WO2017068875A1 - Composition de cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

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

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WO2017068875A1
WO2017068875A1 PCT/JP2016/075972 JP2016075972W WO2017068875A1 WO 2017068875 A1 WO2017068875 A1 WO 2017068875A1 JP 2016075972 W JP2016075972 W JP 2016075972W WO 2017068875 A1 WO2017068875 A1 WO 2017068875A1
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liquid crystal
hydrogen
carbons
fluorine
alkyl
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PCT/JP2016/075972
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English (en)
Japanese (ja)
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将之 齋藤
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Jnc株式会社
Jnc石油化学株式会社
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Priority to CN201680062374.3A priority Critical patent/CN108350362A/zh
Priority to KR1020187009221A priority patent/KR20180074672A/ko
Priority to JP2017546447A priority patent/JPWO2017068875A1/ja
Publication of WO2017068875A1 publication Critical patent/WO2017068875A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—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
    • 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
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • 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
    • 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
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

  • the present invention relates to a liquid crystal composition, a liquid crystal display element containing the composition, and the like.
  • a liquid crystal composition containing a polar compound and a polymerizable compound (or a polymer thereof) and capable of achieving vertical alignment of liquid crystal molecules by the action of these compounds and having a negative dielectric anisotropy, and a liquid crystal display It relates to an element.
  • the classification based on the operation mode of the liquid crystal molecules is as follows: 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) mode.
  • the classification based on the element drive system is PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into TFT (thin film insulator), MIM (metal film insulator), and the like. TFTs are classified into amorphous silicon and polycrystalline silicon. The latter is classified into a high temperature type and a low temperature type according to the manufacturing process.
  • the classification based on the light source includes a reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both natural light and backlight.
  • the liquid crystal display element contains a liquid crystal composition having a nematic phase.
  • This composition has suitable properties. By improving the characteristics of the composition, an AM device having good characteristics can be obtained. The relationship between the two characteristics is summarized in Table 1 below. The characteristics of the composition will be further described based on a commercially available AM device.
  • the temperature range of the nematic phase is related to the temperature range in which the device can be used.
  • a preferred upper limit temperature of the nematic phase is about 70 ° C. or more, and a preferred lower limit temperature of the nematic phase is about ⁇ 10 ° C. or less.
  • the viscosity of the composition is related to the response time of the device. A short response time is preferred for displaying moving images on the device. A shorter response time is desirable even at 1 millisecond. Therefore, a small viscosity in the composition is preferred. A small viscosity at low temperatures is even more preferred.
  • the optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large optical anisotropy or a small optical anisotropy, ie an appropriate 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 value for the product depends on the type of operating mode. This value is in the range of about 0.30 ⁇ m to about 0.40 ⁇ m for the VA mode element and in the range of about 0.20 ⁇ m to about 0.30 ⁇ m for the IPS mode or FFS mode element.
  • a composition having a large optical anisotropy is preferable for a device having a small cell gap.
  • a large dielectric anisotropy in the composition contributes to a low threshold voltage, a small power consumption and a large contrast ratio in the device. Therefore, a large dielectric anisotropy is preferable.
  • a large specific resistance 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 not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase in the initial stage is preferable.
  • 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 after being used for a long time 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 device used in a liquid crystal projector, a liquid crystal television, and 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.
  • the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of the device.
  • the polymerizable compound polymerizes to form a polymer network in the composition.
  • the response time of the device is shortened, and image burn-in is improved.
  • Such an effect of the polymer can be expected for a device having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
  • a liquid crystal composition containing a polymer and a polar compound is used.
  • a composition to which a small amount of a polymerizable compound and a small amount of a polar compound are added is injected into the device.
  • polar compounds are adsorbed and arranged on the substrate surface.
  • the liquid crystal molecules are aligned according to this arrangement.
  • the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of the device.
  • the polymerizable compound is polymerized to stabilize the alignment of the liquid crystal molecules.
  • the orientation of liquid crystal molecules can be controlled by the polymer and the polar compound, the response time of the device is shortened, and image burn-in 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 electrical resistance of the device does not decrease due to the interaction between the alignment film and the composition. Such an effect by the combination of the polymer and the polar compound can be expected for a device having a mode such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
  • a mode such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
  • a composition having a positive dielectric anisotropy is used for an AM device having a TN mode.
  • a composition having a negative dielectric anisotropy is used in an AM device having a VA mode.
  • a composition having a positive or negative dielectric anisotropy is used in an AM device having an IPS mode or an FFS mode.
  • a composition having positive or negative dielectric anisotropy is used in a polymer-supported orientation type AM device.
  • liquid crystal compositions having negative dielectric anisotropy are disclosed in the following Patent Documents 1 to 6.
  • a polar compound and a polymerizable compound (or a polymer thereof) are combined with a liquid crystal compound, and this composition is used for a liquid crystal display element having no alignment film.
  • One object of the present invention is a liquid crystal composition containing a polar compound and a polymerizable compound (or a polymer thereof), wherein the polar compound has high compatibility with the liquid crystal compound.
  • Another object is a liquid crystal composition capable of achieving vertical alignment of liquid crystal molecules by the action of the polymer.
  • Other objectives are: high maximum temperature of nematic phase, low minimum temperature of nematic phase, small viscosity, appropriate optical anisotropy, negatively large dielectric anisotropy, large specific resistance, high stability against ultraviolet rays, high heat resistance It is a liquid crystal composition satisfying at least one characteristic in characteristics such as high stability.
  • Another object is a liquid crystal composition having an appropriate balance between at least two properties.
  • Another object is a liquid crystal display device containing such a composition.
  • Another object is an AM device having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime.
  • the present invention comprises a compound represented by the formula (1) as a first component, a polar compound as a first additive, and a polymerizable compound as a second additive, and having a negative dielectric anisotropy A composition and a liquid crystal display device containing the composition.
  • R 1 is alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine;
  • R 2 is having 1 to 12 carbons Alkyl, 1 to 12 carbon alkoxy, 2 to 12 alkenyl, or 2 to 12 alkenyloxy;
  • ring A and ring C are each independently 1,4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, at least one Naphthalene-2,6-diyl, chroman-2,6-diyl, in which hydrogen is replaced by fluorine or chlorine, or at least one Chroman-2,6-diyl substituted with fluorine or chlorine;
  • ring B is 2,3-difluoro-1,4
  • One advantage of the present invention is a liquid crystal composition containing a polar compound and a polymerizable compound (or a polymer thereof), wherein the polar compound has high compatibility with the liquid crystal compound.
  • Another advantage is a liquid crystal composition capable of achieving vertical alignment of liquid crystal molecules by the action of the polymer.
  • Another advantage is the high maximum temperature of the nematic phase, low minimum temperature of the nematic phase, small viscosity, suitable optical anisotropy, negative large dielectric anisotropy, large specific resistance, high stability against ultraviolet rays, high heat resistance
  • It is a liquid crystal composition satisfying at least one characteristic in characteristics such as high stability.
  • Another advantage is a liquid crystal composition having an appropriate balance between at least two properties.
  • Another advantage is a liquid crystal display device containing such a composition.
  • Another advantage is an AM device having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime.
  • liquid crystal composition and “liquid crystal display element” may be abbreviated as “composition” and “element”, respectively.
  • “Liquid crystal display element” is a general term for liquid crystal display panels and liquid crystal display modules.
  • “Liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and a liquid crystal phase, but has a composition for the purpose of adjusting characteristics such as temperature range, viscosity, and dielectric anisotropy of the nematic phase. It is a general term for compounds mixed with products.
  • This compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-like.
  • the “polymerizable compound” is a compound added for the purpose of forming a polymer in the composition.
  • the liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are added to this liquid crystal composition as necessary.
  • the Liquid crystal compounds and additives are mixed in such a procedure.
  • the ratio (content) of the liquid crystal compound is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition not containing the additive even when the additive is added.
  • the ratio (addition amount) of the additive is expressed as a percentage by weight (% by weight) based on the weight of the liquid crystal composition not containing the additive. Weight parts per million (ppm) may be used.
  • the ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.
