Sp 4 are independently a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one —CH 2 — is replaced by —O— And at least one — (CH 2 ) 2 — may be replaced by —CH = CH—.
　液晶組成物への溶解性により優れる化合物となる等の点から、特に好ましくは、
　Ｓｐ1は、単結合または炭素数１から５のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよく；
　Ｓｐ2、およびＳｐ3は独立して、単結合または炭素数１から５のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよく、さらに好ましくは－ＣＨ2－であり；
　Ｓｐ4は、－ＣＨ2－である。 From the viewpoint of being a compound which is more excellent due to the solubility in liquid crystal composition,
Sp 1 is a single bond or an alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one —CH 2 — may be replaced by —O—;
Sp 2 and Sp 3 are independently a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one —CH 2 — may be replaced by —O—, more preferably -CH 2- and
Sp 4 is -CH 2- .
　Ｓｐ5は、炭素数２から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよい。
　好ましいＳｐ5は、炭素数２から７のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよい。
　Ｓｐ5が炭素数２から７のアルキレンである化合物は、化学的安定性が高く、液晶組成物への溶解性により優れる傾向にある。Ｓｐ5が炭素数２から７のアルキレンの少なくとも１つの－ＣＨ2－が－Ｏ－で置き換えられた基である化合物は、液晶組成物への溶解度が大きく、液晶分子を配向させる能力が高い傾向にある。
　液晶組成物への溶解性により優れる化合物となる等の点から、Ｓｐ5は、特に好ましくは－（ＣＨ2）2－である。 Sp 5 is alkylene having 2 to 10 carbons, and in this alkylene, at least one —CH 2 — may be replaced by —O—.
Preferred Sp 5 is alkylene having 2 to 7 carbon atoms, in which at least one —CH 2 — may be replaced by —O—.
Compounds in which Sp 5 is an alkylene having 2 to 7 carbon atoms have high chemical stability and tend to be more excellent in solubility in liquid crystal compositions. Compounds in which Sp 5 is a group in which at least one —CH 2 — of C 2 to C 7 alkylene is replaced by —O— have a high solubility in liquid crystal compositions and tend to have high ability to align liquid crystal molecules. It is in.
Sp 5 is particularly preferably — (CH 2 ) 2 — from the viewpoint of being a compound which is more excellent due to the solubility in the liquid crystal composition.
　Ｍ1、Ｍ2、Ｍ3、およびＭ4は独立して、水素、フッ素、塩素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルであり、好ましくは、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素で置き換えられた炭素数１から５のアルキルであり、紫外線照射による重合反応性が特に高い化合物となる等の点から、より好ましくは、水素である。 M 1 , M 2 , M 3 and M 4 independently represent hydrogen, fluorine, chlorine, alkyl having 1 to 5 carbon atoms, or 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine Compounds which are alkyl, preferably hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced by fluorine, and which have particularly high polymerization reactivity by ultraviolet irradiation More preferably, hydrogen is used from the viewpoint of
　Ｒ2は、水素または炭素数１から５のアルキルであり、このアルキルにおいて、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。
　好ましいＲ2は、水素または炭素数１から５のアルキルである。液晶組成物への溶解性により優れ、化学的安定性が高く、液晶分子を配向させる能力が高い化合物となる等の点から、より好ましいＲ2は、炭素数１から３のアルキルであり、特に好ましいＲ2は、メチルである。 R 2 is hydrogen or alkyl having 1 to 5 carbon atoms, and in this alkyl, at least one — (CH 2 ) 2 — may be replaced by —CH = CH— or —C≡C—, In these groups, at least one hydrogen may be replaced by fluorine or chlorine.
Preferred R 2 is hydrogen or alkyl having 1 to 5 carbons. More preferable R 2 is alkyl having 1 to 3 carbon atoms, from the viewpoint of being a compound which is more excellent in solubility in liquid crystal composition, high in chemical stability, and high in ability to align liquid crystal molecules, etc. Preferred R 2 is methyl.
　Ｘ1は、－ＯＨ、－ＮＨ2、－ＯＲ3、－Ｎ（Ｒ3）2、－ＣＯＯＨ、－ＳＨ、または－Ｓｉ（Ｒ3）3である。
　液晶組成物への溶解性により優れる化合物となる等の点から、好ましいＸ1は、－ＯＨ、－ＮＨ2、または－ＳＨであり、特に好ましいＸ1は、－ＯＨである。
　ここで、Ｒ3は水素または炭素数１から１０のアルキルであり、このアルキルにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。 X 1 is —OH, —NH 2 , —OR 3 , —N (R 3 ) 2 , —COOH, —SH, or —Si (R 3 ) 3 .
From the viewpoint of being a compound which is more excellent in solubility in a liquid crystal composition, and the like, preferable X 1 is —OH, —NH 2 or —SH, and particularly preferable X 1 is —OH.
Here, R 3 is hydrogen or alkyl having 1 to 10 carbons, and in this alkyl, at least one —CH 2 — may be replaced by —O—, and at least one — (CH 2 ) 2 -May be replaced by -CH = CH-, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine.
　Ｘ1が－ＯＨ、－ＮＨ2、または－ＳＨである化合物は、液晶分子を配向させる能力が高い傾向にある。Ｘ1が－ＯＨである化合物は、化学的安定性が高く、液晶分子を配向させる能力が高く、そして液晶組成物への溶解度が大きい傾向にあり、該化合物を用いることで、電圧保持率が大きい液晶表示素子が得られやすくなる。 Compounds in which X 1 is —OH, —NH 2 , or —SH tend to have high ability to align liquid crystal molecules. Compounds in which X 1 is -OH tend to have high chemical stability, high ability to orient liquid crystal molecules, and high solubility in liquid crystal compositions, and the use of such compounds results in a voltage holding ratio of It becomes easy to obtain a large liquid crystal display element.
　なお、ａが１であり、環Ａ1が１，４－シクロヘキシレンであり、環Ａ2が１，４－フェニレンであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｓｐ5が－（ＣＨ2）2－であり、Ｒ2がメチルであり、Ｘ1が－ＯＨであるときは、Ｓｐ1は、－ＣＨ2－ではなく；
　ａが１であり、環Ａ1が１，４－フェニレンであり、環Ａ2がナフタレン－２，６－ジイルであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｓｐ5が－（ＣＨ2）2－であり、Ｒ2がメチルであり、Ｘ1が－ＯＨであるときは、Ｓｐ1は、－ＣＨ2－ではなく；
　ａが３であり、４つの環がＲ1側からそれぞれ、１，４－フェニレン、２－エチル－１，４－フェニレン、１，４－シクロヘキシレン、および１，４－シクロヘキシレンであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｓｐ5が－（ＣＨ2）2－であり、Ｒ2がメチルであり、Ｘ1が－ＯＨであるときは、Ｓｐ1は、－ＣＨ2－ではない。 In addition, a is 1, ring A 1 is 1,4-cyclohexylene, ring A 2 is 1,4-phenylene, Z 1 is a single bond, Sp 2 , Sp 3 , and Sp 4 Is -CH 2- , Sp 5 is-(CH 2 ) 2- , R 2 is methyl and X 1 is -OH, then Sp 1 is not -CH 2- ;
a is 1, ring A 1 is 1,4-phenylene, ring A 2 is naphthalene-2,6-diyl, Z 1 is a single bond, Sp 2 , Sp 3 , and Sp 4 are When -CH 2- , Sp 5 is-(CH 2 ) 2- , R 2 is methyl and X 1 is -OH, then Sp 1 is not -CH 2- ;
a is 3, and 4 rings from the R 1 side are respectively 1,4-phenylene, 2-ethyl-1,4-phenylene, 1,4-cyclohexylene, and 1,4-cyclohexylene; 1 is a single bond, Sp 2 , Sp 3 and Sp 4 are -CH 2- , Sp 5 is-(CH 2 ) 2- , R 2 is methyl and X 1 is -OH Sometimes, Sp 1 is not -CH 2- .
　好ましい化合物（１）の例は、項４に記載した化合物（１－１）から（１－４）である。より好ましい化合物（１）の例は、項５に記載した化合物（１－５）から（１－７）である。さらに好ましい化合物（１）の例は、項６に記載した化合物（１－８）から（１－１６）である。最も好ましい化合物（１）の例は、項７に記載した化合物（１－１７）から（１－２３）である。 Examples of preferable compound (1) are compounds (1-1) to (1-4) described in Item 4. Examples of more preferable compound (1) are compounds (1-5) to (1-7) described in item 5. Examples of further preferable compound (1) are compounds (1-8) to (1-16) described in Item 6. Examples of the most preferred compound (1) are compounds (1-17) to (1-23) described in Item 7.
２．化合物（１）の合成
　化合物（１）の合成法について説明する。化合物（１）は、有機合成化学の方法を適切に組み合わせることにより合成できる。合成法を記載しなかった化合物は、「オーガニック・シンセシス」（Organic Syntheses, John Wiley & Sons, Inc）、「オーガニック・リアクションズ」（Organic Reactions, John Wiley & Sons, Inc）、「コンプリヘンシブ・オーガニック・シンセシス」（Comprehensive Organic Synthesis, Pergamon Press）、「新実験化学講座」（丸善）などの成書に記載された方法によって合成できる。 2. Synthesis of Compound (1) A synthesis method of compound (1) will be described. The compound (1) can be synthesized by appropriately combining the methods of synthetic organic chemistry. The compounds that did not describe the synthesis method are “Organic Synthesis” (Organic Syntheses, John Wiley & Sons, Inc.), “Organic Reactions” (Organic Reactions, John Wiley & Sons, Inc.), “Comprehensive Organic” Synthesis can be carried out by the method described in the book such as “Comprehensive Organic Synthesis, Pergamon Press”, “New Experimental Chemistry Lecture” (Maruzen).
２－１．結合基の生成
　化合物（１）における結合基を生成する方法の例は、下記のスキームのとおりである。このスキームにおいて、ＭＳＧ1（またはＭＳＧ2）は、少なくとも１つの環を有する一価の有機基である。複数のＭＳＧ1（またはＭＳＧ2）が表す一価の有機基は、同一であってもよいし、または異なってもよい。化合物（１Ａ）から（１Ｇ）は、化合物（１）または化合物（１）の中間体に相当する。 2-1. Formation of Bonding Group An example of a method of generating a bonding group in compound (1) is as shown in the following scheme. In this scheme, MSG 1 (or MSG 2 ) is a monovalent organic group having at least one ring. The monovalent organic groups represented by a plurality of MSG 1 (or MSG 2 ) may be the same or different. Compounds (1A) to (1G) correspond to compound (1) or an intermediate of compound (1).
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
（Ｉ）単結合の生成
　ホウ酸化合物（２１）と化合物（２２）とを、炭酸塩、テトラキス（トリフェニルホスフィン）パラジウム触媒の存在下で反応させ、化合物（１Ａ）を合成する。この化合物（１Ａ）は、化合物（２３）にｎ－ブチルリチウムを、次いで塩化亜鉛を反応させ、ジクロロビス（トリフェニルホスフィン）パラジウム触媒の存在下で化合物（２２）を反応させても合成できる。 (I) Formation of Single Bond The boric acid compound (21) and the compound (22) are reacted in the presence of a carbonate, tetrakis (triphenylphosphine) palladium catalyst to synthesize a compound (1A). This compound (1A) can also be synthesized by reacting compound (23) with n-butyllithium and then with zinc chloride and reacting compound (22) in the presence of dichlorobis (triphenylphosphine) palladium catalyst.
（ＩＩ）－ＣＯＯ－と－ＯＣＯ－の生成
　化合物（２３）にｎ－ブチルリチウムを、次いで二酸化炭素を反応させ、カルボン酸（２４）を得る。このカルボン酸（２４）と、化合物（２１）から誘導したアルコール（２５）とをＤＣＣ（１，３－ジシクロヘキシルカルボジイミド）とＤＭＡＰ（４－ジメチルアミノピリジン）の存在下で脱水させて－ＣＯＯ－を有する化合物（１Ｂ）を合成する。この方法によって－ＯＣＯ－を有する化合物も合成する。 Formation of (II) -COO- and -OCO- Compound (23) is reacted with n-butyllithium and then carbon dioxide to obtain carboxylic acid (24). The carboxylic acid (24) and the alcohol (25) derived from the compound (21) are dehydrated in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) to give -COO- Compound (1B) is synthesized. The compound having -OCO- is also synthesized by this method.
（ＩＩＩ）－ＣＦ2Ｏ－と－ＯＣＦ2－の生成
　化合物（１Ｂ）をローソン試薬で硫黄化し、化合物（２６）を得る。化合物（２６）をフッ化水素ピリジン錯体とＮＢＳ（Ｎ－ブロモスクシンイミド）でフッ素化し、－ＣＦ2Ｏ－を有する化合物（１Ｃ）を合成する。M. Kuroboshi et al., Chem. Lett., 1992，827.を参照。化合物（１Ｃ）は化合物（２６）をＤＡＳＴ（（ジエチルアミノ）サルファートリフルオリド）でフッ素化しても合成できる。W. H. Bunnelle et al., J. Org. Chem.1990, 55, 768.を参照。この方法によって－ＯＣＦ2－を有する化合物も合成できる。 (III) Formation of —CF 2 O— and —OCF 2 — Compound (1B) is sulfurized with Lawesson's reagent to give compound (26). The compound (26) is fluorinated with hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize a compound (1C) having —CF 2 O—. See M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1C) can also be synthesized by fluorinating compound (26) with DAST ((diethylamino) sulfur trifluoride). See W. H. Bunnelle et al., J. Org. Chem. 1990, 55, 768. Compounds having -OCF 2- can also be synthesized by this method.
（ＩＶ）－ＣＨ＝ＣＨ－の生成
　化合物（２２）をｎ－ブチルリチウム、次いでＤＭＦ（Ｎ，Ｎ－ジメチルホルムアミド）と反応させてアルデヒド（２７）を得る。ホスホニウム塩（２８）とカリウムｔｅｒｔ－ブトキシドを反応させて発生させたリンイリドを、アルデヒド（２７）と反応させて化合物（１Ｄ）を合成する。反応条件によってはシス体が生成するので、必要に応じて公知の方法によりシス体をトランス体に異性化する。 (IV) Formation of —CH = CH— Compound (22) is reacted with n-butyllithium and then DMF (N, N-dimethylformamide) to obtain aldehyde (27). Phosphorus ylide generated by reacting phosphonium salt (28) with potassium tert-butoxide is reacted with aldehyde (27) to synthesize compound (1D). Depending on the reaction conditions, a cis form is formed, and if necessary, the cis form is isomerized to a trans form by a known method.
（Ｖ）－ＣＨ2ＣＨ2－の生成
　化合物（１Ｄ）をパラジウム炭素触媒の存在下で水素化し、化合物（１Ｅ）を合成する。 (V) Formation of —CH 2 CH 2 — Compound (1D) is hydrogenated in the presence of a palladium on carbon catalyst to synthesize compound (1E).
（ＶＩ）－Ｃ≡Ｃ－の生成
　ジクロロパラジウムとヨウ化銅の触媒存在下で、化合物（２３）に２－メチル－３－ブチン－２－オールを反応させた後、塩基性条件下で脱保護して化合物（２９）を得る。ジクロロビス（トリフェニルホスフィン）パラジウムとハロゲン化銅との触媒存在下、化合物（２９）を化合物（２２）と反応させて、化合物（１Ｆ）を合成する。 (VI) Formation of -C≡C- After reacting compound (23) with 2-methyl-3-butyn-2-ol in the presence of dichloropalladium and copper iodide as a catalyst, the reaction is carried out under basic conditions Protected to give compound (29). Compound (29) is reacted with compound (22) in the presence of a catalyst of dichlorobis (triphenylphosphine) palladium and copper halide to synthesize compound (1F).
（ＶＩＩ）－ＣＨ2Ｏ－と－ＯＣＨ2－の生成
　化合物（２７）を水素化ホウ素ナトリウムで還元して化合物（３０）を得る。これを臭化水素酸で臭素化して化合物（３１）を得る。炭酸カリウムの存在下、化合物（２５）と化合物（３１）とを反応させて、化合物（１Ｇ）を合成する。この方法によって－ＯＣＨ2－を有する化合物も合成できる。 (VII) Formation of —CH 2 O— and —OCH 2 — Compound (27) is reduced with sodium borohydride to obtain Compound (30). This is brominated with hydrobromic acid to give compound (31). Compound (25) and compound (31) are reacted in the presence of potassium carbonate to synthesize compound (1G). Compounds having -OCH 2- can also be synthesized by this method.
（ＶＩＩＩ）－ＣＦ＝ＣＦ－の生成
　化合物（２３）をｎ－ブチルリチウムで処理した後、テトラフルオロエチレンを反応させて化合物（３２）を得る。化合物（２２）をｎ－ブチルリチウムで処理した後、化合物（３２）と反応させて、化合物（１Ｈ）を合成する。 (VIII) Formation of —CF = CF— Compound (23) is treated with n-butyllithium and then reacted with tetrafluoroethylene to give compound (32). Compound (22) is treated with n-butyllithium and then reacted with compound (32) to synthesize compound (1H).
２－２．環Ａ1およびＡ2の生成
　１，２－シクロプロピレン、１，３－シクロブチレン、１，３－シクロペンチレン、１，４－シクロヘキシレン、１，４－シクロヘプチレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－２，６－ジイル、デカヒドロナフタレン－２，６－ジイル、１，２，３，４－テトラヒドロナフタレン－２，６－ジイル、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、ピリジン－２，５－ジイルなどの環に関しては出発物が市販されているか、または合成法がよく知られている。 2-2. Formation of ring A 1 and A 2 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-cyclohexenylene , 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl Starting materials are commercially available with respect to rings such as 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, etc., or a synthetic method is well known .
２－３．合成例
　化合物（１）を合成する方法の例は、次のとおりである。これらの化合物において、Ｒ1、Ｒ2、Ａ1、Ａ2、Ｚ1、Ｓｐ1、Ｓｐ2、Ｓｐ3、およびａの定義は、項１に記載と同一である。 2-3. Synthesis Example An example of a method of synthesizing the compound (1) is as follows. In these compounds, the definitions of R 1 , R 2 , A 1 , A 2 , Z 1 , Sp 1 , Sp 2 , Sp 3 and a are the same as described in item 1.
　式（１）において、Ｓｐ4が－ＣＨ2－であり、Ｓｐ5が－（ＣＨ2）2－であり、Ｍ1、Ｍ2、Ｍ3、およびＭ4が水素であり、Ｘ1が－ＯＨである化合物（１－５１）は、以下の方法で合成できる。
　化合物（５１）をＤＡＢＣＯ（１，４－ジアザビシクロ［２．２．２］オクタン）の存在下でホルムアルデヒドと反応させ、化合物（５２）を得る。化合物（５２）に対し、トリフルオロメタンスルホン酸無水物（Ｔｆ2Ｏ）およびトリエチルアミンを作用させた後、エチレングリコールと反応させることによって、化合物（５３）を得る。化合物（５３）をＰＰＴＳ（ｐ－トルエンスルホン酸ピリジニウム）の存在下で３,４－ジヒドロ－２Ｈ－ピランと反応させ、化合物（５４）を得る。化合物（５４）を水酸化リチウムを用いて加水分解して、化合物（５５）を得る。公知の方法で合成されるジオール（５６）と化合物（５７）をトリエチルアミンの存在下で反応させ化合物（５８）を得る。化合物（５８）と化合物（５５）をＤＣＣおよびＤＭＡＰの存在下で反応させ、化合物（５９）を得た後、ＰＰＴＳを用いて脱保護させることにより、化合物（１－５１）へと導くことができる。 In the formula (1), Sp 4 is -CH 2- , Sp 5 is-(CH 2 ) 2- , M 1 , M 2 , M 3 and M 4 are hydrogen and X 1 is- The compound (1-51) which is OH can be synthesized by the following method.
Compound (51) is reacted with formaldehyde in the presence of DABCO (1,4-diazabicyclo [2.2.2] octane) to give compound (52). Compound (52) is reacted with trifluoromethanesulfonic anhydride (Tf 2 O) and triethylamine, and then reacted with ethylene glycol to give compound (53). Compound (53) is reacted with 3,4-dihydro-2H-pyran in the presence of PPTS (pyridinium p-toluenesulfonate) to give compound (54). Compound (54) is hydrolyzed with lithium hydroxide to give compound (55). Diol (56) synthesized by a known method and compound (57) are reacted in the presence of triethylamine to obtain compound (58). Compound (58) and Compound (55) are reacted in the presence of DCC and DMAP to obtain Compound (59), and then deprotected using PPTS to lead to Compound (1-51). it can.
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
３．液晶組成物
３－１．成分化合物
　本発明の一実施形態に係る液晶組成物は、化合物（１）を成分Ａとして含む。化合物（１）は、素子の基板との非共有結合的な相互作用によって、液晶分子の配向を制御することができる。この組成物は、化合物（１）を成分Ａとして含み、下記成分Ｂ、Ｃ、Ｄ、およびＥから選択された少なくとも１つの液晶性化合物をさらに含むことが好ましい。成分Ｂは、化合物（２）から（４）より選択される。成分Ｃは、化合物（２）から（４）以外の化合物（５）から（７）より選択される。成分Ｄは、化合物（８）である。成分Ｅは、化合物（１１）から（１９）より選択される。この組成物は、化合物（２）から（８）および（１１）から（１９）とは異なる、その他の液晶性化合物を含んでもよい。この組成物を調製するときには、正または負の誘電率異方性の大きさなどを考慮して成分Ｂ、Ｃ、Ｄ、およびＥを選択することが好ましい。成分を適切に選択した組成物は、高い上限温度、低い下限温度、低粘度、適切な光学異方性（すなわち、大きな光学異方性または小さな光学異方性）、正または負に大きな誘電率異方性、大きな比抵抗、熱または紫外線に対する安定性、および適切な弾性定数（すなわち、大きな弾性定数または小さな弾性定数）を有する。 3. Liquid Crystal Composition 3-1. Component Compound The liquid crystal composition according to an embodiment of the present invention contains the compound (1) as a component A. The compound (1) can control the alignment of liquid crystal molecules by noncovalent interaction with the substrate of the device. It is preferable that this composition contains the compound (1) as the component A, and further contains at least one liquid crystal compound selected from the following components B, C, D, and E. Component B is selected from compounds (2) to (4). Component C is selected from compounds (5) to (7) other than compounds (2) to (4). Component D is a compound (8). Component E is selected from compounds (11) to (19). This composition may contain other liquid crystal compounds different from the compounds (2) to (8) and (11) to (19). When preparing this composition, it is preferable to select components B, C, D, and E in consideration of the magnitude of positive or negative dielectric anisotropy and the like. Compositions with appropriately selected components have high upper limit temperature, lower limit temperature, lower viscosity, suitable optical anisotropy (ie large optical anisotropy or small optical anisotropy), positive or negative large dielectric constant It has anisotropy, high specific resistance, stability to heat or ultraviolet light, and a suitable elastic constant (ie, a large elastic constant or a small elastic constant).
　化合物（１）は、液晶分子の配向を制御する目的で、組成物に添加される。液晶組成物１００重量％に対する化合物（１）の好ましい割合は、液晶分子を容易に配向させることができる等の点から、０．０５重量％以上であり、素子の表示不良をより防ぐことができる等の点から、１０重量％以下であることが好ましい。より好ましい割合は、０．１重量％から７重量％の範囲であり、さらに好ましい割合は、０．４重量％から５重量％の範囲であり、特に好ましい割合は、０．５重量％から５重量％の範囲である。これらの割合は、化合物（２０）を含む組成物に対しても適用される。 The compound (1) is added to the composition for the purpose of controlling the alignment of liquid crystal molecules. The preferred ratio of the compound (1) to 100% by weight of the liquid crystal composition is 0.05% by weight or more from the viewpoint that liquid crystal molecules can be easily aligned, etc., and the display defect of the device can be further prevented. From the point of etc., it is preferable that it is 10 weight% or less. A more preferable ratio is in the range of 0.1% by weight to 7% by weight, and a further preferable ratio is in the range of 0.4% by weight to 5% by weight, and a particularly preferable ratio is 0.5% by weight to 5%. It is the range of weight%. These ratios also apply to the composition containing compound (20).
　成分Ｂは、２つの末端基がアルキルなどである化合物である。成分Ｂは、小さな誘電率異方性を有する。成分Ｂの好ましい例として、化合物（２－１）から（２－１１）、化合物（３－１）から（３－１９）、および化合物（４－１）から（４－７）を挙げることができる。これらの化合物において、Ｒ11およびＲ12は独立して、炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルまたはアルケニルにおいて、少なくとも１つの－ＣＨ2－は－Ｏ－で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよい。 Component B is a compound in which the two end groups are alkyl or the like. Component B has a small dielectric anisotropy. Preferred examples of component B include compounds (2-1) to (2-11), compounds (3-1) to (3-19), and compounds (4-1) to (4-7). it can. In these compounds, R 11 and R 12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl or alkenyl, at least one —CH 2 — is —O— In these groups, at least one hydrogen may be replaced by fluorine.
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
　成分Ｂは、誘電率異方性の絶対値が小さいので、中性に近い化合物である。化合物（２）は、主として粘度の減少または光学異方性の調整に効果がある。化合物（３）および（４）は、上限温度を高くすることによってネマチック相の温度範囲を広げる効果、または光学異方性の調整に効果がある。 The component B is a compound close to neutrality because the absolute value of the dielectric anisotropy is small. The compound (2) is mainly effective in reducing the viscosity or adjusting the optical anisotropy. The compounds (3) and (4) are effective in extending the temperature range of the nematic phase or in adjusting the optical anisotropy by raising the upper limit temperature.
　成分Ｂの含有量を増加させるにつれて組成物の誘電率異方性が小さくなるが粘度は小さくなる。このため、素子のしきい値電圧の要求値を満たす限り、成分Ｂの含有量は多いほうが好ましい。成分Ｂの含有量は、液晶組成物１００重量％に対し、好ましくは３０重量％以上、さらに好ましくは４０重量％以上であり、その上限は特に制限されないが、例えば９９．９５重量％である。 As the content of component B is increased, the dielectric anisotropy of the composition decreases but the viscosity decreases. Therefore, as long as the required value of the threshold voltage of the device is satisfied, it is preferable that the content of the component B be as large as possible. The content of Component B is preferably 30% by weight or more, more preferably 40% by weight or more, based on 100% by weight of the liquid crystal composition, and the upper limit thereof is not particularly limited, and is, for example, 99.95% by weight.