  • the upper limit temperature of the nematic phase may be abbreviated as “the upper limit temperature”.
  • “Lower limit temperature of nematic phase” may be abbreviated as “lower limit temperature”.
  • High specific resistance means that the composition has a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature after long-term use. It means having.
  • “High voltage holding ratio” 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 temperature in the initial stage, and a large voltage not only at room temperature but also at a temperature close to the upper limit temperature after long-term use.
  • compositions or devices characteristics may be examined before and after a aging test (including an accelerated deterioration test).
  • the expression “increasing dielectric anisotropy” means that when the composition has a positive dielectric anisotropy, the value increases positively, and the composition having a negative dielectric anisotropy When it is a thing, it means that the value increases negatively.
  • the compound represented by the formula (1) may be abbreviated as “compound (1)”. At least one compound selected from the group of compounds represented by formula (1) may be abbreviated as “compound (1)”. “Compound (1)” means one compound represented by formula (1), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas.
  • 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'” means that when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is 2 Even when there are more than two, their positions can be selected without restriction. This rule also applies to the expression “at least one 'A' is replaced by 'B'".
  • Expressions such as “at least one —CH 2 — may be replaced by —O—” are used herein.
  • —CH 2 —CH 2 —CH 2 — may be converted to —O—CH 2 —O— by replacing non-adjacent —CH 2 — with —O—.
  • adjacent —CH 2 — is not replaced by —O—.
  • —O—O—CH 2 — (peroxide) is formed by this replacement. That is, this expression includes both “one —CH 2 — may be replaced with —O—” and “at least two non-adjacent —CH 2 — may be replaced with —O—”. means.
  • This rule applies not only to replacement with —O— but also to replacement with a divalent group such as —CH ⁇ CH— or —COO—.
  • alkyl at least one —CH 2 — may be replaced by a cycloalkylene having 3 to 8 carbon atoms. The carbon number of such alkyl increases with this type of replacement. In such a case, the maximum carbon number is 30.
  • This rule applies not only to monovalent groups such as alkyl, but also to divalent groups such as alkylene.
  • the symbol of the terminal group R 2 is used for a plurality of compounds.
  • two groups represented by any two R 2 may be the same or different.
  • R 2 of the compound (1-1) is ethyl and R 2 of the compound (1-2) is ethyl.
  • R 2 of compound (1-1) is ethyl and R 2 of compound (1-2) is propyl.
  • This rule also applies to symbols such as other end groups.
  • Formula (1) when a is 2, two rings A exist. In this compound, the two rings represented by the two rings A may be the same or different. This rule also applies to any two rings A when a is greater than 2. This rule also applies to other symbols.
  • This rule also applies to the case of two -Sp 10 -P 5 in the compound (6-27).
  • Symbols such as A, B, C, and D surrounded by hexagons correspond to rings such as ring A, ring B, ring C, and ring D, respectively, and represent rings such as six-membered rings and condensed rings.
  • oblique lines crossing the hexagon represents that any hydrogen on the ring may be substituted with groups such as -Sp 10 -P 5.
  • a subscript such as “v” indicates the number of replaced groups. When the subscript 'v' is 0, there is no such replacement. When the subscript 'v' is 2 or more, there are a plurality of -Sp 10 -P 5 on the ring U.
  • the plurality of groups represented by —Sp 10 —P 5 may be the same or different.
  • ring A and ring C are independently X, Y, or Z”, “independently” is used because there are plural subjects. When the subject is “ring A is”, “independently” is not used because the subject is singular.
  • Ring A is used in a plurality of formulas, the rule “may be the same or different” applies to “Ring A”. The same applies to other groups.
  • 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 divalent groups generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl.
  • This rule also applies to divalent linking groups such as carbonyloxy (—COO— or —OCO—).
  • the alkyl of the liquid crystal compound is linear or branched and does not include cyclic alkyl. Linear alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl.
  • the configuration of 1,4-cyclohexylene is generally preferably trans rather than cis.
  • the present invention includes the following items.
  • a liquid crystal composition comprising a compound represented by formula (1) as a first component, a polar compound as a first additive, and a polymerizable compound as a second additive, and having negative dielectric anisotropy.
  • R 1 is alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine
  • R 2 is having 1 to 12 carbons Alkyl, 1 to 12 carbon alkoxy, 2 to 12 alkenyl, or 2 to 12 alkenyloxy
  • ring A and ring C are each independently 1,4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, at least one Naphthalene-2,6-diyl, chroman-2,6-d
  • Item 2. The liquid crystal composition according to item 1, comprising a compound selected from the group of compounds represented by formula (1-1) to formula (1-21) as a first component.
  • R 1 is alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine;
  • R 2 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons.
  • Item 3. The liquid crystal composition according to item 1 or 2, wherein the ratio of the first component is in the range of 5% to 85% by weight based on the weight of the liquid crystal composition.
  • Item 4. The liquid crystal composition according to any one of items 1 to 3, comprising a compound represented by formula (2) as a second component.
  • R 3 and R 4 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen is fluorine or chlorine.
  • ring D and ring E are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5 -Difluoro-1,4-phenylene;
  • Z 3 is a single bond, -CH 2 CH 2- , -CH 2 O-, -OCH 2- , -COO-, or -OCO-; 1, 2, or 3.
  • Item 5. The liquid crystal composition according to any one of items 1 to 4, comprising a compound selected from the group of compounds represented by formulas (2-1) to (2-13) as the second component.
  • R 3 and R 4 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or C2-C12 alkenyl in which at least one hydrogen is replaced by fluorine or chlorine.
  • Item 6. The liquid crystal composition according to item 4 or 5, wherein the ratio of the second component is in the range of 5% to 65% by weight based on the weight of the liquid crystal composition.
  • Item 7. The liquid crystal composition according to any one of items 1 to 6, comprising a compound represented by formula (3) as a third component.
  • R 5 and R 6 are independently alkyl having 1 to 12 carbons or alkoxy having 1 to 12 carbons;
  • ring F and ring I are independently 1,4-cyclohexylene 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, Naphthalene-2,6-diyl, chroman-2,6-diyl, in which at least one hydrogen is replaced by fluorine or chlorine, or chroman-2,6-diyl, in which at least one hydrogen is replaced by fluorine or chlorine Ring G is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-pheny
  • Item 8. The liquid crystal composition according to any one of items 1 to 7, comprising a compound selected from the group of compounds represented by formulas (3-1) to (3-21) as a third component.
  • R 5 and R 6 are independently alkyl having 1 to 12 carbons or alkoxy having 1 to 12 carbons.
  • Item 9 The liquid crystal composition according to item 7 or 8, wherein the ratio of the third component is in the range of 5% by weight to 60% by weight based on the weight of the liquid crystal composition.
  • Item 10 The liquid crystal composition according to any one of items 1 to 9, comprising a polar compound having a polar group containing a hetero atom selected from nitrogen, oxygen, sulfur, and phosphorus as the first additive.
  • Item 11 The liquid crystal composition according to any one of items 1 to 10, comprising a polar compound selected from the group of compounds represented by formula (4) and formula (5) as a first additive.
  • MES is a mesogenic group having at least one ring
  • R 7 is alkyl having 4 to 20 carbon atoms, and in this alkyl, at least one —CH 2 — May be replaced with —CH ⁇ CH—, —CF ⁇ CH—, —CH ⁇ CF—, —C ⁇ C—, or cycloalkylene having 3 to 8 carbon atoms, and in these groups, at least one of Hydrogen may be replaced by fluorine or chlorine
  • R 8 is an oxygen atom of OH structure, a sulfur atom of SH structure, and primary, secondary, or primary A polar group having at least one nitrogen atom of a tertiary amine structure; x is 1 or 2.
  • Item 12. The liquid crystal composition according to any one of items 1 to 11, comprising a polar compound represented by formula (4-1) as a first additive.
  • R 9 is hydrogen, fluorine, chlorine, or alkyl having 1 to 25 carbons, and in this alkyl, at least one —CH 2 — is —NR 0 —, —O—.
  • the tertiary carbon (> CH—) may be replaced with nitrogen (> N—), in which at least one hydrogen may be replaced with fluorine or chlorine, where R 0 is Hydrogen or alkyl having 1 to 12 carbons; R 10 is alkyl having 1 to 25 carbons, in which at least one —CH 2 — is —NR 0 —, —O—, —S -, -CO-, -COO , —OCO—, —OCOO—, or a cycloalkylene having 3 to 8 carbon atoms, and at least one tertiary carbon (> CH—) may be replaced with nitrogen (> N—) In these groups, at least one hydrogen may be replaced by fluorine or chlorine, where R 0 is hydrogen or alkyl having 1 to 12 carbon
  • Both may be one hydrogen replaced with a group T, wherein the group T is, -OH, - (CH 2) i -OH, fluorine, chlorine, -CN, -NO 2, -NCO, -NCS, - OCN, —SCN, —C ( ⁇ O) N (R 0 ) 2 , —C ( ⁇ O) R 0 , —N (R 0 ) 2 , — (CH 2 ) i —N (R 0 ) 2 , carbon Aryl having 6 to 20 carbon atoms, heteroaryl having 6 to 20 carbon atoms, alkyl having 1 to 25 carbon atoms, alkoxy having 1 to 25 carbon atoms, alkylcarbonyl having 2 to 25 carbon atoms, alkoxycarbonyl having 2 to 25 carbon atoms, an alkoxycarbonyloxy alkylcarbonyloxy or 2 to 25 carbon atoms, from 25 to 2 carbon atoms, and in the groups, at least one hydrogen may
  • Item 13 The liquid crystal composition according to any one of items 1 to 12, comprising a polar compound represented by formula (5-1) as a first additive.
  • R 13 is alkyl having 4 to 20 carbon atoms, and in this alkyl, at least one —CH 2 — is —CH ⁇ CH—, —CF ⁇ CH—, —CH ⁇ .
  • CF—, —C ⁇ C—, or cycloalkylene having 3 to 8 carbon atoms may be substituted, and in these groups, at least one hydrogen may be replaced with fluorine or chlorine;
  • R 14 is carbon In the alkyl, at least one —CH 2 — is —NR 0 —, —O—, —S—, —CO—, —COO—, —OCO—, —OCOO— Or at least one tertiary carbon (> CH—) may be replaced with nitrogen (> N—), and in these groups, Least one hydrogen may be replaced by fluorine or chlorine, wherein R 0 is hydrogen or alkyl having 1 to 12 carbon atoms, provided that R 14 is an oxygen atom of the OH structure, the sulfur atom of the SH structure And at least one nitrogen atom of a primary, secondary, or tertiary amine structure.
  • Item 14 The formula (4) and the formula (5) according to item 11, wherein R 8 is a monovalent group selected from the group of groups represented by formula (A1) to formula (A4). Liquid crystal composition.
  • Sp 4 , Sp 6 , and Sp 7 are independently a single bond or a group (—Sp ′′ —X ′′ —), where Sp ′′ is , Alkylene having 1 to 20 carbon atoms, wherein at least one —CH 2 — is —O—, —S—, —NH—, —N (R 0 ) —, —CO—, —CO—.
  • Item 15. The liquid crystal composition according to item 11 or 12, wherein the first additive is a compound selected from the group of compounds represented by formula (4-1-1) to formula (4-1-4).
  • R 15 is alkyl having 1 to 8 carbons or fluorine; and the ring Q and the ring R are independently 1,4-cyclohexene.
  • Silene 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-fluoro-1,3-phenylene, 2-ethyl-1,4-phenylene, 2,6-diethyl-1,4-phenylene, 2-trifluoromethyl-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, or 2 , 3,5,6-tetrafluoro-1,4-phenylene; ring S is cyclohexyl or phenyl; Z 10 is a single bond, —CH 2 CH 2 —, —COO—, or —OCO—.
  • Z 11 is A single bond, an alkylene having 1 to 15 carbon atoms, an alicyclic group having 5 or 6 carbon atoms, or a combination thereof, in which at least one hydrogen is —OH, —OR a1 , —COOH , —NH 2 , —NHR a1 , —N (R a1 ) 2 , fluorine, or chlorine, where R a1 is alkyl having 1 to 15 carbons, and in this alkyl, at least 1 Two —CH 2 — may be replaced by —C ⁇ C—, —CH ⁇ CH—, —COO—, —OCO—, —CO—, or —O—, and in these groups, at least one Hydrogen may be replaced by fluorine or chlorine; Sp 4 is a single bond, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 O—, or —OCH 2 —; Sp 7 is a single bond or alkylene having 1 to 5
  • Item 16 The liquid crystal composition according to item 11 or 13, wherein the first additive is a compound selected from the group of compounds represented by formulas (5-1-1) to (5-1-29).
  • Item 17. The liquid crystal composition according to any one of items 1 to 16, wherein the ratio of the first additive is in the range of 0.05% by weight to 10% by weight based on the weight of the liquid crystal composition.
  • Item 18. The liquid crystal composition according to any one of items 1 to 17, comprising a polymerizable compound represented by formula (6) as the second additive.
  • ring T and ring V are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine- 2-yl or pyridin-2-yl, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen.
  • ring U may be 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, -Diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5- Diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5- Diyl, 1,3-dioxane-2,5-
  • P 4 , P 5 and P 6 are each independently selected from the group of groups represented by formula (P-1) to formula (P-5) Item 19.
  • M 1 , M 2 , and M 3 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is fluorine or chlorine 1-5 alkyl substituted with
  • Item 20 The liquid crystal composition according to any one of items 1 to 19, comprising a polymerizable compound selected from the group of compounds represented by formulas (6-1) to (6-28) as a second additive. object.
  • P 4 , P 5 , and P 6 are independently from the group of groups represented by formula (P-1) to formula (P-3).
  • Sp 9 , Sp 10 , and Sp 11 are each independently a single bond or alkylene having 1 to 10 carbons, in which at least one —CH 2 — is —O—, —COO—, —; OCO—, or —OCOO— may be replaced, and at least one —CH 2 CH 2 — may be replaced with —CH ⁇ CH— or —C ⁇ C—, and in these groups, at least One hydrogen may be replaced with fluorine or chlorine.
  • Item 21 The liquid crystal composition according to any one of items 18 to 20, wherein the ratio of the second additive is in the range of 0.03% by weight to 10% by weight based on the weight of the liquid crystal composition.
  • Item 22 A liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 21.
  • Item 23 The liquid crystal display device according to item 22, wherein the operation mode of the liquid crystal display device is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and the driving method of the liquid crystal display device is an active matrix method.
  • Item 24 A liquid crystal display element of a polymer-supported alignment type, comprising the liquid crystal composition according to any one of items 1 to 21, wherein a polymerizable compound in the liquid crystal composition is polymerized.
  • Item 25 Item 21.
  • a liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 21 and having no alignment film, wherein the polymerizable compound in the liquid crystal composition is polymerized.
  • Item 26 Item 21. Use of the liquid crystal composition according to any one of items 1 to 21 in a liquid crystal display device.
  • Item 27 Item 21. Use of the liquid crystal composition according to any one of items 1 to 21 in a polymer supported alignment type liquid crystal display element.
  • Item 28 Item 21. Use of the liquid crystal composition according to any one of items 1 to 21 in a liquid crystal display device having no alignment film.
  • the present invention includes the following items.
  • (A) The liquid crystal composition described above is placed between two substrates, light is applied to the composition while voltage is applied, and the polymerizable compound contained in the composition is polymerized, thereby Of manufacturing a liquid crystal display element.
  • (B) The upper limit temperature of the nematic phase is 70 ° C or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C) is 0.08 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C) ) Is ⁇ 2 or less.
  • the present invention includes the following items.
  • the compounds (5) to (7) described in JP-A-2006-199941 are liquid crystal compounds having positive dielectric anisotropy, but at least selected from the group of these compounds A composition as described above containing one compound.
  • the above composition comprising at least two of the above polar compounds.
  • the above composition further comprising a polar compound different from the above polar compound.
  • One, two, or at least three of additives such as optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds A composition as described above containing one.