　成分Ｃは、少なくとも一方の末端にフッ素、塩素またはフッ素含有基を有する化合物である。成分Ｃは、正に大きな誘電率異方性を有する。成分Ｃの好ましい例として、化合物（５－１）から（５－１６）、化合物（６－１）から（６－１１６）、化合物（７－１）から（７－５９）を挙げることができる。成分Ｃの化合物において、Ｒ13は炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの－ＣＨ2－は－Ｏ－で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく；Ｘ11は、フッ素、塩素、－ＯＣＦ3、－ＯＣＨＦ2、－ＣＦ3、－ＣＨＦ2、－ＣＨ2Ｆ、－ＯＣＦ2ＣＨＦ2、または－ＯＣＦ2ＣＨＦＣＦ3である。 Component C is a compound having a fluorine, chlorine or fluorine-containing group at at least one end. Component C has a large dielectric anisotropy. Preferred examples of component C include compounds (5-1) to (5-16), compounds (6-1) to (6-116), and compounds (7-1) to (7-59). . In the compound of component C, R 13 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O— In these groups, 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
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
　成分Ｃは、誘電率異方性が正であり、熱、光などに対する安定性が非常に良好であるので、ＩＰＳ、ＦＦＳ、ＯＣＢなどのモード用の組成物を調製する場合に好適に用いられる。成分Ｃを用いて誘電率異方性が正である組成物を調製する場合、液晶組成物１００重量％に対する成分Ｃの含有量は、１重量％から９９重量％の範囲が適しており、好ましくは１０重量％から９７重量％の範囲、さらに好ましくは４０重量％から９５重量％の範囲である。成分Ｃを誘電率異方性が負である組成物に添加する場合、成分Ｃの含有量は液晶組成物１００重量％に対し、３０重量％以下が好ましい。成分Ｃを添加することにより、組成物の弾性定数を調整し、素子の電圧－透過率曲線を調整することが可能となる。 Component C has a positive dielectric anisotropy and is very good in stability to heat, light and the like, and thus is suitably used when preparing a composition for modes such as IPS, FFS and OCB. . When component C is used to prepare a composition having positive dielectric anisotropy, the content of component C with respect to 100% by weight of the liquid crystal composition is suitably in the range of 1% by weight to 99% by weight, and preferably Is in the range of 10% by weight to 97% by weight, more preferably in the range of 40% by weight to 95% by weight. When component C is added to a composition having a negative dielectric anisotropy, the content of component C is preferably 30% by weight or less based on 100% by weight of the liquid crystal composition. By adding the component C, it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.
　成分Ｄは、片末端基が－Ｃ≡Ｎまたは－Ｃ≡Ｃ－Ｃ≡Ｎである化合物（８）である。成分Ｄは、シアノ基を有するので正により大きな誘電率異方性を有する。成分Ｄの好ましい例として、化合物（８－１）から（８－６４）を挙げることができる。成分Ｄの化合物において、Ｒ14は炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの－ＣＨ2－は－Ｏ－で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく；－Ｘ12は－Ｃ≡Ｎまたは－Ｃ≡Ｃ－Ｃ≡Ｎである。 Component D is a compound (8) in which one terminal group is —C≡N or —C≡C—C≡N. Component D has a cyano group and thus has a larger dielectric anisotropy positively. As preferred examples of component D, compounds (8-1) to (8-64) can be mentioned. In the compound of component D, R 14 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O— In these groups, at least one hydrogen may be replaced by fluorine; -X 12 is -C≡N or -C≡C-C≡N.
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
　成分Ｄは、誘電率異方性が正であり、その値が大きいので、ＴＮなどのモード用の組成物を調製する場合に主として用いられる。この成分Ｄを添加することにより、組成物の誘電率異方性を大きくすることができる。成分Ｄは、液晶相の温度範囲を広げる、粘度を調整する、または光学異方性を調整する、という効果がある。成分Ｄは、素子の電圧－透過率曲線の調整にも有用である。 Component D is mainly used when preparing a composition for a mode such as TN since the dielectric anisotropy is positive and the value thereof is large. By adding this component D, the dielectric anisotropy of the composition can be increased. Component D has the effect of widening the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. Component D is also useful for adjusting the voltage-transmittance curve of the device.
　成分Ｄを用いて誘電率異方性が正である組成物を調製する場合、液晶組成物１００重量％に対する成分Ｄの含有量は、１重量％から９９重量％の範囲が適しており、好ましくは１０重量％から９７重量％の範囲、さらに好ましくは４０重量％から９５重量％の範囲である。成分Ｄを誘電率異方性が負である組成物に添加する場合、成分Ｄの含有量は液晶組成物１００重量％に対し、３０重量％以下が好ましい。成分Ｄを添加することにより、組成物の弾性定数を調整し、素子の電圧－透過率曲線を調整することが可能となる。 When component D is used to prepare a composition having positive dielectric anisotropy, the content of component D with respect to 100% by weight of the liquid crystal composition is suitably in the range of 1% by weight to 99% by weight, and preferably Is in the range of 10% by weight to 97% by weight, more preferably in the range of 40% by weight to 95% by weight. When component D is added to a composition having a negative dielectric anisotropy, the content of component D is preferably 30% by weight or less based on 100% by weight of the liquid crystal composition. By adding the component D, it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.
　成分Ｅは、化合物（１１）から（１９）より選ばれる。成分Ｅは、負に大きな誘電率異方性を有する。これらの化合物は、２，３－ジフルオロ－１，４－フェニレンのように、ラテラル位が２つのハロゲン（フッ素または塩素）で置換されたフェニレンを有する。成分Ｅの好ましい例として、化合物（１１－１）から（１１－９）、化合物（１２－１）から（１２－１９）、化合物（１３－１）および（１３－２）、化合物（１４－１）から（１４－３）、化合物（１５－１）から（１５－３）、化合物（１６－１）から（１６－１１）、化合物（１７－１）から（１７－３）、化合物（１８－１）から（１８－３）、および化合物（１９－１）を挙げることができる。これらの化合物において、Ｒ15、Ｒ16、およびＲ17は独立して、炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの－ＣＨ2－は－Ｏ－で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく、そしてＲ17は、水素またはフッ素であってもよい。 Component E is selected from compounds (11) to (19). Component E has a large negative dielectric anisotropy. These compounds have phenylene in which lateral position is substituted by two halogens (fluorine or chlorine) like 2,3-difluoro-1,4-phenylene. Preferred examples of component E include compounds (11-1) to (11-9), compounds (12-1) to (12-19), compounds (13-1) and (13-2), and compounds (14-). 1) to (14-3), compounds (15-1) to (15-3), compounds (16-1) to (16-11), compounds (17-1) to (17-3), compounds 18-1) to (18-3) and the compound (19-1) can be mentioned. In these compounds, R 15, R 16, and R 17 are independently alkenyl alkyl carbon atoms or 2 to 10 of 1 to 10 carbon atoms, in the alkyl and alkenyl, at least one -CH 2 - May be replaced by —O—, in these groups at least one hydrogen may be replaced by fluorine and R 17 may be hydrogen or fluorine.
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000052
　成分Ｅは、誘電率異方性が負に大きい。成分Ｅは、ＩＰＳ、ＶＡ、ＰＳＡなどのモード用の組成物を調製する場合に好適に用いられる。成分Ｅの含有量を増加させるにつれて組成物の誘電率異方性が負に大きくなるが、粘度が大きくなる。このため、素子のしきい値電圧の要求値を満たす限り、含有量は少ないほうが好ましい。誘電率異方性が－５程度であることを考慮すると、充分な電圧駆動をさせるには、液晶組成物１００重量％に対する成分Ｅの含有量は、４０重量％以上であることが好ましい。 Component E has a large negative dielectric anisotropy. Component E is suitably used when preparing a composition for modes such as IPS, VA, PSA and the like. As the content of component E is increased, the dielectric anisotropy of the composition increases negatively, but the viscosity increases. Therefore, as long as the required value of the threshold voltage of the device is satisfied, the content is preferably as small as possible. Considering that the dielectric anisotropy is about -5, the content of component E with respect to 100% by weight of the liquid crystal composition is preferably 40% by weight or more in order to achieve sufficient voltage driving.
　成分Ｅのうち、化合物（１１）は二環化合物であるので、粘度を下げる、光学異方性を調整する、または誘電率異方性を上げる効果がある。化合物（１２）および（１３）は三環化合物であり、化合物（１４）は四環化合物であるので、上限温度を上げる、光学異方性を上げる、または誘電率異方性を上げるという効果がある。化合物（１５）から（１９）は、誘電率異方性を上げるという効果がある。 Among the component E, since the compound (11) is a bicyclic compound, it has an effect of lowering the viscosity, adjusting the optical anisotropy or increasing the dielectric anisotropy. Compounds (12) and (13) are tricyclic compounds, and compound (14) is a tetracyclic compound. Therefore, the effects of increasing the maximum temperature, optical anisotropy, or dielectric anisotropy are obtained. is there. Compounds (15) to (19) have the effect of increasing the dielectric anisotropy.
　成分Ｅを用いて誘電率異方性が負である組成物を調製する場合、成分Ｅの含有量は、液晶組成物１００重量％に対し、好ましくは４０重量％以上であり、さらに好ましくは５０重量％から９５重量％の範囲である。成分Ｅを誘電率異方性が正である組成物に添加する場合は、成分Ｅの含有量は、液晶組成物１００重量％に対し、３０重量％以下が好ましい。成分Ｅを添加することにより、組成物の弾性定数を調整し、素子の電圧－透過率曲線を調整することが可能となる。 When using a component E to prepare a composition having a negative dielectric anisotropy, the content of the component E is preferably 40% by weight or more, more preferably 50% by weight, relative to 100% by weight of the liquid crystal composition. % To 95% by weight. When component E is added to a composition having positive dielectric anisotropy, the content of component E is preferably 30% by weight or less based on 100% by weight of the liquid crystal composition. By adding the component E, it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.
　以上に述べた成分Ｂ、Ｃ、Ｄ、およびＥを適切に組み合わせることによって、高い上限温度、低い下限温度、小さな粘度、適切な光学異方性、正または負に大きな誘電率異方性、大きな比抵抗、紫外線に対する高い安定性、熱に対する高い安定性、大きな弾性定数などの特性の少なくとも１つを充足する液晶組成物を調製することができる。 By combining the components B, C, D and E mentioned above appropriately, high upper limit temperature, low lower limit temperature, small viscosity, suitable optical anisotropy, positive or negative large dielectric anisotropy, large It is possible to prepare a liquid crystal composition satisfying at least one of the properties such as specific resistance, high stability to ultraviolet light, high stability to heat, and a large elastic constant.
３－２．添加物
　液晶組成物は公知の方法によって調製される。例えば、前記成分を混合し、そして加熱によって互いに溶解させる方法が挙げられる。用途に応じて、この組成物に添加物を添加してよい。添加物の例は、化合物（１）以外の重合性化合物、重合開始剤、重合禁止剤、光学活性化合物、酸化防止剤、紫外線吸収剤、光安定剤、熱安定剤、色素、消泡剤などである。このような添加物は当業者によく知られており、文献に記載されている。 3-2. Additives The liquid crystal composition is prepared by a known method. For example, there is a method in which the components are mixed and dissolved with one another by heating. Depending on the application, additives may be added to the composition. Examples of additives include polymerizable compounds other than the compound (1), polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dyes, antifoaming agents, etc. It is. Such additives are well known to those skilled in the art and are described in the literature.
　重合性化合物は、液晶組成物中に重合体を生成させる目的で添加される。電極間に電圧を印加した状態で紫外線を照射して、化合物（１）を重合させることによって、重合体を生成させることができる。この際、化合物（１）は、その極性基がガラス（または金属酸化物）の基板表面と非共有結合的に相互作用した状態で固定化される。これにより、液晶分子の配向を制御する能力がさらに向上し、適切なプレチルトが得られるので、応答時間が短縮される。 The polymerizable compound is added in order to form a polymer in the liquid crystal composition. A polymer can be produced | generated by irradiating an ultraviolet-ray in the state which applied the voltage between electrodes, and polymerizing a compound (1). At this time, the compound (1) is immobilized in the state where its polar group interacts non-covalently with the substrate surface of the glass (or metal oxide). As a result, the ability to control the alignment of liquid crystal molecules is further improved, and an appropriate pretilt is obtained, so that the response time is shortened.
　重合性化合物の好ましい例は、アクリレート、メタクリレート、ビニル化合物、ビニルオキシ化合物、プロペニルエーテル、エポキシ化合物（オキシラン、オキセタン）、およびビニルケトンである。さらに好ましい例は、少なくとも１つのアクリロイルオキシを有する化合物および少なくとも１つのメタクリロイルオキシを有する化合物である。さらに好ましい例には、アクリロイルオキシとメタクリロイルオキシの両方を有する化合物も含まれる。
　重合性化合物の特に好ましい例としては、化合物（２０）が挙げられる。化合物（２０）は、化合物（１）とは異なる化合物である。化合物（１）は極性基を有する。一方、化合物（２０）は、極性基を有さないことが好ましい。 Preferred examples of the polymerizable compound are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes), and vinyl ketones. Further preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. Further preferred examples also include compounds having both acryloyloxy and methacryloyloxy.
A particularly preferred example of the polymerizable compound includes the compound (20). The compound (20) is a compound different from the compound (1). The compound (1) has a polar group. On the other hand, it is preferable that a compound (20) does not have a polar group.
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
　式（２０）において、環Ｆおよび環Ｉは独立して、シクロヘキシル、シクロヘキセニル、フェニル、１－ナフチル、２－ナフチル、テトラヒドロピラン－２－イル、１，３－ジオキサン－２－イル、ピリミジン－２－イル、またはピリジン－２－イルであり、これらの環において、少なくとも１つの水素は、ハロゲン、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から１２のアルキルで置き換えられてもよい。 In Formula (20), ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine- 2-yl or pyridin-2-yl in which at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is halogen It may be substituted by substituted C 1 to C 12 alkyl.
　好ましい環Ｆおよび環Ｉは、シクロヘキシル、シクロヘキセニル、フェニル、フルオロフェニル、ジフルオロフェニル、１－ナフチル、または２－ナフチルである。さらに好ましい環Ｆおよび環Ｉは、シクロヘキシル、シクロヘキセニル、またはフェニルである。特に好ましい環Ｆおよび環Ｉは、フェニルである。 Preferred ring F and ring I are cyclohexyl, cyclohexenyl, phenyl, fluorophenyl, difluorophenyl, 1-naphthyl or 2-naphthyl. Further preferred ring F and ring I are cyclohexyl, cyclohexenyl or phenyl. Particularly preferred ring F and ring I are phenyl.
　式（２０）において、環Ｇは、１，４－シクロへキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－１，２－ジイル、ナフタレン－１，３－ジイル、ナフタレン－１，４－ジイル、ナフタレン－１，５－ジイル、ナフタレン－１，６－ジイル、ナフタレン－１，７－ジイル、ナフタレン－１，８－ジイル、ナフタレン－２，３－ジイル、ナフタレン－２，６－ジイル、ナフタレン－２，７－ジイル、フェナントレン－２，７－ジイル、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、またはピリジン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、ハロゲン、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から１２のアルキルで置き換えられてもよい。 In the formula (20), ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene- 1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2, 6-diyl, naphthalene-2,7-diyl, phenanthrene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or Pyridine-2,5-diyl, in these rings, at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, Other at least one hydrogen may be replaced by alkyl having 1 carbon is replaced with halogen 12.
　好ましい環Ｇは、１，４－シクロへキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、２－フルオロ－１，４－フェニレン、ナフタレン－１，２－ジイル、ナフタレン－１，３－ジイル、ナフタレン－１，４－ジイル、ナフタレン－１，５－ジイル、ナフタレン－１，６－ジイル、ナフタレン－１，７－ジイル、ナフタレン－１，８－ジイル、ナフタレン－２，３－ジイル、ナフタレン－２，６－ジイル、ナフタレン－２，７－ジイルである。さらに好ましい環Ｇは、１，４－シクロへキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、または２－フルオロ－１，４－フェニレンである。特に好ましい環Ｇは、１，４－フェニレンまたは２－フルオロ－１，４－フェニレンである。最も好ましい環Ｇは、１，４－フェニレンである。 Preferred ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3 -Diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl Naphthalene-2,6-diyl and naphthalene-2,7-diyl. More preferable ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene or 2-fluoro-1,4-phenylene. Particularly preferred ring G is 1,4-phenylene or 2-fluoro-1,4-phenylene. The most preferred ring G is 1,4-phenylene.
　式（２０）において、Ｚ22およびＺ23は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ2ＣＨ2－は、－ＣＨ＝ＣＨ－、－Ｃ（ＣＨ3）＝ＣＨ－、－ＣＨ＝Ｃ（ＣＨ3）－、または－Ｃ（ＣＨ3）＝Ｃ（ＣＨ3）－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。好ましいＺ22およびＺ23は、単結合、－ＣＨ2ＣＨ2－、－ＣＨ2Ｏ－、－ＯＣＨ2－、－ＣＯＯ－、または－ＯＣＯ－である。さらに好ましいＺ22およびＺ23は、単結合である。 In formula (20), Z 22 and Z 23 independently represent a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —CO—, -COO-, or -OCO- may be replaced, and at least one -CH 2 CH 2 -is -CH = CH-, -C (CH 3 ) = CH-, -CH = C (CH 3 ) -Or -C (CH 3 ) = C (CH 3 )-, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine. Preferred Z 22 and Z 23 are a single bond, -CH 2 CH 2- , -CH 2 O-, -OCH 2- , -COO-, or -OCO-. Further preferred Z 22 and Z 23 are single bonds.
　化合物（２０）において、Ｐ11、Ｐ12、およびＰ13は独立して、重合性基である。好ましいＰ11からＰ13は、式（Ｐ－１）から式（Ｐ－５）で表される重合性基の群から選択された基である。さらに好ましいＰ11からＰ13は、式（Ｐ－１）、式（Ｐ－２）、または式（Ｐ－３）で表される基である。特に好ましいＰ11からＰ13は、式（Ｐ－１）で表される基である。式（Ｐ－１）で表される好ましい基は、アクリロイルオキシ（－ＯＣＯ－ＣＨ＝ＣＨ2）またはメタクリロイルオキシ（－ＯＣＯ－Ｃ（ＣＨ3）＝ＣＨ2）である。式（Ｐ－１）から式（Ｐ－５）の波線は、結合する部位を示す。 In compound (20), P 11 , P 12 and P 13 are independently a polymerizable group. Preferred P 11 to P 13 are groups selected from the group of polymerizable groups represented by formulas (P-1) to (P-5). Further preferable P 11 to P 13 are groups represented by Formula (P-1), Formula (P-2), or Formula (P-3). Particularly preferable P 11 to P 13 are groups represented by formula (P-1). Preferred groups represented by formula (P-1) are acryloyloxy (—OCO—CH = CH 2 ) or methacryloyloxy (—OCO—C (CH 3 ) = CH 2 ). The wavy lines in formulas (P-1) to (P-5) indicate the binding site.
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
　式（Ｐ－１）から式（Ｐ－５）において、Ｍ11、Ｍ12、およびＭ13は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から５のアルキルである。好ましいＭ11、Ｍ12、およびＭ13は、反応性を上げるために水素またはメチルである。さらに好ましいＭ11は水素またはメチルであり、さらに好ましいＭ12およびＭ13は水素である。 In Formula (P-1) to Formula (P-5), M 11 , M 12 and M 13 independently represent hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is replaced by halogen Alkyl having 1 to 5 carbon atoms. Preferred M 11 , M 12 and M 13 are hydrogen or methyl to increase the reactivity. Further preferred M 11 is hydrogen or methyl, and further preferred M 12 and M 13 are hydrogen.
　式（２０）において、Ｓｐ11、Ｓｐ12、およびＳｐ13は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ2ＣＨ2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。好ましいＳｐ11、Ｓｐ12、およびＳｐ13は、単結合である。 In the formula (20), Sp 11 , Sp 12 and Sp 13 are independently a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, -COO-, -OCO-, or -OCOO-, and at least one -CH 2 CH 2 -may be replaced by -CH = CH- or -C≡C-; In groups, at least one hydrogen may be replaced by fluorine or chlorine. Preferred Sp 11 , Sp 12 and Sp 13 are single bonds.
　式（２０）において、ｕは、０、１、または２である。好ましいｕは０または１である。 In formula (20), u is 0, 1 or 2. Preferred u is 0 or 1.
　式（２０）において、ｆ、ｇ、およびｈは独立して、０、１、２、３、または４であり、そして、ｆ、ｇ、およびｈの和は、１以上である。好ましいｆ、ｇ、またはｈは、０、１または２である。好ましい和は、２、３または４である。さらに好ましい和は、２または３である。 In formula (20), f, g and h are independently 0, 1, 2, 3 or 4 and the sum of f, g and h is 1 or more. Preferred f, g or h is 0, 1 or 2. The preferred sum is 2, 3 or 4. More preferable sum is 2 or 3.
　化合物（２０）の好ましい例は、項１５に記載の化合物（２０－１）から化合物（２０－７）および下記化合物（２０－８）から（２０－１１）である。さらに好ましい例は、化合物（２０－１－１）から（２０－１－５）、化合物（２０－２－１）から（２０－２－５）、化合物（２０－４－１）、化合物（２０－５－１）、化合物（２０－６－１）、および化合物（２０－７－１）である。これらの化合物において、Ｒ25からＲ31は独立して、水素またはメチルであり；Ｒ32、Ｒ33、およびＲ34は独立して、水素または炭素数１から５のアルキルであり、Ｒ32、Ｒ33、およびＲ34の少なくとも１つは炭素数１から５のアルキルであり；ｖ、およびｘは独立して、０または１であり；ｔおよびｕは独立して、１から１０の整数であり；ｔ＋ｖおよびｘ＋ｕはそれぞれ最大で１０であり；Ｌ31からＬ36は独立して、水素またはフッ素であり、Ｌ37およびＬ38は独立して、水素、フッ素、またはメチルである。 Preferred examples of the compound (20) are the compounds (20-1) to the compounds (20-7) described in item 15 and the following compounds (20-8) to (20-11). Further preferable examples are compound (20-1-1) to (20-1-5), compound (20-2-1) to (20-2-5), compound (20-4-1), compound ( 20-5-1), a compound (20-6-1), and a compound (20-7-1). In these compounds, 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 alkyl having 1 to 5 carbons; v and x are independently 0 or 1; t and u are independently an integer of 1 to 10 And t + v and x + u are each at most 10; L 31 to L 36 are independently hydrogen or fluorine, and L 37 and L 38 are independently hydrogen, fluorine or methyl.
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
　組成物中の重合性化合物は、光ラジカル重合開始剤などの重合開始剤を用いることによって、速やかに重合させることができる。また、重合の際の反応条件を最適化することによって、残存する重合性化合物の量を減少させることができる。光ラジカル重合開始剤の例は、ＢＡＳＦ社のダロキュアシリーズからＴＰＯ、１１７３、および４２６５が挙げられ、イルガキュアシリーズから１８４、３６９、５００、６５１、７８４、８１９、９０７、１３００、１７００、１８００、１８５０、および２９５９が挙げられる。 The polymerizable compound in the composition can be rapidly polymerized by using a polymerization initiator such as a radical photopolymerization initiator. In addition, the amount of the remaining polymerizable compound can be reduced by optimizing the reaction conditions in the polymerization. Examples of photo radical polymerization initiators include TPO, 1173, and 4265 from Darocure series of BASF, and 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, from Irgacure series. 1850 and 2959 can be mentioned.
　光ラジカル重合開始剤の追加例は、４－メトキシフェニル－２，４－ビス（トリクロロメチル）トリアジン、２－（４－ブトキシスチリル）－５－トリクロロメチル－１，３，４－オキサジアゾール、９－フェニルアクリジン、９，１０－ベンズフェナジン、ベンゾフェノン／ミヒラーズケトン混合物、ヘキサアリールビイミダゾール／メルカプトベンズイミダゾール混合物、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、ベンジルジメチルケタール、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノプロパン－１－オン、２，４－ジエチルキサントン／ｐ－ジメチルアミノ安息香酸メチル混合物、ベンゾフェノン／メチルトリエタノールアミン混合物である。 Additional examples of photo radical polymerization initiators include 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyl Dimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate mixture, benzophenone / methyltriethanolamine mixture It is.
　液晶組成物に光ラジカル重合開始剤を添加した後、電場を印加した状態で紫外線を照射することによって重合を行うことができる。しかし、未反応の重合開始剤または重合開始剤の分解生成物は、素子に画像の焼き付きなどの表示不良を引き起こす可能性がある。これを防ぐために重合開始剤を添加しないまま光重合を行ってもよい。照射する光の好ましい波長は１５０ｎｍから５００ｎｍの範囲である。さらに好ましい波長は２５０ｎｍから４５０ｎｍの範囲であり、最も好ましい波長は３００ｎｍから４００ｎｍの範囲である。 After adding a photo radical polymerization initiator to the liquid crystal composition, polymerization can be performed by irradiating ultraviolet light in a state where an electric field is applied. However, unreacted polymerization initiator or decomposition products of the polymerization initiator may cause display defects such as image sticking to the device. In order to prevent this, photopolymerization may be carried out without adding a polymerization initiator. The preferred wavelength of the light to be irradiated is in the range of 150 nm to 500 nm. A further preferred wavelength is in the range of 250 nm to 450 nm, and the most preferred wavelength is in the range of 300 nm to 400 nm.
　重合性化合物を保管するとき、重合を防止するために重合禁止剤を添加してもよい。重合性化合物に重合禁止剤が含まれる場合は、通常は重合禁止剤を除去しないまま組成物に添加される。重合禁止剤の例は、ヒドロキノン、メチルヒドロキノンなどのヒドロキノン誘導体、４－ｔ－ブチルカテコール、４-メトキシフェノ－ル、フェノチアジンである。 When storing the polymerizable compound, a polymerization inhibitor may be added to prevent polymerization. When the polymerization compound contains a polymerization inhibitor, it is usually added to the composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine.
　光学活性化合物は、液晶分子にらせん構造を誘起して必要なねじれ角を与えることによって逆ねじれを防ぐ、という効果を有する。光学活性化合物を添加することによって、らせんピッチを調整することができる。らせんピッチの温度依存性を調整する目的で２つ以上の光学活性化合物を添加してもよい。光学活性化合物の好ましい例として、下記の化合物（Ｏｐ－１）から（Ｏｐ－１８）を挙げることができる。化合物（Ｏｐ－１８）において、環Ｊは１，４－シクロへキシレンまたは１，４－フェニレンであり、Ｒ28は炭素数１から１０のアルキルである。＊印は不斉炭素を表す。 The optically active compound has an effect of preventing reverse twist by inducing a helical structure to liquid crystal molecules to give a necessary twist angle. The helical pitch can be adjusted by adding an optically active compound. Two or more optically active compounds may be added in order to adjust the temperature dependency of the helical pitch. As preferred examples of the optically active compounds, the following compounds (Op-1) to (Op-18) can be mentioned. In the compound (Op-18), ring J is 1,4-cyclohexylene or 1,4-phenylene, and R 28 is alkyl having 1 to 10 carbons. The symbol * represents an asymmetric carbon.
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000057
　酸化防止剤を用いることは、素子の大きな電圧保持率を維持するために有効である。酸化防止剤の好ましい例として、下記の化合物（ＡＯ－１）および（ＡＯ－２）；Ｉｒｇａｎｏｘ４１５、Ｉｒｇａｎｏｘ５６５、Ｉｒｇａｎｏｘ１０１０、Ｉｒｇａｎｏｘ１０３５、Ｉｒｇａｎｏｘ３１１４、およびＩｒｇａｎｏｘ１０９８（商品名；ＢＡＳＦ社）を挙げることができる。 The use of an antioxidant is effective to maintain a large voltage holding ratio of the device. As preferable examples of the antioxidant, the following compounds (AO-1) and (AO-2); Irganox 415, Irganox 565, Irganox 1010, Irganox 1035, Irganox 3114, and Irganox 1098 (trade name; manufactured by BASF) can be mentioned.
　紫外線吸収剤を用いることは、素子の上限温度の低下を防ぐために有効である。紫外線吸収剤の好ましい例は、ベンゾフェノン誘導体、ベンゾエート誘導体、トリアゾール誘導体などであり、具体例として下記の化合物（ＡＯ－３）および（ＡＯ－４）；Ｔｉｎｕｖｉｎ３２９、ＴｉｎｕｖｉｎＰ、Ｔｉｎｕｖｉｎ３２６、Ｔｉｎｕｖｉｎ２３４、Ｔｉｎｕｖｉｎ２１３、Ｔｉｎｕｖｉｎ４００、Ｔｉｎｕｖｉｎ３２８、およびＴｉｎｕｖｉｎ９９－２（商品名；ＢＡＳＦ社）；および１，４－ジアザビシクロ［２．２．２］オクタン（ＤＡＢＣＯ）を挙げることができる。 The use of a UV absorber is effective to prevent the lowering of the upper limit temperature of the device. Preferred examples of UV absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like, and specific examples thereof include the following compounds (AO-3) and (AO-4); Tinuvin 329, Tinuvin P, Tinuvin 326, Tinuvin 326, Tinuvin 213, Tinuvin 400, There may be mentioned Tinuvin 328, and Tinuvin 99-2 (trade name; BASF AG); and 1,4-diazabicyclo [2.2.2] octane (DABCO).
　立体障害のあるアミンなどの光安定剤を用いることは、素子の大きな電圧保持率を維持するために好ましい。光安定剤の好ましい例として、下記の化合物（ＡＯ－５）、（ＡＯ－６）、および（ＡＯ－７）；Ｔｉｎｕｖｉｎ１４４、Ｔｉｎｕｖｉｎ７６５、およびＴｉｎｕｖｉｎ７７０ＤＦ（商品名；ＢＡＳＦ社）；ＬＡ－７７ＹおよびＬＡ－７７G（商品名；ＡＤＥＫＡ社）を挙げることができる。 The use of light stabilizers such as sterically hindered amines is preferred to maintain high voltage holding of the device. As preferable examples of the light stabilizer, the following compounds (AO-5), (AO-6), and (AO-7); Tinuvin 144, Tinuvin 765, and Tinuvin 770 DF (trade name; BASF Corporation); LA-77Y and LA- 77G (trade name; ADEKA company) can be mentioned.
　熱安定剤を用いることも素子の大きな電圧保持率を維持するために有効であり、好ましい例としてＩｒｇａｆｏｓ１６８（商品名；ＢＡＳＦ社）を挙げることができる。 The use of a heat stabilizer is also effective for maintaining a large voltage holding ratio of the device, and a preferred example is Irgafos 168 (trade name; BASF Corporation).
　ＧＨ（guest host）モードの素子に適合させるために、必要により、アゾ系色素、アントラキノン系色素などの二色性色素（dichroic dye）が組成物に添加される。 In order to conform to a device of guest host (GH) mode, if necessary, a dichroic dye such as an azo dye or an anthraquinone dye is added to the composition.
　消泡剤は、泡立ちを防ぐために有効である。消泡剤の好ましい例は、ジメチルシリコーンオイル、メチルフェニルシリコーンオイルなどである。 Defoamers are effective to prevent foaming. Preferred examples of the antifoaming agent are dimethyl silicone oil, methylphenyl silicone oil and the like.
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
　化合物（ＡＯ－１）において、Ｒ40は炭素数１から２０のアルキル、炭素数１から２０のアルコキシ、－ＣＯＯＲ41、または－ＣＨ2ＣＨ2ＣＯＯＲ41であり、ここでＲ41は炭素数１から２０のアルキルである。化合物（ＡＯ－２）および（ＡＯ－５）において、Ｒ42は炭素数１から２０のアルキルである。化合物（ＡＯ－５）において、Ｒ43は水素、メチルまたはＯ・（酸素ラジカル）であり；環Ｇ1は１，４－シクロヘキシレンまたは１，４－フェニレンであり；化合物（ＡＯ－７）において、環Ｇ2は１，４－シクロヘキシレン、１，４－フェニレン、または１，４－フェニレンの少なくとも１つの水素がフッ素で置き換えられた基であり；化合物（ＡＯ－５）および（ＡＯ－７）において、ｚは、１、２、または３である。 In the compound (AO-1), R 40 is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, -COOR 41 , or -CH 2 CH 2 COOR 41 , wherein R 41 is 1 carbon To 20 alkyl. In compounds (AO-2) and (AO-5), R 42 is alkyl having 1 to 20 carbons. In compound (AO-5), R 43 is hydrogen, methyl or O. (oxygen radical); ring G 1 is 1,4-cyclohexylene or 1,4-phenylene; in compound (AO-7) And ring G 2 is a group in which at least one hydrogen of 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene is replaced by fluorine; compounds (AO-5) and (AO-7) In the above, z is 1, 2 or 3.
４．液晶表示素子
　液晶組成物は、ＰＣ、ＴＮ、ＳＴＮ、ＯＣＢ、ＰＳＡなどの動作モードを有し、アクティブマトリックス方式で駆動する液晶表示素子に好適に使用できる。この組成物は、ＰＣ、ＴＮ、ＳＴＮ、ＯＣＢ、ＶＡ、ＩＰＳなどの動作モードを有し、パッシブマトリクス方式で駆動する液晶表示素子にも好適に使用することができる。これらの素子は、反射型、透過型、半透過型のいずれのタイプにも適用できる。 4. Liquid Crystal Display Element The liquid crystal composition has an operation mode such as PC, TN, STN, OCB or PSA and can be suitably used for a liquid crystal display element driven by an active matrix system. This composition has an operation mode such as PC, TN, STN, OCB, VA, IPS, etc., and can also be suitably used for a liquid crystal display element driven by a passive matrix system. These elements can be applied to any of reflective, transmissive and semi-transmissive types.
　この組成物は、ＮＣＡＰ（nematic curvilinear aligned phase）素子にも適しており、ここでは組成物がマイクロカプセル化されている。この組成物は、ポリマー分散型液晶表示素子（ＰＤＬＣＤ）や、ポリマーネットワーク液晶表示素子（ＰＮＬＣＤ）にも使用できる。これらの組成物においては、重合性化合物が多量に添加される。一方、ＰＳＡモードの液晶表示素子に用いる組成物は、重合性化合物の割合が液晶組成物１００重量％に対し、好ましくは１０重量％以下であり、より好ましい割合は０．１重量％から２重量％の範囲であり、さらに好ましい割合は、０．２重量％から１．０重量％の範囲である。ＰＳＡモードの素子は、アクティブマトリックス方式、パッシブマトリクス方式などの駆動方式で駆動させることができる。このような素子は、反射型、透過型、半透過型のいずれのタイプにも適用できる。 The composition is also suitable for a nematic curvilinear aligned phase (NCAP) device, in which the composition is microencapsulated. This composition can also be used for polymer dispersed liquid crystal display (PDLCD) and polymer network liquid crystal display (PNLCD). In these compositions, a large amount of polymerizable compound is added. On the other hand, in the composition used for the liquid crystal display element in the PSA mode, the ratio of the polymerizable compound is preferably 10% by weight or less with respect to 100% by weight of the liquid crystal composition, and a more preferable ratio is 0.1% by weight to 2% %, And more preferably 0.2% to 1.0% by weight. The element in the PSA mode can be driven by a driving method such as an active matrix method or a passive matrix method. Such an element can be applied to any of reflective, transmissive, and semi-transmissive types.
　高分子支持配向型の素子では、組成物に含まれる重合体が液晶分子を配向させる。極性化合物は、液晶分子が配列するのを援助する。すなわち、極性化合物は、配向膜の代わりに用いることができる。このような素子を製造する方法の一例は、次のとおりである。アレイ基板とカラーフィルター基板と呼ばれる２つの基板を有する素子を用意する。この基板は配向膜を有さない。この基板の少なくとも１つは、電極層を有する。液晶性化合物を混合して液晶組成物を調製する。この組成物に化合物（１）、さらに必要により他の重合性化合物および極性化合物を添加する。必要に応じて添加物をさらに添加してもよい。この組成物を素子に注入する。この素子に電圧を印加した状態で光照射する。紫外線が好ましい。光照射によって重合性化合物を重合させる。この重合によって、重合体を含む組成物が生成し、ＰＳＡモードを有する素子が作製される。 In a polymer-supported alignment device, a polymer contained in the composition aligns liquid crystal molecules. Polar compounds help the liquid crystal molecules to align. That is, a polar compound can be used instead of the alignment film. An example of a method of manufacturing such a device is as follows. An element having two substrates called an array substrate and a color filter substrate is prepared. This substrate does not have an alignment film. At least one of the substrates has an electrode layer. A liquid crystal compound is mixed to prepare a liquid crystal composition. To this composition is added compound (1), and, if necessary, other polymerizable compounds and polar compounds. Additives may be further added as needed. The composition is injected into the device. Light is irradiated in a state where a voltage is applied to this element. UV light is preferred. The polymerizable compound is polymerized by light irradiation. By this polymerization, a composition containing a polymer is formed, and a device having a PSA mode is produced.
　この手順において、極性化合物は、極性基が基板表面と相互作用するので、基板上に配列する。この極性化合物が、液晶分子を配向させる。極性基が複数存在する場合、基板表面との相互作用がより強くなり、低濃度で配向させることができる。電圧を印加したとき、電場の作用によって液晶分子の配向がさらに促進される。この配向に従って重合性化合物も配向する。この状態で重合性化合物が紫外線によって重合するので、この配向を維持した重合体が生成する。この重合体の効果によって、液晶分子の配向が追加的に安定化するので、素子の応答時間が短縮される。画像の焼き付きは、液晶分子の動作不良であるから、この重合体の効果によって焼き付きも同時に改善されることになる。化合物（１）は重合性であるので、重合によって消費される。化合物（１）は、他の重合性化合物と共重合することによっても消費される。したがって、化合物（１）は極性基を有するが、消費されるので、電圧保持率の大きな液晶表示素子が得られる。なお、重合性を有する極性化合物を用いれば、極性化合物と重合性化合物の両方の効果を１つの化合物で達成することが可能である為、極性基を持たない重合性化合物を必要としない場合もある。 In this procedure, polar compounds are arranged on the substrate as the polar groups interact with the substrate surface. This polar compound aligns the liquid crystal molecules. When a plurality of polar groups are present, the interaction with the substrate surface becomes stronger and can be oriented at a low concentration. When a voltage is applied, the alignment of liquid crystal molecules is further promoted by the action of an electric field. The polymerizable compound is also oriented according to this orientation. In this state, since the polymerizable compound is polymerized by ultraviolet light, a polymer maintaining this orientation is formed. The effect of the polymer is to additionally stabilize the orientation of the liquid crystal molecules, thus reducing the response time of the device. Since image sticking is a malfunction of liquid crystal molecules, the effect of the polymer is to simultaneously improve the sticking. Since the compound (1) is polymerizable, it is consumed by polymerization. The compound (1) is also consumed by copolymerizing with other polymerizable compounds. Accordingly, the compound (1) has a polar group but is consumed, so that a liquid crystal display device having a large voltage holding ratio can be obtained. In addition, since the effects of both the polar compound and the polymerizable compound can be achieved with one compound by using the polar compound having the polymerizability, the polymerizable compound having no polar group is not required. is there.
　実施例（合成例、使用例を含む）により、本発明をさらに詳しく説明する。本発明はこれらの実施例によっては制限されない。本発明は、使用例の組成物の少なくとも２つを混合することによって調製した混合物をも含む。 The present invention will be described in more detail by way of examples (including synthesis examples and usage examples). The invention is not limited by these examples. The invention also includes mixtures prepared by mixing at least two of the compositions of the Use Examples.
１．化合物（１）の実施例
　特に記載のない限り、反応は窒素雰囲気下で行った。化合物（１）は、実施例１などに示した手順により合成した。合成した化合物は、ＮＭＲ分析などの方法により同定した。化合物（１）、液晶性化合物、組成物、素子の特性は、下記の方法により測定した。 1. Examples of Compound (1) Unless otherwise stated, reactions were carried out under a nitrogen atmosphere. Compound (1) was synthesized by the procedure shown in Example 1 and the like. The compound synthesized was identified by a method such as NMR analysis. The properties of the compound (1), the liquid crystal compound, the composition and the device were measured by the following methods.
　ＮＭＲ分析：測定には、ブルカーバイオスピン社製のＤＲＸ－５００を用いた。1Ｈ－ＮＭＲの測定では、試料をＣＤＣｌ3などの重水素化溶媒に溶解させ、測定は、室温で、５００ＭＨｚ、積算回数１６回の条件で行った。テトラメチルシランを内部標準として用いた。19Ｆ－ＮＭＲの測定では、ＣＦＣｌ3を内部標準として用い、積算回数２４回の条件で行った。核磁気共鳴スペクトルの説明において、ｓはシングレット、ｄはダブレット、ｔはトリプレット、ｑはカルテット、ｑｕｉｎはクインテット、ｓｅｘｔはセクステット、ｍはマルチプレット、ｂｒはブロードであることを意味する。 NMR analysis: For measurement, DRX-500 manufactured by Bruker Biospin Ltd. was used. In the measurement of 1 H-NMR, the sample was dissolved in a deuterated solvent such as CDCl 3, and the measurement was performed at room temperature under conditions of 500 MHz and 16 integrations. Tetramethylsilane was used as an internal standard. In the measurement of 19 F-NMR, CFCl 3 was used as an internal standard, and the measurement was performed under the condition of 24 times of integration. In the description of nuclear magnetic resonance spectrum, s is singlet, d is doublet, t is triplet, q is quartet, quin is quintet, sext is sextet, m is multiplet, br is broad.
　ガスクロマト分析：測定には、（株）島津製作所製のＧＣ－２０１０型ガスクロマトグラフを用いた。カラムは、Agilent Technologies Inc.製のキャピラリカラムＤＢ－１（長さ６０ｍ、内径０．２５ｍｍ、膜厚０．２５μｍ）を用いた。キャリアーガスとしてはヘリウム（１ｍｌ／分）を用いた。試料気化室の温度を３００℃、検出器（ＦＩＤ）部分の温度を３００℃に設定した。試料はアセトンに溶解させて、１重量％の溶液となるように調製し、得られた溶液１μｌを試料気化室に注入した。記録計には（株）島津製作所製のＧＣＳｏｌｕｔｉｏｎシステムなどを用いた。 Gas Chromatographic Analysis: A GC-2010 gas chromatograph manufactured by Shimadzu Corporation was used for measurement. As a column, capillary columns DB-1 (length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc. were used. Helium (1 ml / min) was used as a carrier gas. The temperature of the sample vaporization chamber was set to 300 ° C., and the temperature of the detector (FID) portion was set to 300 ° C. The sample was dissolved in acetone to prepare a 1% by weight solution, and 1 μl of the resulting solution was injected into the sample vaporization chamber. As a recorder, a GC Solution system manufactured by Shimadzu Corporation was used.
　ＨＰＬＣ分析：測定には、（株）島津製作所製のＰｒｏｍｉｎｅｎｃｅ（ＬＣ－２０ＡＤ；ＳＰＤ－２０Ａ）を用いた。カラムは（株）ワイエムシィ製のＹＭＣ－Ｐａｃｋ　ＯＤＳ－Ａ（長さ１５０ｍｍ、内径４．６ｍｍ、粒子径５μｍ）を用いた。溶出液はアセトニトリルと水を適宜混合して用いた。検出器としてはＵＶ検出器、ＲＩ検出器、ＣＯＲＯＮＡ検出器などを適宜用いた。ＵＶ検出器を用いた場合、検出波長は２５４ｎｍとした。試料はアセトニトリルに溶解して、０．１重量％の溶液となるように調製し、この溶液１μＬを試料室に導入した。記録計としては（株）島津製作所製のＣ－Ｒ７Ａｐｌｕｓを用いた。 HPLC analysis: For measurement, Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used. The column used was YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle diameter 5 μm) manufactured by YMC. The eluate was used by appropriately mixing acetonitrile and water. As a detector, a UV detector, an RI detector, a CORONA detector, etc. were used suitably. When a UV detector was used, the detection wavelength was 254 nm. The sample was dissolved in acetonitrile to prepare a 0.1% by weight solution, and 1 μL of this solution was introduced into the sample chamber. As a recorder, C-R7Aplus manufactured by Shimadzu Corporation was used.
　紫外可視分光分析：測定には、（株）島津製作所製のＰｈａｒｍａＳｐｅｃ　ＵＶ－１７００を用いた。検出波長は１９０ｎｍから７００ｎｍとした。試料はアセトニトリルに溶解して、０．０１ｍｍｏｌ／Ｌの溶液となるように調製し、石英セル（光路長１ｃｍ）に入れて測定した。 Ultraviolet-visible spectroscopy: For measurement, PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used. The detection wavelength was from 190 nm to 700 nm. The sample was dissolved in acetonitrile to prepare a solution of 0.01 mmol / L, and placed in a quartz cell (optical path length: 1 cm) for measurement.
　測定試料：相構造および転移温度（透明点、融点、重合開始温度など）を測定するときには、化合物そのものを試料として用いた。 Measurement sample: When measuring the phase structure and transition temperature (clearing point, melting point, polymerization initiation temperature, etc.), the compound itself was used as a sample.
　測定方法：特性の測定は下記の方法で行った。これらの多くは、社団法人電子情報技術産業協会（ＪＥＩＴＡ；Japan Electronics and Information Technology Industries Association）で審議制定されるＪＥＩＴＡ規格（ＪＥＩＴＡ・ＥＤ－２５２１Ｂ）に記載された方法、またはこれを修飾した方法であった。測定に用いたＴＮ素子には、薄膜トランジスター（ＴＦＴ）を取り付けなかった。 Measurement method: The measurement of the characteristics was performed by the following method. Many of these are described in the JEITA standard (JEITA ED-2521B) deliberated and enacted by the Japan Electronics and Information Technology Industries Association (JEITA), or a modified method thereof. there were. A thin film transistor (TFT) was not attached to the TN device used for the measurement.
（１）相構造
　偏光顕微鏡を備えた融点測定装置のホットプレート（メトラー社製、ＦＰ－５２型ホットステージ）に試料を置いた。この試料を、３℃／分の速度で加熱しながら相状態とその変化を偏光顕微鏡で観察し、相の種類を特定した。 (1) Phase structure The sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarization microscope (model: FP-52 hot stage manufactured by Mettler). While heating this sample at a rate of 3 ° C./min, the phase state and its change were observed with a polarization microscope to identify the type of phase.
（２）転移温度（℃）
　測定には、パーキンエルマー社製の走査熱量計、Ｄｉａｍｏｎｄ　ＤＳＣシステムまたは（株）日立ハイテクサイエンス製の高感度示差走査熱量計、Ｘ－ＤＳＣ７０００を用いた。試料は、３℃／分の速度で昇降温し、試料の相変化に伴う吸熱ピークまたは発熱ピークの開始点を外挿により求め、転移温度を決定した。化合物の融点、重合開始温度もこの装置を使って測定した。化合物が固体からスメクチック相、ネマチック相などの液晶相に転移する温度を「液晶相の下限温度」と略すことがある。化合物が液晶相から液体に転移する温度を「透明点」と略すことがある。 (2) Transition temperature (° C)
For measurement, a scanning calorimeter manufactured by Perkin Elmer, a Diamond DSC system, or a high-sensitivity differential scanning calorimeter manufactured by Hitachi High-Tech Science Co., Ltd., X-DSC7000 was used. The temperature of the sample was raised and lowered at a rate of 3 ° C./min, and the transition point was determined by extrapolating the start point of the endothermic peak or exothermic peak associated with the phase change of the sample. The melting point of the compound and the polymerization initiation temperature were also measured using this apparatus. 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 "the lower limit temperature of the liquid crystal phase". The temperature at which a compound transitions from liquid crystal phase to liquid may be abbreviated as the "clearing point".
　結晶はＣと表した。結晶の種類の区別がつく場合は、それぞれをＣ1、Ｃ2のように表した。スメクチック相はＳ、ネマチック相はＮと表した。スメクチック相の中で、スメクチックＡ相、スメクチックＢ相、スメクチックＣ相、またはスメクチックＦ相の区別がつく場合は、それぞれＳA、ＳB、ＳC、またはＳFと表した。液体（アイソトロピック）はＩと表した。転移温度は、例えば、「Ｃ　５０．０　Ｎ　１００．０　Ｉ」のように表記した。これは、結晶からネマチック相への転移温度が５０．０℃であり、ネマチック相から液体への転移温度が１００．０℃であることを示す。 The crystal is designated C. When the types of crystals can be distinguished, they are represented as C 1 and C 2 respectively. The smectic phase is represented by S and the nematic phase is represented by N. When a smectic A phase, a smectic B phase, a smectic C phase, or a smectic F phase can be distinguished among the smectic phases, they are represented as S A , S B , S C or S F , respectively. The liquid (isotropic) was designated as I. The transition temperature is expressed as, for example, "C 50.0 N 100.0 I". This indicates that the transition temperature from crystal to nematic phase is 50.0 ° C., and the transition temperature from nematic phase to liquid is 100.0 ° C.
（３）ネマチック相の上限温度（ＴNIまたはＮＩ；℃）
　偏光顕微鏡を備えた融点測定装置のホットプレートに試料を置き、１℃／分の速度で加熱した。試料の一部がネマチック相から等方性液体に変化したときの温度を測定した。ネマチック相の上限温度を「上限温度」と略すことがある。試料が化合物（１）と母液晶との混合物であるときは、ＴNIの記号で示した。試料が化合物（１）と成分Ｂ、Ｃ、Ｄのような化合物との混合物であるときは、ＮＩの記号で示した。 (3) Maximum temperature of nematic phase (T NI or NI; ° C.)
The sample was placed on the hot plate of a melting point apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when part of the sample changed from the nematic phase to the isotropic liquid. The upper limit temperature of the nematic phase may be abbreviated as "upper limit temperature". When the sample is a mixture of compound (1) and mother liquid crystals, it is indicated by the symbol TNI . When the sample is a mixture of compound (1) and a compound such as component B, C or D, it is indicated by the symbol NI.
（４）ネマチック相の下限温度（ＴC；℃）
　ネマチック相を有する試料を０℃、－１０℃、－２０℃、－３０℃、および－４０℃のフリーザー中に１０日間保管した後、液晶相を観察した。例えば、試料が－２０℃ではネマチック相のままであり、－３０℃では結晶またはスメクチック相に変化したとき、ＴCを≦－２０℃と記載した。ネマチック相の下限温度を「下限温度」と略すことがある。 (4) Lower limit temperature of nematic phase (T c ; ° C.)
The liquid crystal phase was observed after storing the sample having the nematic phase in a freezer at 0 ° C., -10 ° C., -20 ° C., -30 ° C., and -40 ° C. for 10 days. For example, the sample remained in the -20 ° C. in a nematic phase, when changed to -30 ° C. At crystals or a smectic phase was described as ≦ -20 ° C. The T C. The lower limit temperature of the nematic phase may be abbreviated as "lower limit temperature".
（５）粘度（バルク粘度；η；２０℃で測定；ｍＰａ・ｓ）
　測定には、東京計器（株）製のＥ型回転粘度計を用いた。 (5) Viscosity (bulk viscosity; ;; measured at 20 ° C .; mPa · s)
For measurement, an E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used.
（６）光学異方性（屈折率異方性；２５℃で測定；Δｎ）
　測定は、波長５８９ｎｍの光を用い、接眼鏡に偏光板を取り付けたアッベ屈折計により行なった。主プリズムの表面を一方向にラビングした後、試料を主プリズムに滴下した。屈折率（ｎ∥）は偏光の方向がラビングの方向と平行であるときに測定した。屈折率（ｎ⊥）は偏光の方向がラビングの方向と垂直であるときに測定した。光学異方性（Δｎ）の値は、Δｎ＝ｎ∥－ｎ⊥、の式から計算した。 (6) Optical anisotropy (refractive index anisotropy; measured at 25 ° C .; Δn)
The measurement was performed using an Abbe refractometer with a polarizing plate attached to the eyepiece, using light at a wavelength of 589 nm. After rubbing the surface of the main prism in one direction, a sample was dropped on the main prism. The refractive index (n∥) was measured when the polarization direction was parallel to the rubbing direction. The refractive index (n⊥) was measured when the polarization direction was perpendicular to the rubbing direction. The value of optical anisotropy (Δn) was calculated from the equation Δn = n∥−n⊥.