  • An AM device containing the above composition.
  • (H) A device containing the above composition and having a TN, ECB, OCB, IPS, FFS, VA, or FPA mode.
  • (I) A transmissive element containing the above composition.
  • (J) The above composition is used as a composition having a nematic phase.
  • (K) Use as an optically active composition by adding an optically active compound to the above composition.
  • composition of the present invention will be described in the following order. First, the composition of the composition will be described. Second, the main characteristics of the component compounds and the main effects of the compounds on the composition will be explained. Third, the combination of components in the composition, the preferred ratio of the components, and the basis thereof will be described. Fourth, a preferred form of the component compound will be described. Fifth, preferred component compounds are shown. Sixth, additives that may be added to the composition will be described. Seventh, a method for synthesizing the component compounds will be described. Finally, the use of the composition will be described.
  • composition of the composition will be explained.
  • the composition of the present invention is classified into Composition A and Composition B.
  • the composition A may further contain other liquid crystal compounds, additives and the like in addition to the liquid crystal compounds selected from the compound (1), the compound (2), and the compound (3).
  • the “other liquid crystal compound” is a liquid crystal compound different from the compound (1), the compound (2), and the compound (3).
  • Such compounds are mixed into the composition for the purpose of further adjusting the properties.
  • Additives include optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like.
  • Composition B consists essentially of a liquid crystalline compound selected from compound (1), compound (2), and compound (3). “Substantially” means that the composition may contain an additive but no other liquid crystal compound. Composition B has fewer components than composition A. From the viewpoint of reducing the cost, the composition B is preferable to the composition A. The composition A is preferable to the composition B from the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds.
  • the main characteristics of the component compounds and the main effects of the compounds on the characteristics of the composition will be explained.
  • the main characteristics of the component compounds are summarized in Table 2 based on the effects of the present invention.
  • L means large or high
  • M means moderate
  • S means small or low.
  • L, M, and S are classifications based on a qualitative comparison among the component compounds, and the symbol 0 means that the value is zero or close to zero.
  • the main effects of the component compound on the properties of the composition are as follows.
  • Compound (1) increases the dielectric anisotropy.
  • Compound (2) decreases the viscosity.
  • Compound (3) increases the dielectric anisotropy and decreases the minimum temperature.
  • the compound (4) or the compound (5) is adsorbed on the substrate surface by the action of the polar group and controls the alignment of the liquid crystal molecules. In order to obtain the desired effect, it is essential that these compounds have high compatibility with liquid crystal compounds.
  • Compound (6) gives a polymer by polymerization. This polymer stabilizes the alignment of the liquid crystal molecules, thereby reducing the response time of the device and improving image burn-in.
  • a preferred combination of components in the composition is compound (1) + compound (2), compound (1) + compound (2) + compound (3).
  • a more preferred combination is compound (1) + compound (2) + compound (3).
  • a desirable ratio of compound (1) is approximately 5% by weight or more for increasing the dielectric anisotropy, and approximately 85% by weight or less for decreasing the viscosity.
  • a more desirable ratio is in the range of approximately 10% by weight to approximately 80% by weight.
  • a particularly preferred ratio is in the range of approximately 15% by weight to approximately 75% by weight.
  • a desirable ratio of the compound (2) is approximately 5% by weight or more for increasing the maximum temperature or decreasing the viscosity, and approximately 65% by weight or less for increasing the dielectric anisotropy.
  • a more desirable ratio is in the range of approximately 10% by weight to approximately 60% by weight.
  • a particularly preferred ratio is in the range of approximately 15% by weight to approximately 55% by weight.
  • a desirable ratio of the compound (3) is approximately 5% by weight or more for increasing the dielectric anisotropy, and approximately 60% by weight or less for decreasing the minimum temperature.
  • a more desirable ratio is in the range of approximately 5% by weight to approximately 50% by weight.
  • a particularly preferred ratio is in the range of approximately 5% by weight to approximately 45% by weight.
  • Compound (4) and Compound (5) are added to the composition for the purpose of controlling the alignment of liquid crystal molecules.
  • a desirable ratio of compound (4) or compound (5) is approximately 0.05% by weight or more for aligning liquid crystal molecules, and approximately 10% by weight or less for preventing display defects of the device.
  • a more desirable ratio is in the range of approximately 0.1% by weight to approximately 7% by weight.
  • a particularly desirable ratio is in the range of approximately 0.5% by weight to approximately 5% by weight.
  • Compound (6) is added to the composition for the purpose of adapting to a polymer-supported orientation type device.
  • a desirable ratio of compound (6) is approximately 0.03% by weight or more for improving the long-term reliability of the element, and approximately 10% by weight or less for preventing display defects of the element.
  • a more desirable ratio is in the range of approximately 0.1% by weight to approximately 2% by weight.
  • a particularly preferred ratio is in the range of approximately 0.2% by weight to approximately 1.0% by weight.
  • R 1 is alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. is there.
  • R 2 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons. Desirable R 2 is alkyl having 1 to 12 carbons for increasing the stability, and alkoxy having 1 to 12 carbons for increasing the dielectric anisotropy.
  • R 3 and R 4 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon 2 having at least one hydrogen replaced with fluorine or chlorine.
  • Desirable R 3 or R 4 is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat, and alkenyl having 2 to 12 carbons for decreasing the minimum temperature or decreasing the viscosity.
  • R 5 and R 6 are independently alkyl having 1 to 12 carbons or alkoxy having 1 to 12 carbons. Desirable R 5 or R 6 is alkyl having 1 to 12 carbons for increasing the stability, and alkoxy having 1 to 12 carbons for increasing the dielectric anisotropy.
  • the alkyl of the liquid crystal compound is linear or branched and does not include cyclic alkyl. Linear alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl.
  • Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More desirable alkyl is ethyl, propyl, butyl, pentyl, or heptyl for decreasing the viscosity.
  • Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. More desirable alkoxy is methoxy or ethoxy for decreasing the viscosity.
  • Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More desirable alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for decreasing the viscosity.
  • the preferred configuration of —CH ⁇ CH— in these alkenyls depends on the position of the double bond.
  • Trans is preferable in alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity.
  • Cis is preferred for alkenyl such as 2-butenyl, 2-pentenyl, and 2-hexenyl.
  • Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. More preferable alkenyloxy is allyloxy or 3-butenyloxy for decreasing the viscosity.
  • alkyl in which at least one hydrogen is replaced by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl. Or 8-fluorooctyl. Further preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl or 5-fluoropentyl for increasing the dielectric anisotropy.
  • alkenyl in which at least one hydrogen is replaced by fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro -4-pentenyl, or 6,6-difluoro-5-hexenyl. Further preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl for decreasing the viscosity.
  • Ring A and Ring C are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is replaced by fluorine or chlorine 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl, chroman-2,6-diyl, in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen Chroman-2,6-diyl replaced with fluorine or chlorine.
  • Preferred ring A or ring C is 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2, 3-difluoro-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl. More preferred ring A or ring C is 1,4-cyclohexylene or 1,4-phenylene.
  • preferred ring A or ring C is 1,4-cyclohexylene for decreasing the viscosity, tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and optically anisotropic 1,4-phenylene for increasing the properties.
  • trans is preferable to cis for increasing the maximum temperature.
  • Tetrahydropyran-2,5-diyl is
  • Ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4, 5-trifluoronaphthalene-2,6-diyl or 7,8-difluorochroman-2,6-diyl.
  • Preferred ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, or 7,8-difluorochroman-2,6-diyl. More preferred ring B is 2,3-difluoro-1,4-phenylene or 2-chloro-3-fluoro-1,4-phenylene.
  • Particularly preferred ring B is 2,3-difluoro-1,4-phenylene.
  • preferred ring B is 2,3-difluoro-1,4-phenylene for decreasing the viscosity, and 2-chloro-3-fluoro-1,4-phenylene for decreasing the optical anisotropy.
  • it is 7,8-difluorochroman-2,6-diyl.
  • Ring D and ring E are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene.
  • Preferred ring D or ring E is 1,4-cyclohexylene for decreasing the viscosity or increasing the maximum temperature, and 1,4-phenylene for decreasing the minimum temperature.