（７）比抵抗（ρ；２５℃で測定；Ωｃｍ）
　電極を備えた容器に試料１．０ｍＬを注入した。この容器に直流電圧（１０Ｖ）を印加し、１０秒後の直流電流を測定した。比抵抗は次の式から算出した。（比抵抗）＝｛（電圧）×（容器の電気容量）｝／｛（直流電流）×（真空の誘電率）｝。 (7) Specific resistance (ρ; measured at 25 ° C .; Ω cm)
A sample of 1.0 mL was injected into a container equipped with an electrode. A direct current voltage (10 V) was applied to the container, and a direct current after 10 seconds was measured. The specific resistance was calculated from the following equation. (Specific resistance) = {(voltage) × (electric capacity of container)} / {(direct current) × (dielectric constant of vacuum)}.
　誘電率異方性が正の試料と負の試料とでは、特性の測定法が異なることがある。誘電率異方性が正であるときの測定法は、項（８ａ）から（１２ａ）に記載した。誘電率異方性が負の場合は、項（８ｂ）から（１２ｂ）に記載した。 The measurement method of characteristics may be different between the sample with positive dielectric anisotropy and the sample with negative dielectric anisotropy. The measuring methods when the dielectric anisotropy is positive are described in the items (8a) to (12a). When the dielectric anisotropy is negative, the terms (8b) to (12b) are described.
（８ａ）粘度（回転粘度；γ１；２５℃で測定；ｍＰａ・ｓ）
　正の誘電率異方性：測定は、M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995) に記載された方法に従った。ツイスト角が０度であり、そして２枚のガラス基板の間隔（セルギャップ）が５μｍであるＴＮ素子に試料を入れた。この素子に１６Ｖから１９．５Ｖの範囲で０．５Ｖ毎に段階的に電圧を印加した。０．２秒の無印加の後、ただ１つの矩形波（矩形パルス；０．２秒）と無印加（２秒）の条件で印加を繰り返した。この印加によって発生した過渡電流（transient current）のピーク電流（peak current）とピーク時間（peak time）を測定した。これらの測定値とＭ．Ｉｍａｉらの論文、４０頁の計算式（８）とから回転粘度の値を得た。この計算で必要な誘電率異方性の値は、この回転粘度を測定した素子を用い、下に記載した方法で求めた。 (8a) Viscosity (rotational viscosity; γ1; measured at 25 ° C .; mPa · s)
Positive dielectric anisotropy: The measurement was according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). The sample was placed in a TN device having a twist angle of 0 degree and a distance between two glass substrates (cell gap) of 5 μm. A voltage was applied to this element in steps of 0.5 V in the range of 16 V to 19.5 V. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of transient current generated by this application were measured. These measurements and M. The rotational viscosity was obtained from the paper of Imai et al., Calculation formula (8) on page 40. The value of dielectric anisotropy required for this calculation was determined by the method described below using the device for which this rotational viscosity was measured.
（８ｂ）粘度（回転粘度；γ１；２５℃で測定；ｍＰａ・ｓ）
　負の誘電率異方性：測定は、M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995) に記載された方法に従った。２枚のガラス基板の間隔（セルギャップ）が２０μｍのＶＡ素子に試料を入れた。この素子に３９ボルトから５０ボルトの範囲で１ボルト毎に段階的に電圧を印加した。０．２秒の無印加の後、ただ１つの矩形波（矩形パルス；０．２秒）と無印加（２秒）の条件で印加を繰り返した。この印加によって発生した過渡電流（transient current）のピーク電流（peak current）とピーク時間（peak time）を測定した。これらの測定値とＭ．Ｉｍａｉらの論文、４０頁の計算式（８）とから回転粘度の値を得た。この計算に必要な誘電率異方性は、下記の誘電率異方性の項で測定した値を用いた。 (8b) Viscosity (rotational viscosity; γ1; measured at 25 ° C .; mPa · s)
Negative dielectric anisotropy: Measurement was according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 20 μm. A voltage was applied to the device stepwise in steps of 1 volt in the range of 39 to 50 volts. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of transient current generated by this application were measured. These measurements and M. The rotational viscosity was obtained from the paper of Imai et al., Calculation formula (8) on page 40. The dielectric anisotropy required for this calculation was the value measured in the section of dielectric anisotropy described below.
（９ａ）誘電率異方性（Δε；２５℃で測定）
　正の誘電率異方性：２枚のガラス基板の間隔（セルギャップ）が９μｍであり、そしてツイスト角が８０度であるＴＮ素子に試料を入れた。この素子にサイン波（１０Ｖ、１ｋＨｚ）を印加し、２秒後に液晶分子の長軸方向における誘電率（ε∥）を測定した。この素子にサイン波（０．５Ｖ、１ｋＨｚ）を印加し、２秒後に液晶分子の短軸方向における誘電率（ε⊥）を測定した。誘電率異方性の値は、Δε＝ε∥－ε⊥、の式から計算した。 (9a) Dielectric anisotropy (Δε; measured at 25 ° C.)
Positive dielectric anisotropy: A sample was placed in a TN device in which the distance between two glass substrates (cell gap) is 9 μm and the twist angle is 80 degrees. Sine waves (10 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant (ε∥) in the major axis direction of liquid crystal molecules was measured. Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant (⊥) in the minor axis direction of liquid crystal molecules was measured. The value of dielectric anisotropy was calculated from the equation Δε = εε−ε⊥.
（９ｂ）誘電率異方性（Δε；２５℃で測定）
　負の誘電率異方性：誘電率異方性の値は、Δε＝ε∥－ε⊥、の式から計算した。誘電率（ε∥およびε⊥）は次のように測定した。
１）誘電率（ε∥）の測定：よく洗浄したガラス基板にオクタデシルトリエトキシシラン（０．１６ｍＬ）のエタノール（２０ｍＬ）溶液を塗布した。ガラス基板をスピンナーで回転させた後、１５０℃で１時間加熱した。２枚のガラス基板の間隔（セルギャップ）が４μｍであるＶＡ素子に試料を入れ、この素子を紫外線で硬化する接着剤で密閉した。この素子にサイン波（０．５Ｖ、１ｋＨｚ）を印加し、２秒後に液晶分子の長軸方向における誘電率（ε∥）を測定した。
２）誘電率（ε⊥）の測定：よく洗浄したガラス基板にポリイミド溶液を塗布した。このガラス基板を焼成した後、得られた配向膜にラビング処理をした。２枚のガラス基板の間隔（セルギャップ）が９μｍであり、ツイスト角が８０度であるＴＮ素子に試料を入れた。この素子にサイン波（０．５Ｖ、１ｋＨｚ）を印加し、２秒後に液晶分子の短軸方向における誘電率（ε⊥）を測定した。 (9b) Dielectric anisotropy (Δε; measured at 25 ° C.)
Negative dielectric anisotropy: The value of dielectric anisotropy was calculated from the equation of Δε = ε∥−ε⊥. The dielectric constants (ε∥ and ε⊥) were measured as follows.
1) Measurement of dielectric constant (ε∥): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a well-cleaned glass substrate. The glass substrate was rotated by a spinner and then heated at 150 ° C. for 1 hour. A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 4 μm, and this device was sealed with an adhesive cured with ultraviolet light. Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant (ε∥) in the major axis direction of liquid crystal molecules was measured.
2) Measurement of dielectric constant (ε⊥): A polyimide solution was applied to a well-cleaned glass substrate. After firing the glass substrate, the obtained alignment film was rubbed. The sample was placed in a TN device in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant (⊥) in the minor axis direction of liquid crystal molecules was measured.
（１０ａ）弾性定数（Ｋ；２５℃で測定；ｐＮ）
　正の誘電率異方性：測定にはアジレント・テクノロジー社製のＨＰ４２８４Ａ型ＬＣＲメータを用いた。２枚のガラス基板の間隔（セルギャップ）が２０μｍである水平配向素子に試料を入れた。この素子に０ボルトから２０ボルトの電荷を印加し、静電容量および印加電圧を測定した。測定した静電容量（Ｃ）と印加電圧（Ｖ）の値を「液晶デバイスハンドブック」（日刊工業新聞社）、７５頁にある式（２．９８）、式（２．１０１）を用いてフィッティングし、式（２．９９）からＫ11およびＫ33の値を得た。次に１７１頁にある式（３．１８）に、先ほど求めたＫ11およびＫ33の値を用いてＫ22を算出した。弾性定数Ｋは、このようにして求めたＫ11、Ｋ22およびＫ33の平均値で表した。 (10a) Elastic constant (K; measured at 25 ° C .; pN)
Positive dielectric anisotropy: An HP4284A LCR meter manufactured by Agilent Technologies was used for measurement. The sample was placed in a horizontal alignment device in which the distance between two glass substrates (cell gap) was 20 μm. A charge of 0 to 20 volts was applied to the device, and the capacitance and the applied voltage were measured. Fitting the measured capacitance (C) and applied voltage (V) values using the formula (2.98) and formula (2.101) on page 75 of “Liquid Crystal Device Handbook” (Nippon Kogyo Shimbun Ltd.) And the values of K 11 and K 33 were obtained from equation (2.99). Then the equation (3.18) on page 171, to calculate the K 22 using the values of K 11 and K 33 was determined previously. The elastic constant K was represented by the average value of K 11 , K 22 and K 33 thus determined.
（１０ｂ）弾性定数（Ｋ11およびＫ33；２５℃で測定；ｐＮ）
　負の誘電率異方性：測定には（株）東陽テクニカ製のＥＣ－１型弾性定数測定器を用いた。２枚のガラス基板の間隔（セルギャップ）が２０μｍである垂直配向素子に試料を入れた。この素子に２０ボルトから０ボルトの電荷を印加し、静電容量および印加電圧を測定した。静電容量（Ｃ）と印加電圧（Ｖ）の値を、「液晶デバイスハンドブック」（日刊工業新聞社）、７５頁にある式（２．９８）、式（２．１０１）を用いてフィッティングし、式（２．１００）から弾性定数の値を得た。 (10b) elastic constant (K 11 and K 33 ; measured at 25 ° C .; pN)
Negative dielectric anisotropy: For measurement, an EC-1 type elastic constant measuring device manufactured by Toyo Co., Ltd. was used. The sample was placed in a vertical alignment device in which the distance between two glass substrates (cell gap) was 20 μm. A charge of 20 volts to 0 volts was applied to the device, and the capacitance and the applied voltage were measured. The values of capacitance (C) and applied voltage (V) are fitted using the formula (2.98) and formula (2.101) shown on page 75 of “Liquid Crystal Device Handbook” (Nippon Kogyo Shimbun Ltd.) The value of the elastic constant was obtained from the equation (2.100).
（１１ａ）しきい値電圧（Ｖｔｈ；２５℃で測定；Ｖ）
　正の誘電率異方性：測定には大塚電子（株）製のＬＣＤ５１００型輝度計を用いた。光源はハロゲンランプとした。２枚のガラス基板の間隔（セルギャップ）が０．４５／Δｎ（μｍ）であり、ツイスト角が８０度であるノーマリーホワイトモード（normally white mode）のＴＮ素子に試料を入れた。この素子に印加する電圧（３２Ｈｚ、矩形波）は０Ｖから１０Ｖまで０．０２Ｖずつ段階的に増加させた。この際に、素子に垂直方向から光を照射し、素子を透過した光量を測定した。この光量が最大になったときが透過率１００％であり、この光量が最小であったときが透過率０％である電圧－透過率曲線を作成した。しきい値電圧は透過率が９０％になったときの電圧で表した。 (11a) Threshold voltage (Vth; measured at 25 ° C .; V)
Positive dielectric anisotropy: For measurement, an LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. The sample was placed in a normally white mode TN device in which the distance between two glass substrates (cell gap) is 0.45 / Δn (μm) and the twist angle is 80 degrees. The voltage (32 Hz, rectangular wave) applied to this element was gradually increased by 0.02 V from 0 V to 10 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The threshold voltage was represented by the voltage at 90% transmittance.
（１１ｂ）しきい値電圧（Ｖｔｈ；２５℃で測定；Ｖ）
　負の誘電率異方性：測定には大塚電子（株）製のＬＣＤ５１００型輝度計を用いた。光源はハロゲンランプとした。２枚のガラス基板の間隔（セルギャップ）が４μｍであり、ラビング方向がアンチパラレルであるノーマリーブラックモード（normally black mode）のＶＡ素子に試料を入れ、この素子を紫外線で硬化する接着剤を用いて密閉した。この素子に印加する電圧（６０Ｈｚ、矩形波）は０Ｖから２０Ｖまで０．０２Ｖずつ段階的に増加させた。この際に、素子に垂直方向から光を照射し、素子を透過した光量を測定した。この光量が最大になったときが透過率１００％であり、この光量が最小であったときが透過率０％である電圧－透過率曲線を作成した。しきい値電圧は透過率が１０％になったときの電圧で表した。 (11b) Threshold voltage (Vth; measured at 25 ° C .; V)
Negative dielectric anisotropy: For measurement, an LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. A sample is placed in a normally black mode VA device in which the distance between two glass substrates (cell gap) is 4 μm and the rubbing direction is antiparallel, and an adhesive for curing this device with ultraviolet light is used. Used and sealed. The voltage (60 Hz, rectangular wave) applied to this element was gradually increased by 0.02 V from 0 V to 20 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The threshold voltage was represented by the voltage at 10% transmittance.
（１２ａ）応答時間（τ；２５℃で測定；ｍｓ）
　正の誘電率異方性：測定には大塚電子（株）製のＬＣＤ５１００型輝度計を用いた。光源はハロゲンランプとした。ローパス・フィルター（Low-pass filter）は５ｋＨｚに設定した。２枚のガラス基板の間隔（セルギャップ）が５．０μｍであり、ツイスト角が８０度であるノーマリーホワイトモード（normally white mode）のＴＮ素子に試料を入れた。この素子に矩形波（６０Ｈｚ、５Ｖ、０．５秒）を印加した。この際に、素子に垂直方向から光を照射し、素子を透過した光量を測定した。この光量が最大になったときが透過率１００％であり、この光量が最小であったときが透過率０％であるとみなした。立ち上がり時間（τｒ：rise time；ミリ秒）は、透過率が９０％から１０％に変化するのに要した時間である。立ち下がり時間（τｆ：fall time；ミリ秒）は透過率１０％から９０％に変化するのに要した時間である。応答時間は、このようにして求めた立ち上がり時間と立ち下がり時間との和で表した。 (12a) Response time (τ; measured at 25 ° C; ms)
Positive dielectric anisotropy: For measurement, an LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. The low pass filter (Low-pass filter) was set to 5 kHz. The sample was placed in a normally white mode TN device in which the distance between two glass substrates (cell gap) was 5.0 μm and the twist angle was 80 degrees. A rectangular wave (60 Hz, 5 V, 0.5 seconds) was applied to this element. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. It was considered that the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The rise time (τr: millisecond) is the time taken for the transmittance to change from 90% to 10%. The fall time (τf: milliseconds) is the time taken to change from 10% transmission to 90% transmission. The response time is represented by the sum of the rise time and the fall time obtained in this manner.
（１２ｂ）応答時間（τ；２５℃で測定；ｍｓ）
　負の誘電率異方性：測定には大塚電子（株）製のＬＣＤ５１００型輝度計を用いた。光源はハロゲンランプとした。ローパス・フィルター（Low-pass filter）は５ｋＨｚに設定した。２枚のガラス基板の間隔（セルギャップ）が３．２μｍであり、ラビング方向がアンチパラレルであるノーマリーブラックモード（normally black mode）のＰＶＡ素子に試料を入れた。この素子を紫外線で硬化する接着剤を用いて密閉した。この素子にしきい値電圧を若干超える程度の電圧を１分間印加し、次に５．６Ｖの電圧を印加しながら２３．５ｍＷ／ｃｍ2の紫外線を８分間照射した。この素子に矩形波（６０Ｈｚ、１０Ｖ、０．５秒）を印加した。この際に、素子に垂直方向から光を照射し、素子を透過した光量を測定した。この光量が最大になったときが透過率１００％であり、この光量が最小であったときが透過率０％であるとみなした。応答時間は透過率９０％から１０％に変化するのに要した時間（立ち下がり時間；fall time；ミリ秒）で表した。 (12b) Response time (τ; measured at 25 ° C; ms)
Negative dielectric anisotropy: For measurement, an LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. The low pass filter (Low-pass filter) was set to 5 kHz. The sample was placed in a normally black mode PVA element in which the distance between two glass substrates (cell gap) was 3.2 μm and the rubbing direction was antiparallel. The device was sealed using an adhesive that cures with ultraviolet light. A voltage slightly higher than the threshold voltage was applied to the device for 1 minute, and then ultraviolet light of 23.5 mW / cm 2 was applied for 8 minutes while applying a voltage of 5.6 V. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to this element. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. It was considered that the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The response time is represented by the time (fall time; milliseconds) taken to change from 90% transmittance to 10% transmittance.
（１３）電圧保持率
　アイグラフィックス（株）製ブラックライト、Ｆ４０Ｔ１０／ＢＬ（ピーク波長３６９ｎｍ）を用いて紫外線を照射することによって、重合性化合物を重合させた。この素子に６０℃でパルス電圧（１Ｖで６０マイクロ秒）を印加して充電した。減衰する電圧を高速電圧計で１．６７秒のあいだ測定し、単位周期における電圧曲線と横軸との間の面積Ａを求めた。面積Ｂは減衰しなかったときの面積である。電圧保持率は面積Ｂに対する面積Ａの百分率で表した。 (13) Voltage Holding Ratio A polymerizable compound was polymerized by irradiating ultraviolet light using Blacklight, F40T10 / BL (peak wavelength 369 nm) manufactured by Eye Graphics Co., Ltd. The element was charged by applying a pulse voltage (60 microseconds at 1 V) at 60 ° C. The decaying voltage was measured with a high-speed voltmeter for 1.67 seconds, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined. The area B is the area when not attenuated. The voltage holding ratio was expressed as a percentage of the area A to the area B.
原料
　ソルミックス（登録商標）Ａ－１１は、エタノール（８５．５％）、メタノール（１３．４％）およびイソプロパノール（ＩＰＡ）（１．１％）の混合物であり、日本アルコール販売（株）から入手した。 Raw materials Solmix (registered trademark) A-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (IPA) (1.1%), and is sold by Nippon Alcohol Sales Co., Ltd. obtained.
［合成例１］
化合物（１－２－２）の合成
Figure JPOXMLDOC01-appb-C000059
 Synthesis Example 1
Synthesis of compound (1-2-2)
Figure JPOXMLDOC01-appb-C000059
第１工程
　トリフルオロメタンスルホン酸無水物（２５．０ｇ）およびジクロロメタン（８０．０ｍｌ）を反応器に入れ、０℃に冷却した。そこへ、化合物（Ｔ－１）（１０．３ｇ）およびトリエチルアミン（８．９７ｇ）のジクロロメタン（１６０ｍｌ）溶液をゆっくりと滴下した。得られた溶液をエチレングリコール（１６５ｇ）に注ぎ込み、室温で１２時間撹拌した。反応混合物を水に注ぎ込み、水層をジクロロメタンで抽出した。得られた有機層を水で洗浄し、無水硫酸マグネシウムで乾燥した。この溶液を減圧下で濃縮し、残渣をシリカゲルクロマトグラフィー（容積比、ヘプタン：酢酸エチル＝１：１）で精製して、化合物（Ｔ－２）（６．１８ｇ；４４％）を得た。 Step 1 Trifluoromethanesulfonic anhydride (25.0 g) and dichloromethane (80.0 ml) were charged to the reactor and cooled to 0 ° C. Thereto, a solution of compound (T-1) (10.3 g) and triethylamine (8.97 g) in dichloromethane (160 ml) was slowly added dropwise. The resulting solution was poured into ethylene glycol (165 g) and stirred at room temperature for 12 hours. The reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate = 1: 1) to give compound (T-2) (6.18 g; 44%).
第２工程
　化合物（Ｔ－２）（６．１８ｇ）、３，４－ジヒドロ－２Ｈ－ピラン（３．５７ｇ）、ピリジニウムｐ－トルエンスルホナート（ＰＰＴＳ）（０．９７０ｇ）、およびジクロロメタン（６０．０ｍｌ）を反応器に入れ、室温で１２時間攪拌した。反応混合物を水に注ぎ込み、水層をジクロロメタンで抽出した。得られた有機層を水で洗浄し、無水硫酸マグネシウムで乾燥した。この溶液を減圧下で濃縮し、残渣をシリカゲルクロマトグラフィー（容積比、ヘプタン：酢酸エチル＝４：１）で精製して、化合物（Ｔ－３）（９．１５ｇ；９７％）を得た。なお、ＴＨＰはテトラヒドロピラニル基を示す。 Step 2 Compound (T-2) (6.18 g), 3,4-dihydro-2H-pyran (3.57 g), pyridinium p-toluenesulfonate (PPTS) (0.970 g), and dichloromethane (60. 6). 0 ml) was charged into the reactor and stirred at room temperature for 12 hours. The reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate = 4: 1) to give compound (T-3) (9.15 g; 97%). In addition, THP shows a tetrahydropyranyl group.
第３工程
　化合物（Ｔ－３）（９．１５ｇ）、ＴＨＦ（４５．０ｍｌ）、および水（４５．０ｍｌ）を反応器に入れ、０℃に冷却した。そこへ水酸化リチウム一水和物（３．１４ｇ）を加え、室温に戻しつつ７時間攪拌した。反応混合物を水に注ぎ込み、６Ｎ塩酸（１５ｍｌ）をゆっくりと加え酸性にした後、水層を酢酸エチルで抽出した。得られた有機層を水で洗浄し、無水硫酸マグネシウムで乾燥した。この溶液を減圧下で濃縮して化合物（Ｔ－４）（５．０７ｇ；５９％）を得た。 Step 3 Compound (T-3) (9.15 g), THF (45.0 ml), and water (45.0 ml) were charged into a reactor and cooled to 0 ° C. Lithium hydroxide monohydrate (3.14 g) was added there, and it stirred for 7 hours, returning to room temperature. The reaction mixture was poured into water, 6N hydrochloric acid (15 ml) was slowly added to acidify, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to give compound (T-4) (5.07 g; 59%).
第４工程
　国際公開第２０１４／０９７９５２号に記載された方法に従って合成した化合物（Ｔ－５）（１２４ｇ）、トリエチルアミン（５２．４ｇ）、およびＴＨＦ（３１００ｍｌ）を反応器に入れ０℃に冷却した。そこへ、化合物（Ｔ－６）（５０．０ｇ）をゆっくりと滴下し、５０℃で３時間撹拌した。反応混合物を食塩水に注ぎ込み、水層をｔ－ブチルメチルエーテルで抽出した。得られた有機層を水および食塩水で順次洗浄し、無水硫酸マグネシウムで乾燥した。この溶液を減圧下で濃縮し、残渣をシリカゲルクロマトグラフィー（容積比、ヘプタン：酢酸エチル＝４：１）で精製して、化合物（Ｔ－７）（５５．６ｇ；３７％）を得た。 Step 4 Compound (T-5) (124 g), triethylamine (52.4 g), and THF (3100 ml) synthesized according to the method described in WO 2014/097952 were charged into a reactor and cooled to 0 ° C. . The compound (T-6) (50.0 g) was slowly dropped there, and stirred at 50 ° C. for 3 hours. The reaction mixture was poured into brine and the aqueous layer was extracted with t-butyl methyl ether. The obtained organic layer was washed successively with water and brine, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate = 4: 1) to give compound (T-7) (55.6 g; 37%).
第５工程
　化合物（Ｔ－４）（３．６４ｇ）、化合物（Ｔ－７）（５．００ｇ）、ＤＭＡＰ（０．８０７ｇ）、およびジクロロメタン（７５．０ｍｌ）を反応器に入れ、０℃に冷却した。そこへＤＣＣ（４．０９ｇ）のジクロロメタン（２５．０ｍｌ）溶液をゆっくりと滴下し、室温に戻しつつ１２時間攪拌した。不溶物を濾別した後、反応混合物を水に注ぎ込み、水層をジクロロメタンで抽出した。得られた有機層を水で洗浄し、無水硫酸マグネシウムで乾燥した。この溶液を減圧下で濃縮し、残渣をシリカゲルクロマトグラフィー（容積比、ヘプタン：酢酸エチル＝５：１）で精製して、化合物（Ｔ－８）（７．３５ｇ；９４％）を得た。 Step 5 The compound (T-4) (3.64 g), the compound (T-7) (5.00 g), DMAP (0.807 g), and dichloromethane (75.0 ml) were charged into a reactor, and the mixture was cooled to 0 ° C. It cooled. The dichloromethane (25.0 ml) solution of DCC (4.09g) was dripped slowly there, and it stirred for 12 hours, returning to room temperature. After filtering off insolubles, the reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate = 5: 1) to give compound (T-8) (7.35 g; 94%).
第６工程
　化合物（Ｔ－８）（７．３５ｇ）、ＰＰＴＳ（１．５６ｇ）、ＴＨＦ（３７．０ｍｌ）、およびメタノール（３７．０ｍｌ）を反応器に入れ、５０℃で４時間攪拌した。反応混合物を水に注ぎ込み、水層を酢酸エチルで抽出した。得られた有機層を水で洗浄し、無水硫酸マグネシウムで乾燥した。この溶液を減圧下で濃縮し、残渣をシリカゲルクロマトグラフィー（容積比、トルエン：酢酸エチル＝２：１）で精製した。さらにヘプタンからの再結晶により精製して、化合物（１－２－２）（３．５４ｇ；５６％）を得た。 Step 6 Compound (T-8) (7.35 g), PPTS (1.56 g), THF (37.0 ml), and methanol (37.0 ml) were charged into a reactor, and stirred at 50 ° C. for 4 hours. The reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 2: 1). The residue was further purified by recrystallization from heptane to give compound (1-2-2) (3.54 g; 56%).
　得られた化合物（１－２－２）のＮＭＲ分析値は以下の通りである。
　1Ｈ－ＮＭＲ：化学シフトδ（ｐｐｍ；ＣＤＣｌ3）：６．３０（ｓ，１Ｈ）、６．０９（ｓ，１Ｈ）、５．８８（ｄ，Ｊ＝１．２Ｈｚ，１Ｈ）、５．５７（ｓ，１Ｈ），４．３５－４．２６（ｍ，２Ｈ）、４．２４（ｓ，２Ｈ）、４．２１－４．１４（ｍ，２Ｈ）、３．７８－３．７３（ｍ，２Ｈ）、３．６２（ｔ，Ｊ＝４．７Ｈｚ，２Ｈ）、２．２７（ｔ，Ｊ＝６．３Ｈｚ，１Ｈ）、１．９７－１．９０（ｍ，４Ｈ）、１．８５－１．６４（ｍ，８Ｈ）、１．４８－１．３８（ｍ，１Ｈ）、１．３４－１．１８（ｍ，６Ｈ）、１．１８－０．７８（ｍ，１６Ｈ）． The NMR analysis values of the obtained compound (1-2-2) are as follows.
1 H-NMR: chemical shift δ (ppm; CDCl 3 ): 6.30 (s, 1 H), 6.09 (s, 1 H), 5.88 (d, J = 1.2 Hz, 1 H); 57 (s, 1 H), 4.35-4. 26 (m, 2 H), 4. 24 (s, 2 H), 4.2 1-4. 14 (m, 2 H), 3.78-3. 73 ( m, 2H), 3.62 (t, J = 4.7 Hz, 2 H), 2.27 (t, J = 6.3 Hz, 1 H), 1.97-1.90 (m, 4 H), 85-1.64 (m, 8H), 1.48-1.38 (m, 1H), 1.34-1.18 (m, 6H), 1.18-0.78 (m, 16H).
［合成例２］
化合物（１－２－６）の合成
Figure JPOXMLDOC01-appb-C000060
 Synthesis Example 2
Synthesis of compound (1-2-6)
Figure JPOXMLDOC01-appb-C000060
第１工程
　化合物（Ｔ－９）（３０．０ｇ）、化合物（Ｔ－１０）（２８．２ｇ）、およびトルエン（９０．０ｍｌ）を反応器に入れ、０℃に冷却した。そこへナトリウムエトキシド（２０重量％；エタノール溶液；４２．８ｇ）をゆっくりと加え、０℃で１時間撹拌した。反応混合物を水に注ぎ込み、水層をトルエンで抽出した。得られた有機層を食塩水で洗浄し、無水硫酸マグネシウムで乾燥した。この溶液を減圧下で濃縮し、残渣をシリカゲルクロマトグラフィー（容積比、ヘプタン：酢酸エチル＝９：１）で精製して、化合物（Ｔ－１１）（３６．５ｇ；９５％）を得た。 Step 1 Compound (T-9) (30.0 g), Compound (T-10) (28.2 g), and toluene (90.0 ml) were placed in a reactor and cooled to 0 ° C. Sodium ethoxide (20% by weight; ethanol solution; 42.8 g) was slowly added thereto, and stirred at 0 ° C. for 1 hour. The reaction mixture was poured into water and the aqueous layer was extracted with toluene. The resulting organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate = 9: 1) to give compound (T-11) (36.5 g; 95%).
第２工程
　化合物（Ｔ－１１）（３６．５ｇ）、トルエン（１９０ｍｌ）、ＩＰＡ（１９０ｍｌ）およびパラジウムカーボン触媒（５％Ｐｄ／ＣのＰＨタイプ；川研ファインケミカル（株）製；０．２４２ｇ）を反応器に入れ、水素雰囲気下で１２時間攪拌した。不溶物を濾別した後、反応混合物を水に注ぎ込み、水層をトルエンで抽出した。得られた有機層を水で洗浄し、無水硫酸マグネシウムで乾燥した。この溶液を減圧下で濃縮し、残渣をシリカゲルクロマトグラフィー（容積比、ヘプタン：酢酸エチル＝９：１）で精製して、化合物（Ｔ－１２）（３４．８ｇ；９５％）を得た。 Second step Compound (T-11) (36.5 g), toluene (190 ml), IPA (190 ml) and palladium carbon catalyst (PH type of 5% Pd / C; manufactured by Kawaken Fine Chemical Co., Ltd .; 0.242 g) Was placed in a reactor and stirred for 12 hours under a hydrogen atmosphere. After filtering off insolubles, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate = 9: 1) to give compound (T-12) (34.8 g; 95%).
第３工程
　水素化リチウムアルミニウム（２．４６ｇ）およびＴＨＦ（２００ｍｌ）を反応器に入れ、０℃に冷却した。そこへ、化合物（Ｔ－１２）（３４．８ｇ）のＴＨＦ（１５０ｍｌ）溶液をゆっくりと加え、室温に戻しつつ３時間攪拌した。反応混合物を水に注ぎ込み、不溶物を濾別した後、水層を酢酸エチルで抽出した。得られた有機層を水で洗浄し、無水硫酸マグネシウムで乾燥した。この溶液を減圧下で濃縮し、残渣をヘプタンからの再結晶により精製して、化合物（Ｔ－１３）（１８．３ｇ；６１％）を得た。 Step 3 Lithium aluminum hydride (2.46 g) and THF (200 ml) were charged to the reactor and cooled to 0 ° C. A solution of compound (T-12) (34.8 g) in THF (150 ml) was slowly added thereto, and the mixture was stirred for 3 hours while returning to room temperature. The reaction mixture was poured into water, insolubles were filtered off, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by recrystallization from heptane to give compound (T-13) (18.3 g; 61%).
第４工程
　化合物（Ｔ－１３）（１８．３ｇ）、塩化ｐ－トルエンスルホニル（ＴｓＣｌ）（１３．７ｇ）、Ｎ，Ｎ－ジメチルアミノピリジン（ＤＭＡＰ）（９．５８ｇ）、およびジクロロメタン（２７５ｍｌ）を反応器に入れ、室温で１２時間攪拌した。反応混合物を水に注ぎ込み、水層をジクロロメタンで抽出した。得られた有機層を水および食塩水で順次洗浄し、無水硫酸マグネシウムで乾燥した。この溶液を減圧下で濃縮し、残渣をシリカゲルクロマトグラフィー（容積比、ヘプタン：酢酸エチル＝９：１）で精製した。さらにヘプタンからの再結晶により精製して、化合物（Ｔ－１４）（２３．０ｇ；８１％）を得た。なお、Ｔｓはトシル基を示す。 Step 4 Compound (T-13) (18.3 g), p-toluenesulfonyl chloride (TsCl) (13.7 g), N, N-dimethylaminopyridine (DMAP) (9.58 g), and dichloromethane (275 ml) Was placed in a reactor and stirred at room temperature for 12 hours. The reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed successively with water and brine, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate = 9: 1). The residue was further purified by recrystallization from heptane to give compound (T-14) (23.0 g; 81%). In addition, Ts shows a tosyl group.
第５工程
　化合物（Ｔ－１４）（１９．０ｇ）、ＴＨＦ（１９０ｍｌ）、およびＤＭＦ（１９０ｍｌ）を反応器に入れ、０℃に冷却した。そこへ水素化ナトリウム（３．８１ｇ）をゆっくりと加え、室温に戻しつつ１時間攪拌した。そこへ化合物（Ｔ－１０）（１４．７ｇ）およびヨウ化ナトリウム（１．３２ｇ）を加え、８０℃で２時間撹拌した。反応混合物を水に注ぎ込み、水層を酢酸エチルで抽出した。得られた有機層を食塩水で洗浄し、無水硫酸マグネシウムで乾燥した。この溶液を減圧下で濃縮し、残渣をシリカゲルクロマトグラフィー（容積比、ヘプタン：酢酸エチル＝９：１）で精製して、化合物（Ｔ－１５）（１３．１ｇ；７１％）を得た。 Step 5 Compound (T-14) (19.0 g), THF (190 ml), and DMF (190 ml) were charged into a reactor and cooled to 0 ° C. Sodium hydride (3.81 g) was slowly added there, and it stirred for 1 hour, returning to room temperature. The compound (T-10) (14.7 g) and sodium iodide (1.32 g) were added there, and it stirred at 80 degreeC for 2 hours. The reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The resulting organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate = 9: 1) to give compound (T-15) (13.1 g; 71%).
第６工程
　水素化ホウ素ナトリウム（４．６９ｇ）、塩化リチウム（０．２６３ｇ）、およびエタノール（６５．０ｍｌ）を反応器に入れ、０℃に冷却した。そこへ、化合物（Ｔ－１５）（１３．１ｇ）のＴＨＦ（１３０ｍｌ）溶液をゆっくりと加え、６０℃で３時間攪拌した。反応混合物を１Ｎ塩酸（４００ｍｌ）に注ぎ込み、析出した固体を濾取した。得られた固体を、水および酢酸エチルで順次洗浄して、化合物（Ｔ－１６）（９．３７ｇ；８９％）を得た。 Sixth Step Sodium borohydride (4.69 g), lithium chloride (0.263 g), and ethanol (65.0 ml) were charged into the reactor and cooled to 0 ° C. To this, a solution of compound (T-15) (13.1 g) in THF (130 ml) was slowly added, and the mixture was stirred at 60 ° C. for 3 hours. The reaction mixture was poured into 1N hydrochloric acid (400 ml), and the precipitated solid was collected by filtration. The obtained solid was washed successively with water and ethyl acetate to give compound (T-16) (9.37 g; 89%).
第７工程
　化合物（Ｔ－１６）（４５．０ｇ）、炭酸カリウム（２５．３ｇ）、およびＴＨＦ（１１２０ｍｌ）を反応器に入れ、３０℃に加熱した。そこへ、化合物（Ｔ－１７）（２４．３ｍｌ）をゆっくりと加え、５０℃で１０時間攪拌した。反応混合物を水に注ぎ込み、水層を酢酸エチルで抽出した。得られた有機層を食塩水で洗浄し、無水硫酸マグネシウムで乾燥した。この溶液を減圧下で濃縮し、残渣をシリカゲルクロマトグラフィー（容積比、ヘプタン：酢酸エチル＝４：１）で精製して、化合物（Ｔ－１８）（２２．９ｇ；４２％）を得た。 Step 7 Compound (T-16) (45.0 g), potassium carbonate (25.3 g), and THF (1120 ml) were placed in a reactor and heated to 30 ° C. The compound (T-17) (24.3 ml) was slowly added thereto, and the mixture was stirred at 50 ° C. for 10 hours. The reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The resulting organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate = 4: 1) to give compound (T-18) (22.9 g; 42%).
第８工程
　化合物（Ｔ－１８）（５．００ｇ）を原料として用い、合成例１の第５工程と同様の手法により、化合物（Ｔ－１９）（６．６７ｇ；８８％）を得た。 Step 8 Compound (T-19) (6.67 g; 88%) was obtained in the same manner as in the fifth step of Synthesis Example 1 using compound (T-18) (5.00 g) as a starting material.
第９工程
　化合物（Ｔ－１９）（６．６７ｇ）を原料として用い、合成例１の第６工程と同様の手法により、化合物（１－２－６）（４．３２ｇ；７５％）を得た。 Step 9 Using compound (T-19) (6.67 g) as a starting material, and according to the same method as step 6 of Synthesis Example 1, compound (1-2-6) (4.32 g; 75%) was obtained The
　得られた化合物（１－２－６）のＮＭＲ分析値は以下の通りである。
　1Ｈ－ＮＭＲ：化学シフトδ（ｐｐｍ；ＣＤＣｌ3）：６．３１（ｄ，Ｊ＝０．８Ｈｚ，１Ｈ）、６．１０（ｓ，１Ｈ）、５．８９（ｄ，Ｊ＝１．５Ｈｚ，１Ｈ）、５．５７（ｔ，Ｊ＝１．７Ｈｚ，１Ｈ），４．２７－４．０９（ｍ，６Ｈ）、３．７９－３．７３（ｍ，２Ｈ）、３．６２（ｔ，Ｊ＝４．８Ｈｚ，２Ｈ）、２．２７（ｔ，Ｊ＝６．２Ｈｚ，１Ｈ）、２．１２－２．０３（ｍ，１Ｈ）、１．９４（ｓ，３Ｈ）、１．７８－１．６５（ｍ，８Ｈ）、１．４６－１．３８（ｍ，２Ｈ）、１．３４－１．１８（ｍ，８Ｈ）、１．１８－１．０５（ｍ，４Ｈ）、１．０４－０．９０（ｍ，６Ｈ）、０．９０－０．７８（ｍ，７Ｈ）． The NMR analysis values of the obtained compound (1-2-6) are as follows.
1 H-NMR: chemical shift δ (ppm; CDCl 3 ): 6.31 (d, J = 0.8 Hz, 1 H), 6.10 (s, 1 H), 5.89 (d, J = 1.5 Hz) , 1H), 5.57 (t, J = 1.7 Hz, 1 H), 4.27-4.09 (m, 6 H), 3.79-3. 73 (m, 2 H), 3.62 (t) , J = 4.8 Hz, 2 H), 2.27 (t, J = 6.2 Hz, 1 H), 2.12-2.03 (m, 1 H), 1.94 (s, 3 H), 1.78 -1.65 (m, 8H), 1.46-1.38 (m, 2H), 1.34-1.18 (m, 8H), 1.18-1.05 (m, 4H), 1 .04-0. 90 (m, 6H), 0.90 to 0.78 (m, 7H).
［合成例３］
化合物（１－３－４）の合成
Figure JPOXMLDOC01-appb-C000061
 Synthesis Example 3
Synthesis of compound (1-3-4)
Figure JPOXMLDOC01-appb-C000061
第１工程
　化合物（Ｔ－２０）（２００ｇ）およびＴＨＦ（２０００ｍｌ）を反応器に入れ、０℃に冷却した。そこへ塩化ｉ－プロピルマグネシウム・塩化リチウム錯体（１．３０Ｍ；ｎ－ＴＨＦ溶液；４２１ｍｌ）をゆっくりと滴下し、０℃で６０分間撹拌した。そこへＤＭＦ（４２．４ｍｌ）をゆっくりと滴下し、室温に戻しつつ３時間攪拌した。反応混合物を水に注ぎ込み、水層をトルエンで抽出した。得られた有機層を水で洗浄し、無水硫酸マグネシウムで乾燥した。この溶液を減圧下で濃縮し、残渣をシリカゲルクロマトグラフィー（容積比、ヘプタン：トルエン＝１：１）で精製して、化合物（Ｔ－２１）（１４９ｇ；９６％）を得た。 Step 1 Compound (T-20) (200 g) and THF (2000 ml) were placed in a reactor and cooled to 0 ° C. Thereto, i-propylmagnesium chloride-lithium chloride complex (1.30 M; n-THF solution; 421 ml) was slowly added dropwise, and stirred at 0 ° C. for 60 minutes. The DMF (42.4 ml) was dripped slowly there, and it stirred for 3 hours, returning to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: toluene = 1: 1) to give compound (T-21) (149 g; 96%).
第２工程
　水素化ホウ素ナトリウム（１６．６ｇ）およびメタノール（７４５ｍｌ）を反応器に入れ、０℃に冷却した。そこへ、化合物（Ｔ－２１）（１４９ｇ）のＴＨＦ（７４５ｍｌ）溶液をゆっくりと加え、室温に戻しつつ３時間攪拌した。反応混合物を飽和塩化アンモニウム水溶液に注ぎ込み、水層を酢酸エチルで抽出した。得られた有機層を水で洗浄し、無水硫酸マグネシウムで乾燥した。この溶液を減圧下で濃縮し、残渣をヘプタンからの再結晶により精製して、化合物（Ｔ－２２）（１３７ｇ；９１％）を得た。 Second Step Sodium borohydride (16.6 g) and methanol (745 ml) were charged to the reactor and cooled to 0 ° C. Thereto was slowly added a solution of compound (T-21) (149 g) in THF (745 ml), and the mixture was stirred for 3 hours while returning to room temperature. The reaction mixture was poured into saturated aqueous ammonium chloride solution, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by recrystallization from heptane to give compound (T-22) (137 g; 91%).
第３工程
　化合物（Ｔ－２２）（１３７ｇ）、トリフェニルホスフィン（１１５ｇ）、およびジクロロメタン（８５０ｍｌ）を反応器に入れ、０℃に冷却した。そこへ、四臭化炭素（１４５ｇ）のＴＨＦ（５００ｍｌ）溶液をゆっくりと加え、室温に戻しつつ１２時間攪拌した。反応混合物を水に注ぎ込み、水層をジクロロメタンで抽出した。得られた有機層を水で洗浄し、無水硫酸マグネシウムで乾燥した。この溶液を減圧下で濃縮し、残渣をシリカゲルクロマトグラフィー（ヘプタン）で精製して、化合物（Ｔ－２３）（１３２ｇ；８２％）を得た。 Step 3 Compound (T-22) (137 g), triphenylphosphine (115 g), and dichloromethane (850 ml) were charged into a reactor, and cooled to 0 ° C. Thereto, a solution of carbon tetrabromide (145 g) in THF (500 ml) was slowly added, and stirred for 12 hours while returning to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (heptane) to give compound (T-23) (132 g; 82%).
第４工程
　化合物（Ｔ－２３）（１３２ｇ）、トリフェニルホスフィン（９４．１ｇ）、およびトルエン（２５００ｍｌ）を反応器に入れ、１１０℃で１５時間、加熱還流を行った。反応混合物を０℃に冷却し、析出した結晶を濾取することによって、化合物（Ｔ－２４）（１７８ｇ；８２％）を得た。 Step 4 Compound (T-23) (132 g), triphenylphosphine (94.1 g), and toluene (2500 ml) were placed in a reactor, and heating to reflux was carried out at 110 ° C. for 15 hours. The reaction mixture was cooled to 0 ° C., and the precipitated crystals were collected by filtration to give compound (T-24) (178 g; 82%).
第５工程
　化合物（Ｔ－２４）（１７８ｇ）およびＴＨＦ（９００ｍｌ）を反応器に入れて、－３０℃に冷却した。そこへカリウムｔ－ブトキシド（２９．９ｇ）を加え、－３０℃で１時間撹拌した。次に化合物（Ｔ－２５）（３８．４ｇ）のＴＨＦ（９００ｍｌ）溶液をゆっくりと滴下し、室温に戻しつつ１２時間攪拌した。反応混合物を水へ注ぎ込み、水層をトルエンで抽出した。得られた有機層を水で洗浄し、無水硫酸マグネシウムで乾燥した。この溶液を減圧下で濃縮し、残渣をシリカゲルカラムクロマトグラフィー（トルエン）で精製して、Ｚ体およびＥ体の混合物である化合物（Ｔ－２６）（７８．１ｇ、収率６５％、（Ｚ体：Ｅ体＝９５：５））を得た。 Step 5 Compound (T-24) (178 g) and THF (900 ml) were placed in a reactor and cooled to -30.degree. To this was added potassium t-butoxide (29.9 g), and the mixture was stirred at -30 ° C for 1 hour. Next, a solution of compound (T-25) (38.4 g) in THF (900 ml) was slowly added dropwise, and stirred for 12 hours while returning to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution is concentrated under reduced pressure, and the residue is purified by silica gel column chromatography (toluene) to obtain a mixture of compound Z and compound E (T-26) (78.1 g, yield 65%, (Z Body: E body = 95: 5)) was obtained.
第６工程
　化合物（Ｔ－２６）（７８．１ｇ）を原料として用い、合成例２の第２工程と同様の手法により、化合物（Ｔ－２７）（７８．０ｇ；９９％）を得た。 Step 6 Using compound (T-26) (78.1 g) as a starting material, compound (T-27) (78.0 g; 99%) was obtained in the same manner as in the second step of Synthesis Example 2.
第７工程
　化合物（Ｔ－２７）（７４．６ｇ）、ｐ－トルエンスルホン酸一水和物（ＰＴＳＡ）、トルエン（８００ｍｌ）、およびメタノール（８００ｍｌ）を反応器に入れて、室温で１２時間攪拌した。反応混合物を飽和炭酸水素ナトリウム水溶液へ注ぎ込み、水層を酢酸エチルで抽出した。得られた有機層を水で洗浄し、無水硫酸マグネシウムで乾燥した。この溶液を減圧下で濃縮して化合物（Ｔ－２８）（５９．０ｇ、収率８７％）を得た。 Step 7 The compound (T-27) (74.6 g), p-toluenesulfonic acid monohydrate (PTSA), toluene (800 ml) and methanol (800 ml) were placed in a reactor and stirred at room temperature for 12 hours did. The reaction mixture was poured into saturated aqueous sodium hydrogen carbonate solution, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to give compound (T-28) (59.0 g, yield 87%).
第８工程
　化合物（Ｔ－２８）（１２．９ｇ）を原料として用い、合成例２の第７工程と同様の手法により、化合物（Ｔ－２９）（６．４４ｇ；４３％）を得た。 Step 8 Compound (T-29) (6.44 g; 43%) was obtained in the same manner as in the seventh step of Synthesis Example 2 using compound (T-28) (12.9 g) as a starting material.
第９工程
　化合物（Ｔ－２９）（２２．０ｇ）を原料として用い、合成例１の第５工程と同様の手法により、化合物（Ｔ－３０）（２４．６ｇ；７８％）を得た。 Step 9 Using compound (T-29) (22.0 g) as a starting material, compound (T-30) (24.6 g; 78%) was obtained in the same manner as in the fifth step of Synthesis Example 1.
第１０工程
　化合物（Ｔ－３０）（２４．６ｇ）を原料として用い、合成例１の第６工程と同様の手法により、化合物（１－３－４）（１９．５ｇ；９０％）を得た。 Step 10: Compound (1-3-4) (19.5 g; 90%) was obtained by the same method as in Step 6 of Synthesis Example 1 using compound (T-30) (24.6 g) as a starting material. The
　得られた化合物（１－３－４）のＮＭＲ分析値は以下の通りである。
　1Ｈ－ＮＭＲ：化学シフトδ（ｐｐｍ；ＣＤＣｌ3）：７．１７－７．０９（ｍ，４Ｈ）、６．３３（ｄ，Ｊ＝０．９Ｈｚ，１Ｈ）、６．１３（ｓ，１Ｈ）、５．９１（ｄ，Ｊ＝１．３Ｈｚ，１Ｈ）、５．６０（ｔ，Ｊ＝１．３Ｈｚ，１Ｈ），４．３１－４．１９（ｍ，６Ｈ）、３．８１－３．７５（ｍ，２Ｈ）、３．６４（ｔ，Ｊ＝４．７Ｈｚ，２Ｈ）、２．７０（ｔ，Ｊ＝７．９Ｈｚ，２Ｈ）、２．４４（ｔｔ，Ｊ＝１２．１Ｈｚ，Ｊ＝３．３Ｈｚ，１Ｈ）、２．２５（ｔ，Ｊ＝６．３Ｈｚ，１Ｈ）、２．２３－２．１５（ｍ，１Ｈ）、１．９９－１．７２（ｍ，１３Ｈ）、１．４９－１．３８（ｍ，２Ｈ）、１．３８－０．９７（ｍ，１５Ｈ）、０．９５－０．８３（ｍ，５Ｈ）． The NMR analysis values of the obtained compound (1-3-4) are as follows.
1 H-NMR: chemical shift δ (ppm; CDCl 3 ): 7.17-7.09 (m, 4 H), 6.33 (d, J = 0.9 Hz, 1 H), 6.13 (s, 1 H) ), 5.91 (d, J = 1.3 Hz, 1 H), 5.60 (t, J = 1.3 Hz, 1 H), 4.31-4.19 (m, 6 H), 3.81-3 .75 (m, 2H), 3.64 (t, J = 4.7 Hz, 2 H), 2.70 (t, J = 7.9 Hz, 2 H), 2.44 (tt, J = 12.1 Hz, J = 3.3 Hz, 1 H), 2. 25 (t, J = 6.3 Hz, 1 H), 2.23-2.15 (m, 1 H), 1.99-1.72 (m, 13 H), 1.49-1.38 (m, 2H), 1.38-0.97 (m, 15H), 0.95-0.83 (m, 5H).
［合成例４］
化合物（１－２－１６）の合成
Figure JPOXMLDOC01-appb-C000062
 Synthesis Example 4
Synthesis of compound (1-2-16)
Figure JPOXMLDOC01-appb-C000062
第１工程
　化合物（Ｔ－１）（１４．６ｇ）を原料として用い、エチレングリコールの代わりにジエチレングリコール（４００ｇ）を用いて、合成例１の第１工程と同様の手法により、化合物（Ｔ－３１）（１３．９ｇ；５４％）を得た。 First Step Using a compound (T-1) (14.6 g) as a raw material and diethylene glycol (400 g) instead of ethylene glycol, a compound (T-31) was prepared by the same procedure as in the first step of Synthesis Example 1. ) (13.9 g; 54%) were obtained.
第２工程
　化合物（Ｔ－３１）（１３．９ｇ）を原料として用い、合成例１の第２工程と同様の手法により、化合物（Ｔ－３２）（１９．２ｇ；９８％）を得た。 Second step: Compound (T-32) (19.2 g; 98%) was obtained in the same manner as in the second step of Synthesis Example 1 using compound (T-31) (13.9 g) as a starting material.
第３工程
　化合物（Ｔ－３２）（１９．２ｇ）を原料として用い、合成例１の第３工程と同様の手法により、化合物（Ｔ－３３）（９．７５ｇ；５４％）を得た。 Step 3 Compound (T-33) (9.75 g; 54%) was obtained in the same manner as in the third step of Synthesis Example 1 using compound (T-32) (19.2 g) as a starting material.
第４工程
　化合物（Ｔ－１８）（５．００ｇ）および化合物（Ｔ－３３）（４．７２ｇ）を原料として用い、合成例１の第５工程と同様の手法により、化合物（Ｔ－３４）（７．３２ｇ；９０％）を得た。 Step 4 Using compound (T-18) (5.00 g) and compound (T-33) (4.72 g) as starting materials, compound (T-34) in the same manner as in the fifth step of Synthesis Example 1. Obtained (7.32 g; 90%).
第５工程
　化合物（Ｔ－３４）（７．３２ｇ）を原料として用い、合成例１の第６工程と同様の手法により、化合物（１－２－１６）（４．５６ｇ；７１％）を得た。 Step 5 Using compound (T-34) (7.32 g) as a starting material, and according to a procedure similar to the sixth step of Synthesis Example 1, compound (1-2-16) (4.56 g; 71%) is obtained The
　得られた化合物（１－２－１６）のＮＭＲ分析値は以下の通りである。
　1Ｈ－ＮＭＲ：化学シフトδ（ｐｐｍ；ＣＤＣｌ3）：６．３１（ｄ，Ｊ＝０．８Ｈｚ，１Ｈ）、６．１０（ｓ，１Ｈ）、５．９１（ｄ，Ｊ＝１．４Ｈｚ，１Ｈ）、５．５７（ｔ，Ｊ＝１．７Ｈｚ，１Ｈ），４．２７－４．０９（ｍ，６Ｈ）、３．７７－３．６５（ｍ，６Ｈ）、３．６２（ｔ，Ｊ＝４．３Ｈｚ，２Ｈ）、２．３６（ｔ，Ｊ＝６．３Ｈｚ，１Ｈ）、２．１２－２．０３（ｍ，１Ｈ）、１．９４（ｓ，３Ｈ）、１．７８－１．６５（ｍ，８Ｈ）、１．４６－１．３８（ｍ，２Ｈ）、１．３４－１．１８（ｍ，８Ｈ）、１．１８－１．０５（ｍ，４Ｈ）、１．０４－０．７８（ｍ，１３Ｈ）． The NMR analysis values of the obtained compound (1-2-16) are as follows.