  • trans is preferable to cis for increasing the maximum temperature.
  • Ring F and Ring I are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is replaced by fluorine or chlorine 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl, chroman-2,6-diyl, in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen Chroman-2,6-diyl replaced with fluorine or chlorine.
  • Preferred ring F or ring I is 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2, 3-difluoro-1,4-phenylene, 3,4,5-trifluoronaphthalene, or 7,8-difluorochroman-2,6-diyl. More preferred ring F or ring I is 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4.
  • ring F or ring I is 1,4-cyclohexylene or 1,4-phenylene.
  • preferred ring F or ring I is 1,4-cyclohexylene for decreasing the viscosity, tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and optically anisotropic 1,4-phenylene for increasing the properties.
  • Ring G is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4, 5-trifluoronaphthalene-2,6-diyl or 7,8-difluorochroman-2,6-diyl.
  • Preferred ring G is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, or 7,8-difluorochroman-2,6-diyl. More preferred ring G is 2,3-difluoro-1,4-phenylene.
  • preferred ring G is 2,3-difluoro-1,4-phenylene for decreasing the viscosity, and 2-chloro-3-fluoro-1,4-phenylene for decreasing the optical anisotropy.
  • it is 7,8-difluorochroman-2,6-diyl.
  • Z 1 and Z 2 are each independently a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, or —OCO—.
  • Desirable Z 1 or Z 2 is a single bond for decreasing the viscosity, —CH 2 CH 2 — for decreasing the minimum temperature, and —CH 2 O— or —OCH for increasing the dielectric anisotropy.
  • Z 3 is a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, or —OCO—.
  • Desirable Z 3 is a single bond for decreasing the viscosity, —CH 2 CH 2 — for decreasing the minimum temperature, and —COO— or —OCO— for increasing the maximum temperature.
  • Z 4 and Z 5 are each independently a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, or —OCO—.
  • Preferred Z 4 or Z 5 is a single bond for decreasing the viscosity, —CH 2 CH 2 — for decreasing the minimum temperature, and —CH 2 O— or —OCH for increasing the dielectric anisotropy. 2- .
  • A is 1, 2, or 3, b is 0 or 1, and the sum of a and b is 3 or less.
  • Preferred a is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.
  • Preferred b is 0 for decreasing the viscosity, and 1 for decreasing the minimum temperature.
  • c is 1, 2 or 3.
  • Preferred c is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.
  • d is 1, 2, or 3; e is 0 or 1; and the sum of d and e is 3 or less.
  • Preferred d is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.
  • Preferred e is 0 for decreasing the viscosity, and 1 for decreasing the minimum temperature.
  • MES is a mesogenic group having at least one ring.
  • Mesogenic groups are well known to those skilled in the art.
  • the mesogenic group means a moiety that contributes to the formation of a liquid crystal phase when the compound has a liquid crystal phase (intermediate phase).
  • a preferred example of compound (4) is compound (4-1).
  • R 7 is alkyl having 4 to 20 carbon atoms, and in this alkyl, at least one —CH 2 — is —CH ⁇ CH—, —CF ⁇ CH—, —CH ⁇ CF—, -C ⁇ C-, or cycloalkylene having 3 to 8 carbon atoms may be substituted, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine.
  • x is 1 or 2, preferably 1.
  • R 7 is alkyl having 4 to 20 carbons. More desirable R 7 is alkyl having 6 to 18 carbons. At least one —CH 2 — may be replaced by —CH ⁇ CH—, —CF ⁇ CH—, —CH ⁇ CF—, —C ⁇ C—, or —O—, and at least one hydrogen is It may be replaced with fluorine or chlorine.
  • R 8 is a polar group.
  • Compound (4) and compound (5) are preferably stable because they are added to the composition. When compound (4) and compound (5) are added to the composition, it is preferable that this compound does not lower the voltage holding ratio of the device. It is preferable that the compound (4) and the compound (5) have low volatility.
  • a preferred molar mass is 130 g / mol or more. A more preferred molar mass is in the range of 150 g / mol to 500 g / mol.
  • the polar group has a non-covalent interaction with the surface of the glass substrate or metal oxide film.
  • Preferred polar groups have a heteroatom selected from the group of nitrogen, oxygen, sulfur, and phosphorus. Preferred polar groups have at least one, or at least two of these heteroatoms.
  • Further preferred polar groups include hydrogen from compounds selected from the group of alcohols, primary, secondary, and tertiary amines, ketones, carboxylic acids, thiols, esters, ethers, thioethers, and combinations thereof. It is a monovalent group derived by removing. The structure of these groups may be linear, branched, cyclic, or a combination thereof.
  • Particularly preferred polar groups have at least one oxygen atom of OH structure or nitrogen atom of a primary, secondary or tertiary amine structure.
  • the most preferred polar group is a hydroxy group (carbon-OH).
  • Examples of polar groups R 8 is a group represented by the formula (A1) in formula (A4).
  • Sp 4 , Sp 6 and Sp 7 are independently a single bond or a group (—Sp ′′ —X ′′ —), and X ′′ is a ring It binds to P.
  • Sp ′′ is alkylene having 1 to 20 carbons, preferably alkylene having 1 to 12 carbons, in which at least one —CH 2 — is —O—, —S—, —NH—.
  • Preferred X ′′ is —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR 0 —, —NR 0 —CO—, —NR 0 —. CO—NR 0 — or a single bond.
  • Sp 5 is>CH-,> CR a1 -,> N-, or> C ⁇ . That is, Sp 5 in Formula (A2) is>CH—,> CR a1 —, or> N—, and Sp 5 in Formula (A3) means> C ⁇ .
  • Preferred Sp ′′ is — (CH 2 ) p1 —, — (CH 2 CH 2 O) q1 —CH 2 CH 2 —, —CH 2 CH 2 —S—CH 2 CH 2 —, or —CH 2 CH 2 —NHCH 2 CH 2 —, wherein p1 is an integer from 1 to 12, and q1 is an integer from 1 to 3.
  • Preferred groups are — (CH 2 ) p1 —, — (CH 2 ) p1 —O—, — (CH 2 ) p1 —O—CO—, — (CH 2 ) p1 —O—CO—O—, where p1 and q1 have the meanings indicated above.
  • Sp ′′ are ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methylimino.
  • X 1 is, -NH 2, -NHR a1, -N (R a1) 2, -OR a1, -OH, -COOH, -SH, -SR a1,
  • R a1 is alkyl having 1 to 15 carbons, and in this alkyl, at least one —CH 2 — is —C ⁇ C—, —CH ⁇ CH—, —COO—, —OCO -, -CO-, or -O-, in which at least one hydrogen may be replaced by fluorine or chlorine, and R 0 is hydrogen or C 1-12 Alkyl.
  • X 2 represents —O—, —CO—, —NH— , —NR a1 —, —S—, or a single bond
  • Z 9 represents an alkylene having 1 to 15 carbon atoms or a fat having 5 to 6 carbon atoms. It represents a cyclic group or a combination of at least one ring and alkylene, in which at least one hydrogen is —OH, —OR a1 , —COOH, —NH 2 , —NHR a1 , —N ( R a1 ) 2 , fluorine, or chlorine may be substituted, and R a1 has the meaning indicated above.
  • p is 0, 1, 2, or 3.
  • q is 2, 3, 4, or 5.
  • Ring P is an aromatic group having 6 to 25 carbon atoms or an alicyclic group having 3 to 25 carbon atoms, and these groups may be condensed rings, and in these groups, 1 to 3 hydrogen atoms May be replaced by R L.
  • R L represents —OH, — (CH 2 ) r —OH, fluorine, chlorine, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C ( ⁇ O) N (R 0 ).
  • R 0 is hydrogen or an alkyl having 1 to 12 carbons. It is a kill.