1 H-NMR: chemical shift δ (ppm; CDCl 3 ): 6.31 (d, J = 0.8 Hz, 1 H), 6.10 (s, 1 H), 5.91 (d, J = 1.4 Hz) , 1H), 5.57 (t, J = 1.7 Hz, 1 H), 4.27-4.09 (m, 6 H), 3.77-3. 65 (m, 6 H), 3.62 (t) , J = 4.3 Hz, 2 H), 2.36 (t, J = 6.3 Hz, 1 H), 2.12-2.03 (m, 1 H), 1.94 (s, 3 H), 1.78 -1.65 (m, 8H), 1.46-1.38 (m, 2H), 1.34-1.18 (m, 8H), 1.18-1.05 (m, 4H), 1 .04-0.78 (m, 13H).
［合成例５］
化合物（１－２－１７）の合成
Figure JPOXMLDOC01-appb-C000063
 Synthesis Example 5
Synthesis of compound (1-2-17)
Figure JPOXMLDOC01-appb-C000063
第１工程
　化合物（Ｔ－１）（１０．３ｇ）を原料として用い、エチレングリコールの代わりに１，６－ヘキサンジオール（３１４ｇ）を用いて、合成例１の第１工程と同様の手法により、化合物（Ｔ－３５）（１１．３ｇ；５９％）を得た。 First step: Compound (T-1) (10.3 g) was used as a raw material, and 1,6-hexanediol (314 g) was used instead of ethylene glycol, in the same manner as in the first step of Synthesis Example 1, Compound (T-35) (11.3 g; 59%) was obtained.
第２工程
　化合物（Ｔ－３５）（１１．３ｇ）を原料として用い、合成例１の第２工程と同様の手法により、化合物（Ｔ－３６）（１５．０ｇ；９６％）を得た。 Second step: Compound (T-36) (15.0 g; 96%) was obtained in the same manner as in the second step of Synthesis Example 1 using compound (T-35) (11.3 g) as a starting material.
第３工程
　化合物（Ｔ－３６）（１５．０ｇ）を原料として用い、合成例１の第３工程と同様の手法により、化合物（Ｔ－３７）（１３．０ｇ；９１％）を得た。 Step 3 Compound (T-37) (13.0 g; 91%) was obtained in the same manner as in the third step of Synthesis Example 1 using compound (T-36) (15.0 g) as a starting material.
第４工程
　化合物（Ｔ－１８）（５．００ｇ）および化合物（Ｔ－３７）（４．２３ｇ）を原料として用い、合成例１の第５工程と同様の手法により、化合物（Ｔ－３８）（６．８４ｇ；８２％）を得た。 Step 4 Using the compound (T-18) (5.00 g) and the compound (T-37) (4.23 g) as starting materials, the compound (T-38) is prepared in the same manner as in the fifth step of Synthesis Example 1. (6.84 g; 82%) were obtained.
第５工程
　化合物（Ｔ－３８）（６．８４ｇ）を原料として用い、合成例１の第６工程と同様の手法により、化合物（１－２－１７）（２．３３ｇ；３９％）を得た。 Step 5 Using compound (T-38) (6.84 g) as a starting material, and according to a method similar to the sixth step of Synthesis Example 1, compound (1-2-17) (2.33 g; 39%) is obtained The
　得られた化合物（１－２－１７）のＮＭＲ分析値は以下の通りである。
　1Ｈ－ＮＭＲ：化学シフトδ（ｐｐｍ；ＣＤＣｌ3）：６．２８（ｓ，１Ｈ）、６．１０（ｓ，１Ｈ）、５．８８（ｄ，Ｊ＝１．３Ｈｚ，１Ｈ）、５．５７（ｓ，１Ｈ），４．２４－４．０８（ｍ，６Ｈ）、３．６９－３．６１（ｍ，２Ｈ）、３．５２－３．４５（ｍ，２Ｈ）、２．０６（ｔ，Ｊ＝６．４Ｈｚ，１Ｈ）、１．９４（ｓ，３Ｈ）、１．７８－１．５３（ｍ，１２Ｈ）、１．４６－１．３５（ｍ，６Ｈ）、１．３４－１．１８（ｍ，９Ｈ）、１．１８－１．０５（ｍ，４Ｈ）、１．０４－０．７８（ｍ，１３Ｈ）． The NMR analysis values of the obtained compound (1-2-17) are as follows.
1 H-NMR: chemical shift δ (ppm; CDCl 3 ): 6.28 (s, 1 H), 6.10 (s, 1 H), 5.88 (d, J = 1.3 Hz, 1 H), 57 (s, 1 H), 4.24-4. 08 (m, 6 H), 3.69-3. 61 (m, 2 H), 3.52-3. 45 (m, 2 H), 2.06 ( t, J = 6.4 Hz, 1 H), 1.94 (s, 3 H), 1.78-1.53 (m, 12 H), 1.46-1.35 (m, 6 H), 1.34- 1.18 (m, 9H), 1.18-1.05 (m, 4H), 1.04 to 0.78 (m, 13H).
　合成例に記載された方法や、「２．化合物（１）の合成」の項を参考にしながら、以下の化合物（１－１－１）から（１－４－４０）を合成することが可能である。 It is possible to synthesize (1-4-40) from the following compounds (1-1-1), referring to the method described in the synthesis example and the section “2. synthesis of compound (1)”. It is.
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000067
Figure JPOXMLDOC01-appb-C000067
Figure JPOXMLDOC01-appb-C000068
Figure JPOXMLDOC01-appb-C000068
Figure JPOXMLDOC01-appb-C000069
Figure JPOXMLDOC01-appb-C000069
Figure JPOXMLDOC01-appb-C000070
Figure JPOXMLDOC01-appb-C000070
Figure JPOXMLDOC01-appb-C000071
Figure JPOXMLDOC01-appb-C000071
Figure JPOXMLDOC01-appb-C000072
Figure JPOXMLDOC01-appb-C000072
Figure JPOXMLDOC01-appb-C000073
Figure JPOXMLDOC01-appb-C000073
Figure JPOXMLDOC01-appb-C000074
Figure JPOXMLDOC01-appb-C000074
Figure JPOXMLDOC01-appb-C000075
Figure JPOXMLDOC01-appb-C000075
Figure JPOXMLDOC01-appb-C000076
Figure JPOXMLDOC01-appb-C000076
［比較例１］
　比較化合物として、国際公開第２０１７／０４７１７７号に記載されている下記化合物（Ｓ－１）を、該公報の記載に基づいて合成し、その特性を測定した。 Comparative Example 1
As a comparison compound, the following compound (S-1) described in WO 2017/047177 was synthesized based on the description of the publication, and the characteristics thereof were measured.
Figure JPOXMLDOC01-appb-C000077
Figure JPOXMLDOC01-appb-C000077
　比較化合物（Ｓ－１）のＮＭＲ分析値は以下の通りであった。
　1Ｈ－ＮＭＲ：化学シフトδ（ｐｐｍ；ＣＤＣｌ3）：７．４８－７．４６（ｍ，２Ｈ）、７．２７－７．２６（ｍ，２Ｈ）、６．７５（ｄ，Ｊ＝２．３Ｈｚ，２Ｈ）、６．４７－６．４６（ｍ，１Ｈ）、６．３０（ｓ，２Ｈ）、５．８６（ｄ，Ｊ＝１．１Ｈｚ，２Ｈ）、４．５４（ｔ，４．４Ｈｚ，４Ｈ）、４．３３（ｓ，４Ｈ）、４．２７－４．２５（ｍ，４Ｈ）、２．５２－２．４７（ｍ，１Ｈ）、２．３４（ｓ，２Ｈ）、１．９８－１．８３（ｍ，４Ｈ）、１．５１－１．４４（ｍ，２Ｈ）、１．３５－１．２０（ｍ，９Ｈ）、１．０９－１．０２（ｍ，２Ｈ）、０．９０（ｔ，Ｊ＝６．９Ｈｚ，３Ｈ）． The NMR analysis values of the comparative compound (S-1) were as follows.
1 H-NMR: chemical shift δ (ppm; CDCl 3 ): 7.48-7.46 (m, 2H), 7.27-7.26 (m, 2H), 6.75 (d, J = 2) .3 Hz, 2 H), 6.47-6.46 (m, 1 H), 6.30 (s, 2 H), 5.86 (d, J = 1.1 Hz, 2 H), 4.54 (t, 4) .4 Hz, 4 H), 4.33 (s, 4 H), 4.27-4. 25 (m, 4 H), 2.52-2.47 (m, 1 H), 2. 34 (s, 2 H), 1.98-1.83 (m, 4 H), 1.51-1. 44 (m, 2 H), 1.35-1. 20 (m, 9 H), 1.09-1.0 2 (m, 2 H) ), 0.90 (t, J = 6.9 Hz, 3 H).
　比較化合物（Ｓ－１）の物性は、次のとおりであった。
　転移温度：Ｃ　５８．８　Ｉ． Physical properties of comparative compound (S-1) were as described below.
Transition temperature: C 58.8 I.
　化合物（１－２－２）、化合物（１－２－６）、化合物（１－３－４）、化合物（１－２－１６）、および化合物（１－２－１７）と比較化合物（Ｓ－１）との液晶組成物への相溶性を比較した。評価には、下記の化合物（ｉ－１）～（ｉ－９）を含む組成物（ｉ）を用いた。 Compound (1-2-2), Compound (1-2-6), Compound (1-3-4), Compound (1-2-16), and Compound (1-2-17) and Comparison Compound (S The compatibility of the liquid crystal composition with No. -1) was compared. The composition (i) containing the following compounds (i-1) to (i-9) was used for the evaluation.
　組成物（ｉ）の成分の割合を重量％で示す。 The proportions of the components of composition (i) are indicated in% by weight.
Figure JPOXMLDOC01-appb-C000078
Figure JPOXMLDOC01-appb-C000078
　組成物（ｉ）１００重量％に対し、化合物（１－２－２）、化合物（１－２－６）、化合物（１－３－４）、化合物（１－２－１６）、および化合物（１－２－１７）、または比較化合物（Ｓ－１）を、表Ａに示す０．１重量％から１．０重量％のいずれかの割合で添加した試料を作成した。この試料を２５℃で７日間静置した後、目視により観察し、ネマチック相を維持している場合は○、結晶またはスメクチック相が析出している場合は×と表した。 The compound (1-2-2), the compound (1-2-6), the compound (1-3-4), the compound (1-2-16), and the compound (I) per 100% by weight of the composition (i) 1-2-17), or a comparison compound (S-1) was added at a ratio of 0.1 wt% to 1.0 wt% shown in Table A to prepare a sample. The sample was allowed to stand at 25 ° C. for 7 days and then visually observed. When the nematic phase was maintained, it was represented by ○, and when the crystal or smectic phase was precipitated, it was represented by x.
Figure JPOXMLDOC01-appb-T000079
Figure JPOXMLDOC01-appb-T000079
　相溶性を比較した結果、化合物（１－２－２）、化合物（１－２－６）、化合物（１－３－４）、化合物（１－２－１６）、および化合物（１－２－１７）は、母液晶（組成物（ｉ））に１．０重量％添加してもネマチック相を維持したのに対し、比較化合物（Ｓ－１）は０．２重量％の添加でも結晶が析出した。これらの化合物は、複数の重合性基を有している点で類似した化合物であるが、両者の母液晶に対する相溶性は大きく異なる。これは、比較化合物（Ｓ－１）は極性基として水酸基を複数有するのに対し、化合物（１－２－２）、化合物（１－２－６）、化合物（１－３－４）、化合物（１－２－１６）、および化合物（１－２－１７）は極性基として水酸基を１つしか持たないため、母液晶への親和性が改善したと考察できる。化合物（１）は複数の重合性基を有し、かつ実用的な相溶性を有する優れた化合物であるといえる。 As a result of comparing the compatibility, the compound (1-2-2), the compound (1-2-6), the compound (1-3-4), the compound (1-2-16), and the compound (1-2-2) 17) maintained the nematic phase even when added to the mother liquid crystal (composition (i)) at 1.0% by weight, whereas the comparative compound (S-1) maintained 0.2% by weight for crystals. It precipitated. These compounds are similar compounds in that they have a plurality of polymerizable groups, but their compatibility with the mother liquid crystals is largely different. The compound (1-2-2), the compound (1-2-6), the compound (1-3-4), the compound, while the comparative compound (S-1) has a plurality of hydroxyl groups as a polar group. Since (1-2-16) and compound (1-2-17) have only one hydroxyl group as a polar group, it can be considered that the affinity to the base liquid crystal is improved. The compound (1) can be said to be an excellent compound having a plurality of polymerizable groups and having practical compatibility.
２．組成物の実施例
　実施例における化合物は、下記の表２の定義に基づいて記号により表した。表２において、１，４－シクロヘキシレンに関する立体配置はトランスである。記号の後にあるかっこ内の番号は化合物の番号に対応する。（－）の記号はその他の液晶性化合物を意味する。液晶性化合物の割合（百分率）は、液晶組成物の重量に基づいた重量百分率（重量％）である。最後に、液晶組成物の特性値をまとめた。特性は、先に記載した方法にしたがって測定し、測定値を（外挿することなく）そのまま記載した。 2. Composition Examples The compounds in the examples are represented by symbols based on the definition of Table 2 below. In Table 2, the configuration for 1,4-cyclohexylene is trans. The numbers in parentheses after the symbols correspond to the compound numbers. The symbol (-) means other liquid crystal compounds. The proportion (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition. Finally, the characteristic values of the liquid crystal composition were summarized. The properties were measured according to the method described above and the measured values were described as they were (without extrapolation).
Figure JPOXMLDOC01-appb-T000080
Figure JPOXMLDOC01-appb-T000080
［使用例１］
１－ＢＢ－３　　　　　　　　　　　　　　（２－８）　　　　　　５％
１－ＢＢ－５　　　　　　　　　　　　　　（２－８）　　　　　　８％
２－ＢＴＢ－１　　　　　　　　　　　　　（２－１０）　　　　　２％
３－ＨＨＢ－１　　　　　　　　　　　　　（３－１）　　　　　　６％
３－ＨＨＢ－３　　　　　　　　　　　　　（３－１）　　　　　１４％
３－ＨＨＢ－Ｏ１　　　　　　　　　　　　（３－１）　　　　　　５％
３－ＨＨＢ－Ｆ　　　　　　　　　　　　　（６－１）　　　　　　４％
２－ＨＨＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２）　　　　　　７％
３－ＨＨＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２）　　　　　　８％
５－ＨＨＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２）　　　　　　８％
３－ＨＨＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　（６－３）　　　　　　５％
３－ＨＨＥＢ－Ｆ　　　　　　　　　　　　（６－１０）　　　　　４％
５－ＨＨＥＢ－Ｆ　　　　　　　　　　　　（６－１０）　　　　　５％
２－ＨＢ－Ｃ　　　　　　　　　　　　　　（８－１）　　　　　　５％
３－ＨＢ－Ｃ　　　　　　　　　　　　　　（８－１）　　　　　１４％ [Example 1]
1-BB-3 (2-8) 5%
1-BB-5 (2-8) 8%
2-BTB-1 (2-10) 2%
3-HHB-1 (3-1) 6%
3-HHB-3 (3-1) 14%
3-HHB-O1 (3-1) 5%
3-HHB-F (6-1) 4%
2-HHB (F) -F (6-2) 7%
3-HHB (F) -F (6-2) 8%
5-HHB (F) -F (6-2) 8%
3-HHB (F, F) -F (6-3) 5%
3-HHEB-F (6-10) 4%
5-HHEB-F (6-10) 5%
2-HB-C (8-1) 5%
3-HB-C (8-1) 14%
　これらの成分を含む組成物１００重量％に下記の化合物（１－２－２）を１重量％の割合で添加した。 The following compound (1-2-2) was added at a ratio of 1% by weight to 100% by weight of a composition containing these components.
Figure JPOXMLDOC01-appb-C000081
Figure JPOXMLDOC01-appb-C000081
　ＮＩ＝９８．１℃；η＝１８．８ｍＰａ・ｓ；Δｎ＝０．１０７；Δε＝５．１． NI = 98.1 ° C .; = 1 = 18.8 mPa · s; Δn = 0.107; Δε = 5.1.
［使用例２］
３－ＨＨ－４　　　　　　　　　　　　　　（２－１）　　　　　１１％
７－ＨＢ－１　　　　　　　　　　　　　　（２－５）　　　　　　１％
５－ＨＢ－Ｏ２　　　　　　　　　　　　　（２－５）　　　　　　７％
５－ＨＢＢ（Ｆ）Ｂ－２　　　　　　　　　（４－５）　　　　　　６％
５－ＨＢＢ（Ｆ）Ｂ－３　　　　　　　　　（４－５）　　　　　　６％
３－ＨＢ－ＣＬ　　　　　　　　　　　　　（５－２）　　　　　１５％
３－ＨＨＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　（６－３）　　　　　　４％
３－ＨＢＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　（６－２４）　　　　２８％
５－ＨＢＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　（６－２４）　　　　２２％ [Example 2]
3-HH-4 (2-1) 11%
7-HB-1 (2-5) 1%
5-HB-O2 (2-5) 7%
5-HBB (F) B-2 (4-5) 6%
5-HBB (F) B-3 (4-5) 6%
3-HB-CL (5-2) 15%
3-HHB (F, F) -F (6-3) 4%
3-HBB (F, F) -F (6-24) 28%
5-HBB (F, F) -F (6-24) 22%
　これらの成分を含む組成物１００重量％に下記の化合物（１－２－６）を０．５重量％の割合で添加した。 The following compound (1-2-6) was added in a proportion of 0.5% by weight to 100% by weight of the composition containing these components.
Figure JPOXMLDOC01-appb-C000082
Figure JPOXMLDOC01-appb-C000082
　ＮＩ＝７３．１℃；η＝１９．３ｍＰａ・ｓ；Δｎ＝０．１１６；Δε＝５．７． NI = 73.1 ° C .; = 1 = 19.3 mPa · s; Δn = 0.116; Δε = 5.7.
［使用例３］
１Ｖ２－ＨＨ－１　　　　　　　　　　　　（２－１）　　　　　　３％
１Ｖ２－ＨＨ－３　　　　　　　　　　　　（２－１）　　　　　　５％
７－ＨＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　　（５－４）　　　　　　３％
２－ＨＨＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２）　　　　　１１％
３－ＨＨＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２）　　　　　１１％
５－ＨＨＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２）　　　　　１０％
２－ＨＢＢ－Ｆ　　　　　　　　　　　　　（６－２２）　　　　　５％
３－ＨＢＢ－Ｆ　　　　　　　　　　　　　（６－２２）　　　　　４％
５－ＨＢＢ－Ｆ　　　　　　　　　　　　　（６－２２）　　　　　３％
２－ＨＢＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２３）　　　　　９％
３－ＨＢＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２３）　　　　　８％
５－ＨＢＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２３）　　　　１５％
３－ＨＢＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　（６－２４）　　　　　４％
５－ＨＢＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　（６－２４）　　　　　９％ [Example 3]
1V2-HH-1 (2-1) 3%
1V2-HH-3 (2-1) 5%
7-HB (F, F) -F (5-4) 3%
2-HHB (F) -F (6-2) 11%
3-HHB (F) -F (6-2) 11%
5-HHB (F) -F (6-2) 10%
2-HBB-F (6-22) 5%
3-HBB-F (6-22) 4%
5-HBB-F (6-22) 3%
2-HBB (F) -F (6-23) 9%
3-HBB (F) -F (6-23) 8%
5-HBB (F) -F (6-23) 15%
3-HBB (F, F) -F (6-24) 4%
5-HBB (F, F) -F (6-24) 9%
　これらの成分を含む組成物１００重量％に下記の化合物（１－３－４）を２重量％の割合で添加した。 The following compound (1-3-4) was added in a proportion of 2% by weight to 100% by weight of the composition containing these components.
Figure JPOXMLDOC01-appb-C000083
Figure JPOXMLDOC01-appb-C000083
　ＮＩ＝８５．７℃；η＝２４．４ｍＰａ・ｓ；Δｎ＝０．１１０；Δε＝５．５． NI = 85.7 ° C .; = 2 = 24.4 mPa · s; Δn = 0.110; Δε = 5.5.
［使用例４］
２－ＨＨ－３　　　　　　　　　　　　　　（２－１）　　　　　　４％
３－ＨＨ－４　　　　　　　　　　　　　　（２－１）　　　　　１２％
１Ｏ１－ＨＢＢＨ－５　　　　　　　　　　（４－１）　　　　　　４％
５－ＨＢ－ＣＬ　　　　　　　　　　　　　（５－２）　　　　　１６％
３－ＨＨＢ－Ｆ　　　　　　　　　　　　　（６－１）　　　　　　４％
３－ＨＨＢ－ＣＬ　　　　　　　　　　　　（６－１）　　　　　　３％
４－ＨＨＢ－ＣＬ　　　　　　　　　　　　（６－１）　　　　　　４％
３－ＨＨＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２）　　　　　１２％
４－ＨＨＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２）　　　　　　９％
５－ＨＨＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２）　　　　　　９％
７－ＨＨＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２）　　　　　　７％
５－ＨＢＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２３）　　　　　５％
３－ＨＨＢＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（７－６）　　　　　　２％
４－ＨＨＢＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（７－６）　　　　　　３％
５－ＨＨＢＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（７－６）　　　　　　２％
３－ＨＨ２ＢＢ（Ｆ，Ｆ）－Ｆ　　　　　　（７－１５）　　　　　２％
４－ＨＨ２ＢＢ（Ｆ，Ｆ）－Ｆ　　　　　　（７－１５）　　　　　２％ [Example 4]
2-HH-3 (2-1) 4%
3-HH-4 (2-1) 12%
1O1-HBBH-5 (4-1) 4%
5-HB-CL (5-2) 16%
3-HHB-F (6-1) 4%
3-HHB-CL (6-1) 3%
4-HHB-CL (6-1) 4%
3-HHB (F) -F (6-2) 12%
4-HHB (F) -F (6-2) 9%
5-HHB (F) -F (6-2) 9%
7-HHB (F) -F (6-2) 7%
5-HBB (F) -F (6-23) 5%
3-HBBB (F, F) -F (7-6) 2%
4-HBBB (F, F)-F (7-6) 3%
5-HBBB (F, F) -F (7-6) 2%
3-HH2BB (F, F) -F (7-15) 2%
4-HH2BB (F, F) -F (7-15) 2%
　これらの成分を含む組成物１００重量％に下記の化合物（１－３－２１）を５重量％の割合で添加した。 The following compound (1-3-21) was added in a proportion of 5% by weight to 100% by weight of the composition containing these components.
Figure JPOXMLDOC01-appb-C000084
Figure JPOXMLDOC01-appb-C000084
　ＮＩ＝１１３．１℃；η＝１８．０ｍＰａ・ｓ；Δｎ＝０．０９０；Δε＝３．７． NI = 113.1 ° C .; = 1 = 18.0 mPa · s; Δn = 0.090; Δε = 3.7.
［使用例５］
Ｖ－ＨＢＢ－２　　　　　　　　　　　　　（３－４）　　　　　１２％
１Ｏ１－ＨＢＢＨ－４　　　　　　　　　　（４－１）　　　　　　５％
１Ｏ１－ＨＢＢＨ－５　　　　　　　　　　（４－１）　　　　　　４％
３－ＨＨＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　（６－３）　　　　　　９％
３－Ｈ２ＨＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（６－１５）　　　　　９％
４－Ｈ２ＨＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（６－１５）　　　　　９％
５－Ｈ２ＨＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（６－１５）　　　　　８％
３－ＨＢＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　（６－２４）　　　　１１％
５－ＨＢＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　（６－２４）　　　　１８％
３－Ｈ２ＢＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（６－２７）　　　　　９％
５－ＨＨＢＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（７－６）　　　　　　２％
３－ＨＨ２ＢＢ（Ｆ，Ｆ）－Ｆ　　　　　　（７－１５）　　　　　２％
５－ＨＨＥＢＢ－Ｆ　　　　　　　　　　　（７－１７）　　　　　２％ [Example 5]
V-HBB-2 (3-4) 12%
1O1-HBBH-4 (4-1) 5%
1O1-HBBH-5 (4-1) 4%
3-HHB (F, F) -F (6-3) 9%
3-H2HB (F, F) -F (6-15) 9%
4-H2HB (F, F) -F (6-15) 9%
5-H2HB (F, F) -F (6-15) 8%
3-HBB (F, F) -F (6-24) 11%
5-HBB (F, F) -F (6-24) 18%
3-H2BB (F, F) -F (6-27) 9%
5-HBBB (F, F) -F (7-6) 2%
3-HH2BB (F, F) -F (7-15) 2%
5-HHEBB-F (7-17) 2%
　これらの成分を含む組成物１００重量％に下記の化合物（１－３－６６）を１．５重量％の割合で添加した。 The following compound (1-3-66) was added at a ratio of 1.5% by weight to 100% by weight of a composition containing these components.
Figure JPOXMLDOC01-appb-C000085
Figure JPOXMLDOC01-appb-C000085
　ＮＩ＝１０７．４℃；η＝３１．４ｍＰａ・ｓ；Δｎ＝０．１２３；Δε＝８．０． NI = 107.4 ° C .; = 3 = 31.4 mPa · s; Δn = 0.123; Δε = 8.0.