  • Particularly preferred nitrogen-containing groups R 8 are —NH 2 , —NH— (CH 2 ) n 3 H, — (CH 2 ) n —NH 2 , — (CH 2 ) n —NH— (CH 2 ) n 3 H, — NH— (CH 2 ) n —NH 2 , —NH— (CH 2 ) n —NH— (CH 2 ) n 3 H, — (CH 2 ) n 1 —NH— (CH 2 ) n 2 —NH 2 , — (CH 2 ) n1 —NH— (CH 2 ) n2 —NH— (CH 2 ) n3 H, —O— (CH 2 ) n —NH 2 , — (CH 2 ) n1 —O— (CH 2 ) n —NH 2 , — (CH 2 ) n1 —NH— (CH 2 ) n2 —OH, —O— (CH 2 )
  • Particularly preferred nitrogen-free groups R 8 are —OH, — (CH 2 ) n —OH, —O— (CH 2 ) n —OH, — [O— (CH 2 ) n1 —] n2 —OH, —COOH. , — (CH 2 ) n —COOH, —O— (CH 2 ) n —COOH, or — [O— (CH 2 ) n1 —] n2 —COOH, where n, n1, and n2 are independently And an integer of 1 to 12, preferably 1, 2, 3, or 4.
  • R 8 is particularly preferably —OH or —NH 2 .
  • —OH is preferable to —O—, —CO—, or —COO— because it has a high anchoring force.
  • Groups having a plurality of heteroatoms are particularly preferred. The compound having such a polar group is effective even at a low concentration.
  • R 9 is hydrogen, fluorine, chlorine, alkyl having 1 to 25 carbon atoms, and in this alkyl, at least one —CH 2 — is —NR 0 —, —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, or cycloalkylene having 3 to 8 carbon atoms may be substituted, and at least one third
  • the secondary carbon (> CH—) may be replaced with nitrogen (> N—), in which at least one hydrogen may be replaced with fluorine or chlorine, where R 0 is hydrogen Or alkyl having 1 to 12 carbons.
  • R 10 is alkyl having 1 to 25 carbon atoms, and in this alkyl, at least one —CH 2 — is —NR 0 —, —O—, —S—, —CO—, —COO—, —OCO.
  • R 0 is hydrogen or alkyl having 1 to 12 carbon atoms, and at least one tertiary carbon (> CH -) May be replaced by nitrogen (> N-) and at least one hydrogen may be replaced by fluorine or chlorine, provided that R 10 is an oxygen atom of OH structure, a sulfur atom of SH structure Or having at least one nitrogen atom of a primary, secondary, or tertiary amine structure.
  • Ring J and Ring K are independently an aromatic group having 6 to 25 carbon atoms, a heteroaromatic group having 5 to 25 carbon atoms, an alicyclic group having 3 to 25 carbon atoms, or a complex having 4 to 25 carbon atoms.
  • Alicyclic groups these groups may be fused rings, in which at least one hydrogen may be replaced by a group T, wherein the group T is —OH, — (CH 2 ) i —OH, fluorine, chlorine, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C ( ⁇ O) N (R 0 ) 2 , —C ( ⁇ O) R 0 , —N (R 0 ) 2 , — (CH 2 ) i —N (R 0 ) 2 , aryl having 6 to 20 carbon atoms, heteroaryl having 6 to 20 carbon atoms, alkyl having 1 to 25 carbon atoms, carbon number 1 to 25
  • Z 6 represents —O—, —S—, —CO—, —CO—O—, —OCO—, —O—CO—O—, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, — (CH 2 ) i —, —CF 2 CH 2 —, —CH 2 CF 2 —, — (CF 2 ) i —, —CH ⁇ CH—, —CF ⁇ CF—, —C ⁇ C—, —CH ⁇ CH—COO—, —OCO—CH ⁇ CH—, —C (R 0 ) 2 — , Or a single bond, wherein R 0 is hydrogen or alkyl having 1 to 12 carbons, and i is 1, 2, 3, or 4.
  • F is 0, 1, 2, 3, 4, or 5.
  • R 13 is alkyl having 4 to 20 carbon atoms, and in this alkyl, at least one —CH 2 — is —CH ⁇ CH—, —CF ⁇ CH—, —CH ⁇ . CF—, —C ⁇ C—, or cycloalkylene having 3 to 8 carbon atoms may be substituted, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine.
  • R 14 is alkyl having 1 to 25 carbon atoms, and in this alkyl, at least one —CH 2 — is —NR 0 —, —O—, —S—, —CO—, —COO—, —OCO.
  • R 0 is hydrogen or alkyl having 1 to 12 carbon atoms, and at least one tertiary carbon (> CH -) May be replaced with nitrogen (> N-) and at least one hydrogen may be replaced with fluorine or chlorine, provided that R 14 is an oxygen atom of OH structure, a sulfur atom of SH structure And at least one nitrogen atom of a primary, secondary, or tertiary amine structure.
  • R 15 is alkyl having 1 to 8 carbons or fluorine.
  • Ring Q and Ring R are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-fluoro-1,3-phenylene, 2-ethyl-1,4 -Phenylene, 2,6-diethyl-1,4-phenylene, 2-trifluoromethyl-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene 2,6-difluoro-1,4-phenylene or 2,3,5,6-tetrafluoro-1,4-phenylene.
  • Ring S is cyclohexyl or phenyl.
  • Z 10 is a single bond, —CH 2 CH 2 —, —COO—, or —OCO—.
  • Z 11 is a single bond, alkylene having 1 to 15 carbons, alicyclic group having 5 or 6 carbons, or a combination thereof, and in these groups, at least one hydrogen is —OH, —OR a1 , —COOH, —NH 2 , —NHR a1 , —N (R a1 ) 2 , fluorine, or chlorine;
  • R a1 is alkyl having 1 to 15 carbons, in which at least One —CH 2 — may be replaced by —C ⁇ C—, —CH ⁇ CH—, —COO—, —OCO—, —CO—, or —O—, and in these groups, at least 1 One hydrogen may be replaced with fluorine or chlorine.
  • Sp 4 is a single bond, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 O—, or —OCH 2 —.
  • Sp 7 is a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, —CH 2 — may be replaced by —O— or —NH—.
  • X 3 is —OH, —COOH, —SH, —OCH 3 , or —NH 2 .
  • X 4 is a single bond or —O—. s is 0, 1, 2, 3, 4, or 5.
  • Aromatic group refers to aryl or substituted aryl.
  • Heteroaryl represents an aromatic group having at least one heteroatom.
  • Aryl and heteroaryl may be monocyclic or polycyclic. That is, these groups have at least one ring, which may be fused (eg, naphthyl), the two rings may be covalently linked (eg, biphenyl), or the fused ring and linked It may have a combination of rings.
  • Preferred heteroaryls have at least one heteroatom selected from the group of nitrogen, oxygen, sulfur, and phosphorus.
  • Preferred aryl or heteroaryl has 6 to 25 carbon atoms and may be a 5-membered ring, 6-membered ring, or 7-membered ring.
  • Preferred aryl or heteroaryl may be monocyclic, bicyclic or tricyclic. These groups may be condensed rings or may be substituted.
  • Preferred aryls are benzene, biphenyl, terphenyl, [1,1 ′: 3 ′, 1 ′′] terphenyl, naphthalene, anthracene, binaphthyl, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene.
  • Preferred heteroaryls are pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole.
  • Preferred heteroaryls are indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthaimidazole, phenanthrimidazole, pyridaimidazole, pyrazineimidazole, quinoxaline imidazole, benzoxazole, naphthoxazole, anthroxax Sol, phenanthroxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, Benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthy
  • Preferred heteroaryl is also a monovalent group derived by removing one hydrogen from a ring formed by combining two groups selected from these five-membered, six-membered and condensed rings. These heteroaryls may be substituted with alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl, aryl, or heteroaryl.
  • the alicyclic group may be saturated or unsaturated. That is, these groups may have only a single bond or a combination of a single bond and multiple bonds. Saturated rings are preferred over unsaturated rings.
  • the alicyclic group may be a single ring or a plurality of rings.
  • these groups are monocyclic, bicyclic or tricyclic having 3 to 25 carbon atoms, and these groups may be condensed rings or may be substituted.
  • Preferred examples of these groups are five-membered rings, six-membered rings, seven-membered rings, or eight-membered rings, in which at least one carbon may be replaced by silicon, and at least one> CH - May be replaced by> N- and at least one -CH 2 -may be replaced by -O- or -S-.