［使用例６］
５－ＨＢＢＨ－３　　　　　　　　　　　　（４－１）　　　　　　３％
３－ＨＢ（Ｆ）ＢＨ－３　　　　　　　　　（４－２）　　　　　　３％
５－ＨＢ－Ｆ　　　　　　　　　　　　　　（５－２）　　　　　１２％
６－ＨＢ－Ｆ　　　　　　　　　　　　　　（５－２）　　　　　　９％
７－ＨＢ－Ｆ　　　　　　　　　　　　　　（５－２）　　　　　　７％
２－ＨＨＢ－ＯＣＦ３　　　　　　　　　　（６－１）　　　　　　７％
３－ＨＨＢ－ＯＣＦ３　　　　　　　　　　（６－１）　　　　　　９％
４－ＨＨＢ－ＯＣＦ３　　　　　　　　　　（６－１）　　　　　　７％
５－ＨＨＢ－ＯＣＦ３　　　　　　　　　　（６－１）　　　　　　５％
３－ＨＨＢ（Ｆ，Ｆ）－ＯＣＦ２Ｈ　　　　（６－３）　　　　　　６％
３－ＨＨＢ（Ｆ，Ｆ）－ＯＣＦ３　　　　　（６－３）　　　　　　４％
３－ＨＨ２Ｂ－ＯＣＦ３　　　　　　　　　（６－４）　　　　　　３％
５－ＨＨ２Ｂ－ＯＣＦ３　　　　　　　　　（６－４）　　　　　　４％
３－ＨＨ２Ｂ（Ｆ）－Ｆ　　　　　　　　　（６－５）　　　　　　３％
３－ＨＢＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２３）　　　　　９％
５－ＨＢＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２３）　　　　　９％ [Example 6]
5-HBBH-3 (4-1) 3%
3-HB (F) BH-3 (4-2) 3%
5-HB-F (5-2) 12%
6-HB-F (5-2) 9%
7-HB-F (5-2) 7%
2-HHB-OCF3 (6-1) 7%
3-HHB-OCF3 (6-1) 9%
4-HHB-OCF3 (6-1) 7%
5-HHB-OCF3 (6-1) 5%
3-HHB (F, F) -OCF2H (6-3) 6%
3-HHB (F, F) -OCF3 (6-3) 4%
3-HH2B-OCF3 (6-4) 3%
5-HH2B-OCF3 (6-4) 4%
3-HH2B (F) -F (6-5) 3%
3-HBB (F) -F (6-23) 9%
5-HBB (F) -F (6-23) 9%
　これらの成分を含む組成物１００重量％に下記の化合物（１－３－６２）を２重量％の割合で添加した。 The following compound (1-3-62) was added in a proportion of 2% by weight to 100% by weight of the composition containing these components.
Figure JPOXMLDOC01-appb-C000086
Figure JPOXMLDOC01-appb-C000086
　ＮＩ＝８５．８℃；η＝１５．０ｍＰａ・ｓ；Δｎ＝０．０９１；Δε＝４．５． NI = 85.8 ° C .; = 1 = 15.0 mPa · s; Δn = 0.091; Δε = 4.5.
［使用例７］
２－ＨＨ－５　　　　　　　　　　　　　　（２－１）　　　　　　６％
３－ＨＨ－４　　　　　　　　　　　　　　（２－１）　　　　　　５％
５－Ｂ（Ｆ）ＢＢ－２　　　　　　　　　　（３－８）　　　　　　５％
５－ＨＢ－ＣＬ　　　　　　　　　　　　　（５－２）　　　　　１１％
３－ＨＨＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　（６－３）　　　　　　８％
３－ＨＨＥＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（６－１２）　　　　１０％
４－ＨＨＥＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（６－１２）　　　　　３％
５－ＨＨＥＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（６－１２）　　　　　４％
３－ＨＢＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　（６－２４）　　　　２０％
５－ＨＢＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　（６－２４）　　　　１５％
２－ＨＢＥＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（６－３９）　　　　　２％
３－ＨＢＥＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（６－３９）　　　　　４％
５－ＨＢＥＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（６－３９）　　　　　２％
３－ＨＨＢＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（７－６）　　　　　　５％ [Example 7]
2-HH-5 (2-1) 6%
3-HH-4 (2-1) 5%
5-B (F) BB-2 (3-8) 5%
5-HB-CL (5-2) 11%
3-HHB (F, F) -F (6-3) 8%
3-HHEB (F, F) -F (6-12) 10%
4-HHEB (F, F) -F (6-12) 3%
5-HHEB (F, F) -F (6-12) 4%
3-HBB (F, F) -F (6-24) 20%
5-HBB (F, F) -F (6-24) 15%
2-HBEB (F, F)-F (6-39) 2%
3-HBEB (F, F) -F (6-39) 4%
5-HBEB (F, F) -F (6-39) 2%
3-HBBB (F, F) -F (7-6) 5%
　これらの成分を含む組成物１００重量％に下記の化合物（１－３－８８）を０．８重量％の割合で添加した。 The following compound (1-3-88) was added at a ratio of 0.8% by weight to 100% by weight of a composition containing these components.
Figure JPOXMLDOC01-appb-C000087
Figure JPOXMLDOC01-appb-C000087
　ＮＩ＝７５．９℃；η＝２０．８ｍＰａ・ｓ；Δｎ＝０．１０７；Δε＝７．８． NI = 75.9 ° C; = 2 = 20.8 mPa · s; Δn = 0.107; Δε = 7.8.
［使用例８］
Ｖ２－ＨＨＢ－１　　　　　　　　　　　　（３－１）　　　　　　７％
３－ＨＢ－ＣＬ　　　　　　　　　　　　　（５－２）　　　　　　７％
５－ＨＢ－ＣＬ　　　　　　　　　　　　　（５－２）　　　　　　５％
３－ＨＨＢ－ＯＣＦ３　　　　　　　　　　（６－１）　　　　　　５％
５－ＨＨＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２）　　　　　　４％
Ｖ－ＨＨＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２）　　　　　　５％
３－Ｈ２ＨＢ－ＯＣＦ３　　　　　　　　　（６－１３）　　　　　５％
５－Ｈ２ＨＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（６－１５）　　　　　４％
５－Ｈ４ＨＢ－ＯＣＦ３　　　　　　　　　（６－１９）　　　　１５％
５－Ｈ４ＨＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（６－２１）　　　　　７％
３－Ｈ４ＨＢ（Ｆ，Ｆ）－ＣＦ３　　　　　（６－２１）　　　　　８％
５－Ｈ４ＨＢ（Ｆ，Ｆ）－ＣＦ３　　　　　（６－２１）　　　　１０％
２－Ｈ２ＢＢ（Ｆ）－Ｆ　　　　　　　　　（６－２６）　　　　　５％
３－Ｈ２ＢＢ（Ｆ）－Ｆ　　　　　　　　　（６－２６）　　　　　９％
３－ＨＢＥＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（６－３９）　　　　　４％ [Example 8]
V2-HHB-1 (3-1) 7%
3-HB-CL (5-2) 7%
5-HB-CL (5-2) 5%
3-HHB-OCF3 (6-1) 5%
5-HHB (F) -F (6-2) 4%
V-HHB (F) -F (6-2) 5%
3-H2HB-OCF3 (6-13) 5%
5-H2HB (F, F) -F (6-15) 4%
5-H4HB-OCF3 (6-19) 15%
5-H4HB (F, F) -F (6-21) 7%
3-H4HB (F, F) -CF3 (6-21) 8%
5-H4HB (F, F) -CF3 (6-21) 10%
2-H2BB (F) -F (6-26) 5%
3-H2BB (F) -F (6-26) 9%
3-HBEB (F, F) -F (6-39) 4%
　これらの成分を含む組成物１００重量％に下記の化合物（１－２－２）を３重量％の割合で添加した。 The following compound (1-2-2) was added in a proportion of 3% by weight to 100% by weight of the composition containing these components.
Figure JPOXMLDOC01-appb-C000088
Figure JPOXMLDOC01-appb-C000088
　ＮＩ＝７２．１℃；η＝２３．５ｍＰａ・ｓ；Δｎ＝０．０９９；Δε＝７．８． NI = 72.1 ° C; = 2 = 23.5 mPa · s; Δn = 0.099; Δε = 7.8.
［使用例９］
３－ＨＨ－４　　　　　　　　　　　　　　（２－１）　　　　　１０％
３－ＨＨ－５　　　　　　　　　　　　　　（２－１）　　　　　　５％
３－ＨＢ－Ｏ２　　　　　　　　　　　　　（２－５）　　　　　１５％
３－ＨＨＢ－１　　　　　　　　　　　　　（３－１）　　　　　１０％
３－ＨＨＢ－Ｏ１　　　　　　　　　　　　（３－１）　　　　　　６％
５－ＨＢ－ＣＬ　　　　　　　　　　　　　（５－２）　　　　　１７％
７－ＨＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　　（５－４）　　　　　　４％
２－ＨＨＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２）　　　　　　７％
３－ＨＨＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２）　　　　　　７％
５－ＨＨＢ（Ｆ）－Ｆ　　　　　　　　　　（６－２）　　　　　　６％
３－ＨＨＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　（６－３）　　　　　　５％
３－Ｈ２ＨＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（６－１５）　　　　　４％
４－Ｈ２ＨＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（６－１５）　　　　　４％ [Example 9]
3-HH-4 (2-1) 10%
3-HH-5 (2-1) 5%
3-HB-O2 (2-5) 15%
3-HHB-1 (3-1) 10%
3-HHB-O1 (3-1) 6%
5-HB-CL (5-2) 17%
7-HB (F, F) -F (5-4) 4%
2-HHB (F) -F (6-2) 7%
3-HHB (F) -F (6-2) 7%
5-HHB (F) -F (6-2) 6%
3-HHB (F, F) -F (6-3) 5%
3-H2HB (F, F) -F (6-15) 4%
4-H2HB (F, F) -F (6-15) 4%
　これらの成分を含む組成物１００重量％に下記の化合物（１－２－６）を４重量％の割合で添加した。 The following compound (1-2-6) was added in a proportion of 4% by weight to 100% by weight of the composition containing these components.
Figure JPOXMLDOC01-appb-C000089
Figure JPOXMLDOC01-appb-C000089
　ＮＩ＝７２．２℃；η＝１３．１ｍＰａ・ｓ；Δｎ＝０．０７４；Δε＝２．６． NI = 72.2 ° C .; = 1 = 13.1 mPa · s; Δn = 0.074; Δε = 2.6.
［使用例１０］
３－ＨＨ－４　　　　　　　　　　　　　　（２－１）　　　　　１０％
３－ＨＨ－５　　　　　　　　　　　　　　（２－１）　　　　　１１％
３－ＨＨＢ－１　　　　　　　　　　　　　（３－１）　　　　　１２％
５－ＨＢ－ＣＬ　　　　　　　　　　　　　（５－２）　　　　　　３％
７－ＨＢ（Ｆ）－Ｆ　　　　　　　　　　　（５－３）　　　　　　７％
２－ＨＨＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　（６－３）　　　　　　５％
３－ＨＨＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　（６－３）　　　　　　６％
３－ＨＨＥＢ－Ｆ　　　　　　　　　　　　（６－１０）　　　　　８％
５－ＨＨＥＢ－Ｆ　　　　　　　　　　　　（６－１０）　　　　　９％
３－ＨＨＥＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（６－１２）　　　　１０％
４－ＨＨＥＢ（Ｆ，Ｆ）－Ｆ　　　　　　　（６－１２）　　　　　４％
３－ＧＨＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　（６－１０９）　　　　４％
４－ＧＨＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　（６－１０９）　　　　５％
５－ＧＨＢ（Ｆ，Ｆ）－Ｆ　　　　　　　　（６－１０９）　　　　６％ [Usage example 10]
3-HH-4 (2-1) 10%
3-HH-5 (2-1) 11%
3-HHB-1 (3-1) 12%
5-HB-CL (5-2) 3%
7-HB (F) -F (5-3) 7%
2-HHB (F, F) -F (6-3) 5%
3-HHB (F, F) -F (6-3) 6%
3-HHEB-F (6-10) 8%
5-HHEB-F (6-10) 9%
3-HHEB (F, F) -F (6-12) 10%
4-HHEB (F, F)-F (6-12) 4%
3-GHB (F, F)-F (6-109) 4%
4-GHB (F, F)-F (6-109) 5%
5-GHB (F, F)-F (6-109) 6%
　これらの成分を含む組成物１００重量％に下記の化合物（１－３－４）を５重量％の割合で添加した。 The following compound (1-3-4) was added in a proportion of 5% by weight to 100% by weight of the composition containing these components.
Figure JPOXMLDOC01-appb-C000090
Figure JPOXMLDOC01-appb-C000090
　ＮＩ＝８７．７℃；η＝２０．３ｍＰａ・ｓ；Δｎ＝０．０７０；Δε＝５．５． NI = 87.7 ° C .; = 2 = 20.3 mPa · s; Δn = 0.070; Δε = 5.5.
［使用例１１］
３－ＨＨ－ＶＦＦ　　　　　　　　　　　　（２－１）　　　　　　６％
５－ＨＨ－ＶＦＦ　　　　　　　　　　　　（２－１）　　　　　２５％
２－ＢＴＢ－１　　　　　　　　　　　　　（２－１０）　　　　１０％
３－ＨＨＢ－１　　　　　　　　　　　　　（３－１）　　　　　　５％
ＶＦＦ－ＨＨＢ－１　　　　　　　　　　　（３－１）　　　　　　９％
ＶＦＦ２－ＨＨＢ－１　　　　　　　　　　（３－１）　　　　　１２％
３－Ｈ２ＢＴＢ－２　　　　　　　　　　　（３－１７）　　　　　５％
３－Ｈ２ＢＴＢ－３　　　　　　　　　　　（３－１７）　　　　　３％
３－Ｈ２ＢＴＢ－４　　　　　　　　　　　（３－１７）　　　　　３％
３－ＨＢ－Ｃ　　　　　　　　　　　　　　（８－１）　　　　　１７％
１Ｖ２－ＢＥＢ（Ｆ，Ｆ）－Ｃ　　　　　　（８－１５）　　　　　５％ [Example 11 of use]
3-HH-VFF (2-1) 6%
5-HH-VFF (2-1) 25%
2-BTB-1 (2-10) 10%
3-HHB-1 (3-1) 5%
VFF-HHB-1 (3-1) 9%
VFF2-HHB-1 (3-1) 12%
3-H2BTB-2 (3-17) 5%
3-H2BTB-3 (3-17) 3%
3-H2BTB-4 (3-17) 3%
3-HB-C (8-1) 17%
1V2-BEB (F, F) -C (8-15) 5%
　これらの成分を含む組成物１００重量％に下記の化合物（１－３－２１）を１．５重量％の割合で添加した。 The following compound (1-3-21) was added at a ratio of 1.5% by weight to 100% by weight of a composition containing these components.
Figure JPOXMLDOC01-appb-C000091
Figure JPOXMLDOC01-appb-C000091
　ＮＩ＝８２．０℃；η＝１０．２ｍＰａ・ｓ；Δｎ＝０．１２６；Δε＝５．８． NI = 82.0 ° C .; = 1 = 10.2 mPa · s; Δn = 0.126; Δε = 5.8.
　化合物（１）含む液晶組成物は、液晶プロジェクター、液晶テレビなどの表示素子に用いることができる。 The liquid crystal composition containing the compound (1) can be used for display elements such as a liquid crystal projector and a liquid crystal television.

Claims (17)

  1. 　式（１）で表される化合物：
    Figure JPOXMLDOC01-appb-C000001
     式（１）において、
    　Ｒ1は、水素または炭素数１から１５のアルキルであり、このアルキルにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－または－Ｓ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
    　環Ａ1および環Ａ2は独立して、１，２－シクロプロピレン、１，３－シクロブチレン、１，３－シクロペンチレン、１，４－シクロヘキシレン、１，４－シクロヘプチレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－２，６－ジイル、デカヒドロナフタレン－２，６－ジイル、１，２，３，４－テトラヒドロナフタレン－２，６－ジイル、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、またはピリジン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１０のアルキル、炭素数２から１０のアルケニル、炭素数１から９のアルコキシ、または炭素数２から９のアルケニルオキシで置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
    　ａは、０、１、２、３、または４であり；
    　Ｚ1は、単結合または炭素数１から６のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
    　Ｓｐ1、Ｓｐ2、Ｓｐ3、およびＳｐ4は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
    　Ｓｐ5は、炭素数２から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよく；
    　Ｍ1、Ｍ2、Ｍ3、およびＭ4は独立して、水素、フッ素、塩素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルであり；
    　Ｒ2は、水素または炭素数１から５のアルキルであり、このアルキルにおいて、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
    　Ｘ1は、－ＯＨ、－ＮＨ2、－ＯＲ3、－Ｎ（Ｒ3）2、－ＣＯＯＨ、－ＳＨ、または－Ｓｉ（Ｒ3）3であり；
    －ＯＲ3、－Ｎ（Ｒ3）2、および－Ｓｉ（Ｒ3）3において、
    　Ｒ3は水素または炭素数１から１０のアルキルであり、このアルキルにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
    　ａが１であり、環Ａ1が１，４－シクロヘキシレンであり、環Ａ2が１，４－フェニレンであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｓｐ5が－（ＣＨ2）2－であり、Ｒ2がメチルであり、Ｘ1が－ＯＨであるときは、Ｓｐ1は、－ＣＨ2－ではなく；
    　ａが１であり、環Ａ1が１，４－フェニレンであり、環Ａ2がナフタレン－２，６－ジイルであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｓｐ5が－（ＣＨ2）2－であり、Ｒ2がメチルであり、Ｘ1が－ＯＨであるときは、Ｓｐ1は、－ＣＨ2－ではなく；
    　ａが３であり、４つの環がＲ1側からそれぞれ、１，４－フェニレン、２－エチル－１，４－フェニレン、１，４－シクロヘキシレン、および１，４－シクロヘキシレンであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｓｐ5が－（ＣＨ2）2－であり、Ｒ2がメチルであり、Ｘ1が－ＯＨであるときは、Ｓｐ1は、－ＣＨ2－ではない。     The compound represented by the formula (1):
    Figure JPOXMLDOC01-appb-C000001
     In equation (1),
    R 1 is hydrogen or alkyl having 1 to 15 carbons, and in this alkyl, at least one —CH 2 — may be replaced by —O— or —S—, and at least one — (CH 2) ) 2 -may be replaced by -CH = CH- or -C≡C-, and in these groups at least one hydrogen may be replaced by fluorine or chlorine;
    Ring A 1 and ring A 2 are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4 -Cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2 , 5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl in which at least one hydrogen is fluorine, chlorine , Alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyloxy having 2 to 9 carbons. Or in these groups at least one hydrogen may be replaced by fluorine or chlorine;
    a is 0, 1, 2, 3 or 4;
    Z 1 represents a single bond or an alkylene having 1 to 6 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —CO—, —COO—, —OCO—, or —OCOO— And at least one — (CH 2 ) 2 — may be replaced by —CH = CH— or —C≡C—, and in these groups at least one hydrogen is fluorine or May be replaced by chlorine;
    Sp 1 , Sp 2 , Sp 3 and Sp 4 are each independently a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —CO— And -COO-, -OCO-, or -OCOO-, and at least one-(CH 2 ) 2 -may be replaced with -CH = CH- or -C≡C-, In these groups, at least one hydrogen may be replaced by fluorine or chlorine;
    Sp 5 is alkylene having 2 to 10 carbons, and in this alkylene, at least one —CH 2 — may be replaced by —O—;
    M 1 , M 2 , M 3 and M 4 independently represent hydrogen, fluorine, chlorine, alkyl having 1 to 5 carbon atoms, or 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine Alkyl;
    R 2 is hydrogen or alkyl having 1 to 5 carbon atoms, and in this alkyl, at least one — (CH 2 ) 2 — may be replaced by —CH = CH— or —C≡C—, In these groups, at least one hydrogen may be replaced by fluorine or chlorine;
    X 1 is —OH, —NH 2 , —OR 3 , —N (R 3 ) 2 , —COOH, —SH, or —Si (R 3 ) 3 ;
    In -OR 3 , -N (R 3 ) 2 , and -Si (R 3 ) 3 ,
    R 3 is hydrogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one —CH 2 — may be replaced by —O—, and at least one — (CH 2 ) 2 — is -CH = CH- may be replaced, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine;
    a is 1, ring A 1 is 1,4-cyclohexylene, ring A 2 is 1,4-phenylene, Z 1 is a single bond, Sp 2 , Sp 3 , and Sp 4 are When CH 2- , Sp 5 is-(CH 2 ) 2- , R 2 is methyl and X 1 is -OH, then Sp 1 is not -CH 2- ;
    a is 1, ring A 1 is 1,4-phenylene, ring A 2 is naphthalene-2,6-diyl, Z 1 is a single bond, Sp 2 , Sp 3 , and Sp 4 are When -CH 2- , Sp 5 is-(CH 2 ) 2- , R 2 is methyl and X 1 is -OH, then Sp 1 is not -CH 2- ;
    a is 3, and 4 rings from the R 1 side are respectively 1,4-phenylene, 2-ethyl-1,4-phenylene, 1,4-cyclohexylene, and 1,4-cyclohexylene; 1 is a single bond, Sp 2 , Sp 3 and Sp 4 are -CH 2- , Sp 5 is-(CH 2 ) 2- , R 2 is methyl and X 1 is -OH Sometimes, Sp 1 is not -CH 2- .
  2. 　式（１）において、
    　Ｚ1が、単結合、－（ＣＨ2）2－、－（ＣＨ2）4－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＦ2Ｏ－、－ＯＣＦ2－、－ＣＨ2Ｏ－、－ＯＣＨ2－、または－ＣＦ＝ＣＦ－である、請求項１に記載の化合物。     In equation (1),
    Z 1 is a single bond, - (CH 2) 2 - , - (CH 2) 4 -, - CH = CH -, - C≡C -, - COO -, - OCO -, - CF 2 O -, - The compound according to claim 1, wherein OCF 2- , -CH 2 O-, -OCH 2- , or -CF = CF-.
  3. 　式（１）において、
    　環Ａ1および環Ａ2が独立して、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－２，６－ジイル、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、またはピリジン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１０のアルキル、炭素数２から１０のアルケニル、炭素数１から９のアルコキシ、または炭素数２から９のアルケニルオキシで置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい、請求項１または２に記載の化合物。     In equation (1),
    Ring A 1 and ring A 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, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, and in these rings, at least one hydrogen is fluorine, chlorine, carbon number 1 10 alkyl, alkenyl of 2 to 10 carbons, alkoxy of 1 to 9 carbons, or alkenyloxy of 2 to 9 carbons, and in these groups, at least one hydrogen is fluorine or chlorine The compound according to claim 1 or 2, which may be replaced by
  4. 　式（１－１）から式（１－４）のいずれか１つで表される、請求項１から３のいずれか１項に記載の化合物：
    Figure JPOXMLDOC01-appb-C000002
     式（１－１）から式（１－４）において、
    　Ｒ1は、炭素数１～１５のアルキル、炭素数２～１５のアルケニル、炭素数１～１４のアルコキシ、または炭素数２～１４のアルケニルオキシであり、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；
    　環Ａ1、環Ａ2、環Ａ3、および環Ａ4は独立して、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－２，６－ジイル、テトラヒドロピラン－２，５－ジイル、または１，３－ジオキサン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、炭素数１から１０のアルキル、炭素数２から１０のアルケニル、炭素数１から９のアルコキシ、または炭素数２から９のアルケニルオキシで置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；
    　Ｚ1、Ｚ2、およびＺ3は独立して、単結合、－（ＣＨ2）2－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＦ2Ｏ－、－ＯＣＦ2－、－ＣＨ2Ｏ－、－ＯＣＨ2－、または－ＣＦ＝ＣＦ－であり；
    　Ｓｐ1、Ｓｐ2、Ｓｐ3、およびＳｐ4は独立して、単結合または炭素数１から７のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；
    　Ｓｐ5は、炭素数２から７のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよく；
    　Ｍ1、Ｍ2、Ｍ3、およびＭ4は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素で置き換えられた炭素数１から５のアルキルであり；
    　Ｒ2は、水素または炭素数１から５のアルキルであり；
    　Ｘ1は、－ＯＨ、－ＮＨ2、または－ＳＨであり；
    式（１－２）において、
    　環Ａ1が１，４－シクロヘキシレンであり、環Ａ2が１，４－フェニレンであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｓｐ5が－（ＣＨ2）2－であり、Ｒ2がメチルであり、Ｘ1が－ＯＨであるときは、Ｓｐ1は、－ＣＨ2－ではなく；
    式（１－２）において、
    　環Ａ1が１，４－フェニレンであり、環Ａ2がナフタレン－２，６－ジイルであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｓｐ5が－（ＣＨ2）2
    －であり、Ｒ2がメチルであり、Ｘ1が－ＯＨであるときは、Ｓｐ1は、－ＣＨ2－ではなく；
    式（１－４）において、
    　環Ａ1が１，４－フェニレンであり、環Ａ2が２－エチル－１，４－フェニレンであり、環Ａ3および環Ａ4が共に１，４－シクロヘキシレンであり、Ｚ1、Ｚ2、およびＺ3が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｓｐ5が－（ＣＨ2）2－であり、Ｒ2がメチルであり、Ｘ1が－ＯＨであるときは、Ｓｐ1は、－ＣＨ2－ではない。     The compound according to any one of claims 1 to 3, which is represented by any one of formulas (1-1) to (1-4):
    Figure JPOXMLDOC01-appb-C000002
     In formulas (1-1) to (1-4),
    R 1 is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 14 carbons, or alkenyloxy having 2 to 14 carbons, and in these groups, at least one hydrogen is , May be replaced by fluorine;
    Ring A 1 , ring A 2 , ring A 3 and ring A 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, Tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl, in which ring at least one hydrogen is fluorine, alkyl having 1 to 10 carbons, 2 to 10 carbons Of C 1 to C 9 alkoxy or C 2 to C 9 alkenyloxy, and in these groups, at least one hydrogen may be replaced by fluorine;
    Z 1 , Z 2 and Z 3 independently represent a single bond,-(CH 2 ) 2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CF 2 O- , -OCF 2- , -CH 2 O-, -OCH 2- , or -CF = CF-;
    Sp 1 , Sp 2 , Sp 3 and Sp 4 independently represent a single bond or an alkylene having 1 to 7 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —COO— Or -OCO-, and at least one-(CH 2 ) 2 -may be replaced by -CH = CH-, and in these groups, at least one hydrogen is replaced by fluorine May be
    Sp 5 is alkylene having 2 to 7 carbon atoms, and in this alkylene, at least one —CH 2 — may be replaced by —O—;
    M 1 , M 2 , M 3 and M 4 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine;
    R 2 is hydrogen or alkyl having 1 to 5 carbons;
    X 1 is -OH, -NH 2 , or -SH;
    In equation (1-2),
    Ring A 1 is 1,4-cyclohexylene, Ring A 2 is 1,4-phenylene, Z 1 is a single bond, Sp 2 , Sp 3 and Sp 4 are —CH 2 — When Sp 5 is-(CH 2 ) 2- , R 2 is methyl and X 1 is -OH, Sp 1 is not -CH 2- ;
    In equation (1-2),
    Ring A 1 is 1,4-phenylene, ring A 2 is naphthalene-2,6-diyl, Z 1 is a single bond, Sp 2 , Sp 3 , and Sp 4 are —CH 2 — , Sp 5- (CH 2 ) 2
    Sp 1 is not —CH 2 —, when —, R 2 is methyl and X 1 is —OH;
    In formula (1-4),
    Ring A 1 is 1,4-phenylene, ring A 2 is 2-ethyl-1,4-phenylene, ring A 3 and ring A 4 are both 1,4-cyclohexylene, Z 1 , Z 2 and Z 3 are a single bond, Sp 2 , Sp 3 and Sp 4 are -CH 2- , Sp 5 is-(CH 2 ) 2- and R 2 is methyl, X 1 When is -OH, Sp 1 is not -CH 2- .