  • Preferred alicyclic groups include five-membered rings such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran and pyrrolidine, six-membered rings such as cyclohexane, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane and piperidine.
  • ring Membered ring, seven-membered ring such as cycloheptane, tetrahydronaphthalene, decahydronaphthalene, indane, bicyclo [1.1.1] pentane, bicyclo [2.2.2] octane, spiro [3.3] heptane, octahydro- It is a divalent group derived by removing two hydrogens from a condensed ring such as 4,7-methanoindane.
  • P 4 , P 5 and P 6 are independently a polymerizable group.
  • Preferred P 4 , P 5 , or P 6 is a polymerizable group selected from the group of groups represented by formula (P-1) to formula (P-5). More desirable P 4 , P 5 or P 6 is a group represented by the formula (P-1), the formula (P-2) or the formula (P-3). Particularly preferred P 4 , P 5 or P 6 is a group represented by the formula (P-1) or the formula (P-2). Most preferred P 4 , P 5 or P 6 is a group represented by the formula (P-1).
  • a preferred group represented by the formula (P-1) is —OCO—CH ⁇ CH 2 or —OCO—C (CH 3 ) ⁇ CH 2 .
  • the wavy lines in the formulas (P-1) to (P-5) indicate the binding sites.
  • M 1 , M 2 , and M 3 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is fluorine or chlorine 1-5 alkyl substituted with Preferred M 1 , M 2 or M 3 is hydrogen or methyl for increasing the reactivity. More preferred M 1 is hydrogen or methyl, and more preferred M 2 or M 3 is hydrogen.
  • Sp 9 , Sp 10 , and Sp 11 are each 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 with —CH ⁇ CH— or —C ⁇ C—, and in these groups, at least 1 One hydrogen may be replaced with fluorine or chlorine.
  • Ring T and Ring V are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl, or pyridine -2-yl, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is replaced by fluorine or chlorine. Further, it may be substituted with alkyl having 1 to 12 carbons.
  • Preferred ring T or ring V is phenyl.
  • Ring U 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, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, At least one hydrogen is fluorine, chlorine,
  • Z 12 and Z 13 are each independently a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH 2 — is —O—, —CO—, —COO—, or — OCO— may be replaced and at least one —CH 2 CH 2 — may be —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 with fluorine or chlorine.
  • Preferred Z 12 or Z 13 is a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, or —OCO—. Further preferred Z 12 or Z 13 is a single bond.
  • T is 0, 1, or 2.
  • Preferred t is 0 or 1.
  • u, v, and w are independently 0, 1, 2, 3, or 4, and the sum of u, v, and w is 1 or greater.
  • Preferred u, v, or w is 1 or 2.
  • Desirable compounds (1) are the compounds (1-1) to (1-21) described in item 2.
  • at least one of the first components is compound (1-1), compound (1-3), compound (1-4), compound (1-6), compound (1-8), or compound (1-10) is preferred.
  • At least two of the first components are compound (1-1) and compound (1-6), compound (1-1) and compound (1-10), compound (1-3) and compound (1-6), A compound (1-3) and a compound (1-10), a compound (1-4) and a compound (1-6), or a combination of a compound (1-4) and a compound (1-8) is preferable.
  • Desirable compound (2) is the compound (2-1) to the compound (2-13) according to item 5.
  • at least one of the second components is the compound (2-1), the compound (2-3), the compound (2-5), the compound (2-6), the compound (2-8), or the compound (2-9) is preferred.
  • At least two of the second components are compound (2-1) and compound (2-3), compound (2-1) and compound (2-5), or compound (2-1) and compound (2-6). A combination is preferred.
  • Desirable compound (3) is the compound (3-1) to the compound (3-21) according to item 8.
  • at least one of the third components is compound (3-1), compound (3-3), compound (3-4), compound (3-6), compound (3-8), or compound (3-10) is preferred.
  • At least two of the third components are compound (3-1) and compound (3-6), compound (3-1) and compound (3-10), compound (3-3) and compound (3-6), A compound (3-3) and a compound (3-10), a compound (3-4) and a compound (3-6), or a combination of a compound (3-4) and a compound (3-8) is preferable.
  • Desirable compound (4) is the compound (4-1-1) to the compound (4-1-4) according to Item 15.
  • Desirable compounds (5) are the compounds (5-1-1) to (5-1-29) according to item 16.
  • the compound (4) is preferable to the compound (5).
  • Particularly preferred compound (4-1) is selected from the following compounds.
  • R 15 is alkyl having 1 to 8 carbons or fluorine.
  • Particularly preferred compound (5-1) is selected from the following compounds (5-1-1-1) and compounds (5-1-29-1).
  • Desirable compound (6) is the compound (6-1) to the compound (6-28) according to item 20.
  • at least one of the second additives is compound (6-1), compound (6-2), compound (6-24), compound (6-25), compound (6-26), or The compound (6-27) is preferable.
  • At least two of the second additives are compound (6-1) and compound (6-2), compound (6-1) and compound (6-18), compound (6-2) and compound (6-24).
  • additives that may be added to the composition will be described.
  • Such additives are optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like.
  • An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules to give a twist angle. Examples of such a compound are the compound (7-1) to the compound (7-5).
  • a desirable ratio of the optically active compound is approximately 5% by weight or less. A more desirable ratio is in the range of approximately 0.01% by weight to approximately 2% by weight.
  • an antioxidant is composed. Added to the product.
  • a preferred example of the antioxidant is a compound (8) wherein n is an integer of 1 to 9.
  • n 1, 3, 5, 7, or 9. Further preferred n is 7. Since the compound (8) in which n is 7 has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after the device has been used for a long time.
  • a desirable ratio of the antioxidant is approximately 50 ppm or more for achieving its effect, and is approximately 600 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature.
  • a more desirable ratio is in the range of approximately 100 ppm to approximately 300 ppm.
  • the ultraviolet absorber examples include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Also preferred are light stabilizers such as sterically hindered amines.
  • a desirable ratio of these absorbers and stabilizers is approximately 50 ppm or more for achieving the effect thereof, and approximately 10,000 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 10,000 ppm.
  • a dichroic dye such as an azo dye or an anthraquinone dye is added to the composition in order to adapt it to a GH (guest host) mode element.
  • a preferred ratio of the dye is in the range of approximately 0.01% by weight to approximately 10% by weight.
  • an antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is added to the composition.
  • a desirable ratio of the antifoaming agent is approximately 1 ppm or more for obtaining the effect thereof, and approximately 1000 ppm or less for preventing a display defect.
  • a more desirable ratio is in the range of approximately 1 ppm to approximately 500 ppm.
  • a polymerizable compound is used to adapt to a polymer support alignment (PSA) type device.
  • Compound (6) is suitable for this purpose.
  • Other polymerizable compounds different from the compound (6) may be added to the composition together with the compound (6).
  • Preferable examples of other polymerizable compounds are compounds such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. Further preferred examples are acrylate or methacrylate.
  • a desirable ratio of compound (6) is approximately 10% by weight or more based on the total weight of the polymerizable compound.
  • a more desirable ratio is about 50% by weight or more.
  • a particularly desirable ratio is approximately 80% by weight or more.
  • a particularly desirable ratio is also 100% by weight.
  • the reactivity of the polymerizable compound and the pretilt angle of the liquid crystal molecules can be adjusted by changing the type of the compound (6) or combining the compound (6) with another polymerizable compound in an appropriate ratio. By optimizing the pretilt angle, a short response time of the element can be achieved. Since the alignment of the liquid crystal molecules is stabilized, a large contrast ratio and a long lifetime can be achieved.
  • Polymerizable compound is polymerized by ultraviolet irradiation.
  • the polymerization may be performed in the presence of a suitable initiator such as a photopolymerization initiator.
  • a suitable initiator such as a photopolymerization initiator.
  • Appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those skilled in the art and are described in the literature.