  5. 　式（１－５）から式（１－７）のいずれか１つで表される、請求項１から４のいずれか１項に記載の化合物：
    Figure JPOXMLDOC01-appb-C000003
     　式（１－５）から式（１－７）において、
    　Ｒ1は、炭素数１～１０のアルキル、炭素数２～１０のアルケニル、または炭素数１～９のアルコキシであり；
    　環Ａ1、環Ａ2、環Ａ3、および環Ａ4は独立して、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－２，６－ジイル、テトラヒドロピラン－２，５－ジイル、または１，３－ジオキサン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、炭素数１から５のアルキル、炭素数２から５のアルケニル、または炭素数１から４のアルコキシで置き換えられてもよく；
    　Ｚ1、Ｚ2、およびＺ3は独立して、単結合、－（ＣＨ2）2－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＨ2Ｏ－、または－ＯＣＨ2－であり；
    　Ｓｐ1、Ｓｐ2、Ｓｐ3、およびＳｐ4は独立して、単結合または炭素数１から５のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよく、少なくとも１つの－（ＣＨ2）2－は、－ＣＨ＝ＣＨ－で置き換えられてもよく；

    　Ｒ2は、炭素数１から３のアルキルであり；
    式（１－５）において、
    　環Ａ1が１，４－シクロヘキシレンであり、環Ａ2が１，４－フェニレンであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｒ2がメチルであるときは、Ｓｐ1は、－ＣＨ2－ではなく；
    式（１－５）において、
    　環Ａ1が１，４－フェニレンであり、環Ａ2がナフタレン－２，６－ジイルであり、Ｚ1が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｒ2がメチルであるときは、Ｓｐ1は、－ＣＨ2－ではなく；
    式（１－７）において、
    　環Ａ1が１，４－フェニレンであり、環Ａ2が２－エチル－１，４－フェニレンであり、環Ａ3および環Ａ4が共に１，４－シクロヘキシレンであり、Ｚ1、Ｚ2、およびＺ3が単結合であり、Ｓｐ2、Ｓｐ3、およびＳｐ4が－ＣＨ2－であり、Ｒ2がメチルであるときは、Ｓｐ1は、－ＣＨ2－ではない。     The compound according to any one of claims 1 to 4, which is represented by any one of formulas (1-5) to (1-7):
    Figure JPOXMLDOC01-appb-C000003
     In formulas (1-5) to (1-7),
    R 1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkoxy having 1 to 9 carbons;
    Ring A 1 , ring A 2 , ring A 3 and ring A 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, Tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl, in which ring at least one hydrogen is fluorine, alkyl having 1 to 5 carbons, 2 to 5 carbons Or alkenyl of 1 to 4 carbon atoms;
    Z 1 , Z 2 and Z 3 are independently a single bond,-(CH 2 ) 2- , -CH = CH-, -C≡C-, -CH 2 O-, or -OCH 2- ;
    Sp 1 , Sp 2 , Sp 3 , and Sp 4 are independently a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one —CH 2 — is replaced by —O— It may be, at least one - (CH 2) 2 - may be replaced by -CH = CH-;

    R 2 is alkyl having 1 to 3 carbons;
    In formula (1-5),
    Ring A 1 is 1,4-cyclohexylene, Ring A 2 is 1,4-phenylene, Z 1 is a single bond, Sp 2 , Sp 3 and Sp 4 are —CH 2 — When R 2 is methyl, then Sp 1 is not -CH 2- ;
    In formula (1-5),
    Ring A 1 is 1,4-phenylene, ring A 2 is naphthalene-2,6-diyl, Z 1 is a single bond, Sp 2 , Sp 3 , and Sp 4 are —CH 2 — , When R 2 is methyl, Sp 1 is not -CH 2- ;
    In equation (1-7),
    Ring A 1 is 1,4-phenylene, ring A 2 is 2-ethyl-1,4-phenylene, ring A 3 and ring A 4 are both 1,4-cyclohexylene, Z 1 , Z When 2 and Z 3 are a single bond, Sp 2 , Sp 3 and Sp 4 are -CH 2- and R 2 is methyl, Sp 1 is not -CH 2- .
  6. 　式（１－８）から式（１－１６）のいずれか１つで表される、請求項１から５のいずれか１項に記載の化合物：
    Figure JPOXMLDOC01-appb-C000004
     式（１－８）から式（１－１６）において、
    　Ｒ1は、炭素数１～１０のアルキル、炭素数２～１０のアルケニル、または炭素数１～９のアルコキシであり；
    　Ｚ1およびＺ2は独立して、単結合または－（ＣＨ2）2－であり；
    　Ｓｐ1、Ｓｐ2、およびＳｐ3は独立して、単結合または炭素数１から５のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよく；
    　Ｙ1、Ｙ2、Ｙ3、Ｙ4、Ｙ5、およびＹ6は独立して、水素、フッ素、炭素数１から５のアルキル、炭素数２から５のアルケニル、または炭素数１から４のアルコキシであり；
    式（１－９）において、
    　Ｚ1が単結合であり、Ｓｐ2およびＳｐ3が－ＣＨ2－であり、Ｙ1およびＹ2が水素であるときは、Ｓｐ1は、－ＣＨ2－ではない。     The compound according to any one of claims 1 to 5, which is represented by any one of formulas (1-8) to (1-16):
    Figure JPOXMLDOC01-appb-C000004
     In formulas (1-8) to (1-16),
    R 1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkoxy having 1 to 9 carbons;
    Z 1 and Z 2 are independently a single bond or-(CH 2 ) 2- ;
    Sp 1 , Sp 2 and Sp 3 are independently a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one —CH 2 — may be replaced by —O—;
    Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons, or 1 to 4 carbons Is alkoxy;
    In formula (1-9),
    When Z 1 is a single bond, Sp 2 and Sp 3 are -CH 2- , and Y 1 and Y 2 are hydrogen, Sp 1 is not -CH 2- .
  7. 　式（１－１７）から式（１－２３）のいずれか１つで表される、請求項１から６のいずれか１項に記載の化合物：
    Figure JPOXMLDOC01-appb-C000005
     式（１－１７）から式（１－２３）において、
    　Ｒ1は、炭素数１～１０のアルキルであり；
    　Ｙ1、Ｙ2、Ｙ3、Ｙ4、Ｙ5、およびＹ6は独立して、水素、フッ素、メチル、またはエチルであり、
    　Ｓｐ1は単結合または炭素数１から５のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－で置き換えられてもよく；
    式（１－１８）において、
    　Ｙ1およびＹ2が水素であるときは、Ｓｐ1は、－ＣＨ2－ではない。     The compound according to any one of claims 1 to 6, which is represented by any one of formulas (1-17) to (1-23):
    Figure JPOXMLDOC01-appb-C000005
     In formulas (1-17) to (1-23),
    R 1 is alkyl having 1 to 10 carbons;
    Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 are independently hydrogen, fluorine, methyl or ethyl;
    Sp 1 is a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one —CH 2 — may be replaced by —O—;
    In formula (1-18),
    When Y 1 and Y 2 are hydrogen, Sp 1 is not —CH 2 —.
  8. 　請求項１から７のいずれか１項に記載の化合物の少なくとも１つを含有する液晶組成物。 A liquid crystal composition comprising at least one of the compounds according to any one of claims 1 to 7.
  9. 　式（２）から（４）で表される化合物の群から選択された少なくとも１つの化合物を含有する、請求項８に記載の液晶組成物：
    Figure JPOXMLDOC01-appb-C000006
     式（２）から（４）において、
    　Ｒ11およびＲ12は独立して、炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの－ＣＨ2－は－Ｏ－で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく；
    　環Ｂ1、環Ｂ2、環Ｂ3、および環Ｂ4は独立して、１，４－シクロヘキシレン、１，４－フェニレン、２－フルオロ－１，４－フェニレン、２，５－ジフルオロ－１，４－フェニレン、またはピリミジン－２，５－ジイルであり；
    　Ｚ11、Ｚ12、およびＺ13は独立して、単結合、－ＣＯＯ－、－ＣＨ2ＣＨ2－、－ＣＨ＝ＣＨ－、または－Ｃ≡Ｃ－である。     The liquid crystal composition according to claim 8, containing at least one compound selected from the group of compounds represented by formulas (2) to (4):
    Figure JPOXMLDOC01-appb-C000006
     In equations (2) to (4),
    R 11 and R 12 independently represent alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one of —CH 2 — is replaced by —O— Well, in these groups at least one hydrogen may be replaced by fluorine;
    Ring B 1 , ring B 2 , ring B 3 and ring B 4 are each independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene, or pyrimidine-2,5-diyl;
    Z 11 , Z 12 and Z 13 are independently a single bond, -COO-, -CH 2 CH 2- , -CH = CH-, or -C≡C-.
  10. 　式（５）から（７）で表される化合物の群から選択された少なくとも１つの化合物を含有する、請求項８または９に記載の液晶組成物：
    Figure JPOXMLDOC01-appb-C000007
     式（５）から（７）において、
    　Ｒ13は炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの－ＣＨ2－は－Ｏ－で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく；
    　Ｘ11は、フッ素、塩素、－ＯＣＦ3、－ＯＣＨＦ2、－ＣＦ3、－ＣＨＦ2、－ＣＨ2Ｆ、－ＯＣＦ2ＣＨＦ2、または－ＯＣＦ2ＣＨＦＣＦ3であり；
    　環Ｃ1、環Ｃ2、および環Ｃ3は独立して、１，４－シクロヘキシレン、１，４－フェニレン、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、または少なくとも１つの水素がフッ素で置き換えられた１，４－フェニレンであり；
    　Ｚ14、Ｚ15、およびＺ16は独立して、単結合、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ2Ｏ－、－ＯＣＨ2－、－ＣＦ2Ｏ－、－ＯＣＦ2－、－ＣＨ2ＣＨ2－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、または－（ＣＨ2）4－であり；
    　Ｌ11およびＬ12は独立して、水素またはフッ素である。     10. The liquid crystal composition according to claim 8, which contains at least one compound selected from the group of compounds represented by formulas (5) to (7):
    Figure JPOXMLDOC01-appb-C000007
     In equations (5) to (7),
    R 13 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—, and in these groups, 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 ;
    Ring C 1 , ring C 2 and ring C 3 are independently 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl Pyrimidine-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine;
    Z 14, Z 15, and Z 16 are independently a single bond, -COO -, - OCO -, - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 -, - CH 2 CH 2 -, - CH = CH -, - C≡C-, or - (CH 2) 4 - a and;
    L 11 and L 12 are independently hydrogen or fluorine.
  11. 　式（８）で表される化合物の群から選択された少なくとも１つの化合物を含有する、請求項８から１０のいずれか１項に記載の液晶組成物：
    Figure JPOXMLDOC01-appb-C000008
     式（８）において、
    　Ｒ14は炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの－ＣＨ2－は－Ｏ－で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく；
    　Ｘ12は－Ｃ≡Ｎまたは－Ｃ≡Ｃ－Ｃ≡Ｎであり；
    　環Ｄ1は、１，４－シクロヘキシレン、１，４－フェニレン、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、または少なくとも１つの水素がフッ素で置き換えられた１，４－フェニレンであり；
    　Ｚ17は、単結合、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ2Ｏ－、－ＯＣＨ2－、－ＣＦ2Ｏ－、－ＯＣＦ2－、－ＣＨ2ＣＨ2－、または－Ｃ≡Ｃ－であり；
    　Ｌ13およびＬ14は独立して、水素またはフッ素であり；
    　ｉは、１、２、３、または４である。     The liquid crystal composition according to any one of claims 8 to 10, which contains at least one compound selected from the group of compounds represented by formula (8):
    Figure JPOXMLDOC01-appb-C000008
     In equation (8),
    R 14 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—, and in these groups, At least one hydrogen may be replaced by fluorine;
    X 12 is -C≡N or -C≡C-C≡N;
    Ring D 1 is 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or at least 1 Four hydrogens are substituted with fluorine and 1,4-phenylene;
    Z 17 represents a single bond, -COO-, -OCO-, -CH 2 O-, -OCH 2- , -CF 2 O-, -OCF 2- , -CH 2 CH 2- , or -C≡C- And
    L 13 and L 14 are independently hydrogen or fluorine;
    i is 1, 2, 3 or 4;
  12. 　式（１１）から（１９）で表される化合物の群から選択された少なくとも１つの化合物を含有する、請求項８から１１のいずれか１項に記載の液晶組成物：
    Figure JPOXMLDOC01-appb-C000009
     式（１１）から（１９）において、
    　Ｒ15、Ｒ16、およびＲ17は独立して、炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの－ＣＨ2－は－Ｏ－で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく、そしてＲ17は、水素またはフッ素であってもよく；
    　環Ｅ1、環Ｅ2、環Ｅ3、および環Ｅ4は独立して、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、テトラヒドロピラン－２，５－ジイル、デカヒドロナフタレン－２，６－ジイル、または少なくとも１つの水素がフッ素で置き換えられた１，４－フェニレンであり；
    　環Ｅ5および環Ｅ6は独立して、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、テトラヒドロピラン－２，５－ジイル、またはデカヒドロナフタレン－２，６－ジイルであり；
    　Ｚ18、Ｚ19、Ｚ20、およびＺ21は独立して、単結合、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ2Ｏ－、－ＯＣＨ2－、－ＣＦ2Ｏ－、－ＯＣＦ2－、－ＣＨ2ＣＨ2－、－ＣＦ2ＯＣＨ2ＣＨ2－、または－ＯＣＦ2ＣＨ2ＣＨ2－であり；
    　Ｌ15およびＬ16は独立して、フッ素または塩素であり；
    　Ｓ11は、水素またはメチルであり；
    　Ｘは、－ＣＨＦ－または－ＣＦ2－であり；
    　ｊ、ｋ、ｍ、ｎ、ｐ、ｑ、ｒ、およびｓは独立して、０または１であり、ｋ、ｍ、ｎ、およびｐの和は、１または２であり、ｑ、ｒ、およびｓの和は、０、１、２、または３であり、
    　ｔは、１、２、または３である。     The liquid crystal composition according to any one of claims 8 to 11, containing at least one compound selected from the group of compounds represented by formulas (11) to (19):
    Figure JPOXMLDOC01-appb-C000009
     In equations (11) to (19),
    R 15, R 16, and R 17 are independently alkenyl alkyl carbon atoms or 2 to 10 of 1 to 10 carbon atoms, in the alkyl and alkenyl, at least one of -CH 2 - by -O- Which may be replaced, in these groups at least one hydrogen may be replaced by fluorine, and R 17 may be hydrogen or fluorine;
    Ring E 1 , ring E 2 , ring E 3 and ring E 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl Decahydronaphthalene-2,6-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine;
    Ring E 5 and ring E 6 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6 -Is diil;
    Z 18, Z 19, Z 20 , and Z 21 are independently a single bond, -COO -, - OCO -, - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 -, -CH 2 CH 2- , -CF 2 OCH 2 CH 2- , or -OCF 2 CH 2 CH 2- ;
    L 15 and L 16 are independently fluorine or chlorine;
    S 11 is hydrogen or methyl;
    X is -CHF- or -CF 2- ;
    j, k, m, n, p, q, r, and s are independently 0 or 1, and the sum of k, m, n, and p is 1 or 2, q, r, and The sum of s is 0, 1, 2 or 3 and
    t is 1, 2 or 3.
  13. 　式（１）で表される化合物以外の、式（２０）で表される少なくとも１つの重合性化合物を含有する、請求項８から１２のいずれか１項に記載の液晶組成物：
    Figure JPOXMLDOC01-appb-C000010
     式（２０）において、
    　環Ｆおよび環Ｉは独立して、シクロヘキシル、シクロヘキセニル、フェニル、１－ナフチル、２－ナフチル、テトラヒドロピラン－２－イル、１，３－ジオキサン－２－イル、ピリミジン－２－イル、またはピリジン－２－イルであり、これらの環において、少なくとも１つの水素は、ハロゲン、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；
    　環Ｇは、１，４－シクロへキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－１，２－ジイル、ナフタレン－１，３－ジイル、ナフタレン－１，４－ジイル、ナフタレン－１，５－ジイル、ナフタレン－１，６－ジイル、ナフタレン－１，７－ジイル、ナフタレン－１，８－ジイル、ナフタレン－２，３－ジイル、ナフタレン－２，６－ジイル、ナフタレン－２，７－ジイル、フェナントレン－２，７－ジイル、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、またはピリジン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、ハロゲン、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；
    　Ｚ22およびＺ23は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ2ＣＨ2－は、－ＣＨ＝ＣＨ－、－Ｃ（ＣＨ3）＝ＣＨ－、－ＣＨ＝Ｃ（ＣＨ3）－、または－Ｃ（ＣＨ3）＝Ｃ（ＣＨ3）－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
    　Ｐ11、Ｐ12、およびＰ13は独立して、重合性基であり；
    　Ｓｐ11、Ｓｐ12、およびＳｐ13は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ2ＣＨ2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
    　ｕは、０、１、または２であり；
    　ｆ、ｇ、およびｈは独立して、０、１、２、３、または４であり、そしてｆ、ｇ、およびｈの和は、１以上である。     The liquid crystal composition according to any one of claims 8 to 12, containing at least one polymerizable compound represented by formula (20) other than the compound represented by formula (1):
    Figure JPOXMLDOC01-appb-C000010
     In equation (20),
    Ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl or pyridine -2-yl, in these rings, at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 1 carbon having at least one hydrogen replaced with halogen May be replaced by 12 alkyls;
    Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene- 2,7-diyl, phenanthrene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5- In these rings, at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one of Element may be replaced by alkyl having 1 carbon is replaced by a halogen 12;
    Z 22 and Z 23 are independently a single bond or alkylene having 1 to 10 carbons, and in this alkylene, at least one —CH 2 — is —O—, —CO—, —COO—, or — OCO- may be replaced, and at least one -CH 2 CH 2 -is -CH = CH-, -C (CH 3 ) = CH-, -CH = C (CH 3 )-, or -C ( CH 3 ) = C (CH 3 ) — may be replaced and in these groups at least one hydrogen may be replaced by fluorine or chlorine;
    P 11 , P 12 and P 13 are independently polymerizable groups;
    Sp 11 , Sp 12 and Sp 13 independently represent a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —COO—, —OCO At least one of —CH 2 CH 2 — may be replaced by —CH = CH— or —C≡C—, and at least one of these groups may be replaced by Hydrogen may be replaced by fluorine or chlorine;
    u is 0, 1 or 2;
    f, g and h are independently 0, 1, 2, 3 or 4 and the sum of f, g and h is 1 or more.
  14. 　式（２０）において、
    　Ｐ11、Ｐ12、およびＰ13が独立して、式（Ｐ－１）から式（Ｐ－５）で表される重合性基の群から選択された基である、請求項１３に記載の液晶組成物：
    Figure JPOXMLDOC01-appb-C000011
     式（Ｐ－１）から式（Ｐ－５）において、
    　Ｍ11、Ｍ12、およびＭ13は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から５のアルキルである。     In equation (20),
    14. The method according to claim 13 , wherein P 11 , P 12 and P 13 are independently a group selected from the group of polymerizable groups represented by formulas (P-1) to (P-5). Liquid crystal composition:
    Figure JPOXMLDOC01-appb-C000011
     In formulas (P-1) to (P-5),
    M 11 , M 12 and M 13 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen.
  15. 　式（２０）で表される重合性化合物が、式（２０－１）から式（２０－７）で表される重合性化合物の群から選択された少なくとも１つの化合物である、請求項１３または１４に記載の液晶組成物：
    Figure JPOXMLDOC01-appb-C000012
     式（２０－１）から式（２０－７）において、
    　Ｌ31、Ｌ32、Ｌ33、Ｌ34、Ｌ35、Ｌ36、Ｌ37、およびＬ38は独立して、水素、フッ素、またはメチルであり；
    　Ｓｐ11、Ｓｐ12、およびＳｐ13は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ2ＣＨ2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
    　Ｐ11、Ｐ12、およびＰ13は独立して、式（Ｐ－１）から式（Ｐ－３）で表される重合性基の群から選択された基であり、
    Figure JPOXMLDOC01-appb-C000013
     式（Ｐ－１）から式（Ｐ－３）において、
    　Ｍ11、Ｍ12、およびＭ13は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から５のアルキルである。     The polymerizing compound represented by the formula (20) is at least one compound selected from the group of polymerizing compounds represented by the formulas (20-1) to (20-7). The liquid crystal composition according to 14:
    Figure JPOXMLDOC01-appb-C000012
     In formulas (20-1) to (20-7),
    L 31 , L 32 , L 33 , L 34 , L 35 , L 36 , L 37 and L 38 are independently hydrogen, fluorine or methyl;
    Sp 11 , Sp 12 and Sp 13 independently represent a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —COO—, —OCO At least one of —CH 2 CH 2 — may be replaced by —CH = CH— or —C≡C—, and at least one of these groups may be replaced by Hydrogen may be replaced by fluorine or chlorine;
    P 11 , P 12 and P 13 independently represent a group selected from the group of polymerizable groups represented by Formula (P-1) to Formula (P-3),
    Figure JPOXMLDOC01-appb-C000013
     In formulas (P-1) to (P-3),
    M 11 , M 12 and M 13 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen.
  16. 　式（１）および式（２０）で表される化合物とは異なる重合性化合物、重合開始剤、重合禁止剤、光学活性化合物、酸化防止剤、紫外線吸収剤、光安定剤、熱安定剤、色素、ならびに消泡剤の群から選択された少なくとも１つを含有する、請求項８から１５のいずれか１項に記載の液晶組成物：
    Figure JPOXMLDOC01-appb-C000014
     式（２０）において、
    　環Ｆおよび環Ｉは独立して、シクロヘキシル、シクロヘキセニル、フェニル、１－ナフチル、２－ナフチル、テトラヒドロピラン－２－イル、１，３－ジオキサン－２－イル、ピリミジン－２－イル、またはピリジン－２－イルであり、これらの環において、少なくとも１つの水素は、ハロゲン、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；
    　環Ｇは、１，４－シクロへキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－１，２－ジイル、ナフタレン－１，３－ジイル、ナフタレン－１，４－ジイル、ナフタレン－１，５－ジイル、ナフタレン－１，６－ジイル、ナフタレン－１，７－ジイル、ナフタレン－１，８－ジイル、ナフタレン－２，３－ジイル、ナフタレン－２，６－ジイル、ナフタレン－２，７－ジイル、フェナントレン－２，７－ジイル、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、またはピリジン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、ハロゲン、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；
    　Ｚ22およびＺ23は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ2ＣＨ2－は、－ＣＨ＝ＣＨ－、－Ｃ（ＣＨ3）＝ＣＨ－、－ＣＨ＝Ｃ（ＣＨ3）－、または－Ｃ（ＣＨ3）＝Ｃ（ＣＨ3）－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
    　Ｐ11、Ｐ12、およびＰ13は独立して、重合性基であり；
    　Ｓｐ11、Ｓｐ12、およびＳｐ13は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ2－は、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ2ＣＨ2－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
    　ｕは、０、１、または２であり；
    　ｆ、ｇ、およびｈは独立して、０、１、２、３、または４であり、そしてｆ、ｇ、およびｈの和は、１以上である。     Polymerizable compounds different from the compounds represented by the formulas (1) and (20), polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dyes The liquid crystal composition according to any one of claims 8 to 15, containing at least one selected from the group of antifoaming agents, and:
    Figure JPOXMLDOC01-appb-C000014
     In equation (20),
    Ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl or pyridine -2-yl, in these rings, at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 1 carbon having at least one hydrogen replaced with halogen May be replaced by 12 alkyls;
    Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene- 2,7-diyl, phenanthrene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5- In these rings, at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one of Element may be replaced by alkyl having 1 carbon is replaced by a halogen 12;
    Z 22 and Z 23 are independently a single bond or alkylene having 1 to 10 carbons, and in this alkylene, at least one —CH 2 — is —O—, —CO—, —COO—, or — OCO- may be replaced, and at least one -CH 2 CH 2 -is -CH = CH-, -C (CH 3 ) = CH-, -CH = C (CH 3 )-, or -C ( CH 3 ) = C (CH 3 ) — may be replaced and in these groups at least one hydrogen may be replaced by fluorine or chlorine;
    P 11 , P 12 and P 13 are independently polymerizable groups;
    Sp 11 , Sp 12 and Sp 13 independently represent a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —COO—, —OCO At least one of —CH 2 CH 2 — may be replaced by —CH = CH— or —C≡C—, and at least one of these groups may be replaced by Hydrogen may be replaced by fluorine or chlorine;
    u is 0, 1 or 2;
    f, g and h are independently 0, 1, 2, 3 or 4 and the sum of f, g and h is 1 or more.
  17. 　請求項８から１６のいずれか１項に記載の液晶組成物、および請求項８から１６のいずれか１項に記載の液晶組成物の少なくとも一部が重合したものからなる群より選択された少なくとも１つ含有する液晶表示素子。 17. At least one selected from the group consisting of the liquid crystal composition according to any one of claims 8 to 16, and at least a part of the liquid crystal composition according to any one of claims 8 to 16 polymerized. Liquid crystal display element containing one.
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