  • Irgacure 651 registered trademark; BASF
  • Irgacure 184 registered trademark; BASF
  • Darocur 1173 registered trademark; BASF
  • a desirable ratio of the photopolymerization initiator is in the range of approximately 0.1% by weight to approximately 5% by weight based on the total weight of the polymerizable compound.
  • a more desirable ratio is in the range of approximately 1% by weight to approximately 3% by weight.
  • a polymerization inhibitor When storing the polymerizable compound, a polymerization inhibitor may be added to prevent polymerization.
  • the polymerizable compound is usually added to the composition without removing the polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine and the like.
  • the polar compound is an organic compound having polarity.
  • a compound having an ionic bond is not included.
  • Atoms such as oxygen, sulfur, and nitrogen are more electronegative and tend to have partial negative charges.
  • Carbon and hydrogen tend to be neutral or have a partial positive charge.
  • Polarity arises from the fact that partial charges are not evenly distributed among different types of atoms in a compound.
  • the polar compound has at least one of partial structures such as —OH, —COOH, —SH, —NH 2 ,>NH,> N—.
  • Compound (1-6) is synthesized by the method described in Japanese Patent Application Laid-Open No. 2000-053602.
  • Compound (2-1) is synthesized by the method described in JP-A-59-176221.
  • Compound (3-1) is synthesized by the method described in JP-T-2-503441.
  • Compound (4-1) is synthesized by the method described in International Publication No. 2012-038026.
  • a part of the compound (5) is commercially available.
  • Compound (6-18) is synthesized by the method described in JP-A-7-101900.
  • a part of the compound (8) is commercially available.
  • Compounds of formula (8) where n is 1 are available from Sigma-Aldrich Corporation.
  • Compound (8) or the like in which n is 7 is synthesized by the method described in US Pat. No. 3,660,505.
  • compositions are prepared from the compound thus obtained by known methods. For example, the component compounds are mixed and dissolved in each other by heating.
  • compositions have a minimum temperature of about ⁇ 10 ° C. or lower, a maximum temperature of about 70 ° C. or higher, and an optical anisotropy in the range of about 0.07 to about 0.20.
  • a composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the ratio of the component compounds or by mixing other liquid crystal compounds.
  • a composition having optical anisotropy in the range of about 0.10 to about 0.30 may be prepared by trial and error.
  • a device containing this composition has a large voltage holding ratio.
  • This composition is suitable for an AM device.
  • This composition is particularly suitable for a transmissive AM device.
  • This composition can be used as a composition having a nematic phase, or can be used as an optically active composition by adding an optically active compound.
  • This composition can be used for an AM device. Further, it can be used for PM elements.
  • This composition can be used for an AM device and a PM device having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, and FPA.
  • Use for an AM device having a mode such as TN, OCB, IPS, or FFS is particularly preferable.
  • the alignment of liquid crystal molecules may be parallel to or perpendicular to the glass substrate.
  • These elements may be reflective, transmissive, or transflective. Use in a transmissive element is preferred. It can also be used for an amorphous silicon-TFT device or a polycrystalline silicon-TFT device.
  • NCAP non-curvilinear-aligned-phase
  • PD polymer-dispersed
  • An example of a method for producing a conventional polymer-supported orientation type device is as follows. An element having two substrates called an array substrate and a color filter substrate is assembled. This substrate has an alignment film. At least one of the substrates has an electrode layer. A liquid crystal compound is prepared by mixing a liquid crystal compound. A polymerizable compound is added to the composition. You may add an additive further as needed. This composition is injected into the device. The device is irradiated with light with a voltage applied. Ultraviolet light is preferred. The polymerizable compound is polymerized by light irradiation. By this polymerization, a composition containing a polymer is generated. The polymer-supported orientation type element is manufactured by such a procedure.
  • An example of a method for manufacturing an element having no alignment film is as follows. A mixture of a liquid crystal compound, a polymerizable compound, and a polar compound is injected into an element having no alignment film. The device is irradiated with light with a voltage applied. The polymerizable compound is polymerized by light irradiation. By this polymerization, a layer of a composition containing a polymer and a polar compound is formed on the substrate.
  • polar compounds are arranged on the substrate because polar groups interact with the substrate surface.
  • This polar compound aligns the liquid crystal molecules.
  • the polymerizable compound is also aligned according to this alignment.
  • the polymerizable compound is polymerized by ultraviolet rays, so that a polymer maintaining this orientation is formed.
  • the effect of this polymer additionally stabilizes the orientation of the liquid crystal molecules and shortens the response time of the device. Since image sticking is a malfunction of the liquid crystal molecules, the effect of this polymer also improves the image sticking.
  • the present invention will be described in more detail with reference to examples. The invention is not limited by these examples.
  • the present invention includes a mixture of the composition (M1) and the composition (M2).
  • the invention also includes a mixture of at least two of the example compositions.
  • the synthesized compound was identified by a method such as NMR analysis. The characteristics of the compound, composition and device were measured by the following methods.
  • NMR analysis DRX-500 manufactured by Bruker BioSpin Corporation was used for measurement.
  • the sample was dissolved in a deuterated solvent such as CDCl 3, and the measurement was performed at room temperature, 500 MHz, and 16 times of integration.
  • Tetramethylsilane was used as an internal standard.
  • CFCl 3 was used as an internal standard and the number of integrations was 24.
  • s is a singlet
  • d is a doublet
  • t is a triplet
  • q is a quartet
  • quint is a quintet
  • sex is a sextet
  • m is a multiplet
  • br is broad.
  • GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for measurement.
  • the carrier gas is helium (2 mL / min).
  • the sample vaporization chamber was set at 280 ° C, and the detector (FID) was set at 300 ° C.
  • capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m; stationary liquid phase is dimethylpolysiloxane; nonpolar) manufactured by Agilent Technologies Inc. was used.
  • the column was held at 200 ° C. for 2 minutes and then heated to 280 ° C. at a rate of 5 ° C./min.
  • a sample was prepared in an acetone solution (0.1% by weight), and 1 ⁇ L thereof was injected into the sample vaporization chamber.
  • the recorder is a C-R5A Chromatopac manufactured by Shimadzu Corporation, or an equivalent product.
  • the obtained gas chromatogram showed the peak retention time and peak area corresponding to the component compounds.
  • capillary column As a solvent for diluting the sample, chloroform, hexane or the like may be used.
  • the following capillary column may be used.
  • HP-1 from Agilent Technologies Inc. (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m), Rtx-1 from Restek Corporation (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m), BP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m) manufactured by SGE International Pty.
  • a capillary column CBP1-M50-025 length 50 m, inner diameter 0.25 mm, film thickness 0.25 ⁇ m
  • Shimadzu Corporation may be used.
  • the ratio of the liquid crystal compound contained in the composition may be calculated by the following method.
  • the mixture of liquid crystal compounds is analyzed by gas chromatography (FID).
  • FID gas chromatography
  • the area ratio of peaks in the gas chromatogram corresponds to the ratio of liquid crystal compounds.
  • the correction coefficient of each liquid crystal compound may be regarded as 1. Therefore, the ratio (% by weight) of the liquid crystal compound can be calculated from the peak area ratio.
  • Measurement sample When measuring the characteristics of the composition and the device, the composition was used as it was as a sample.
  • a sample for measurement was prepared by mixing this compound (15% by weight) with mother liquid crystals (85% by weight). The characteristic value of the compound was calculated from the value obtained by the measurement by extrapolation.
  • (Extrapolated value) ⁇ (Measured value of sample) ⁇ 0.85 ⁇ (Measured value of mother liquid crystal) ⁇ / 0.15.
  • the ratio of the compound and the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% by weight in this order. changed.
  • the maximum temperature, optical anisotropy, viscosity, and dielectric anisotropy values for the compound were determined.
  • the following mother liquid crystals were used.
  • the ratio of the component compounds is shown by weight%.
  • Measurement method The characteristics were measured by the following method. Many of these are the methods described in the JEITA standard (JEITA ED-2521B) deliberated and established by the Japan Electronics and Information Technology Industries Association (JEITA), or a modified method thereof. Met. No thin film transistor (TFT) was attached to the TN device used for the measurement.
  • JEITA Japan Electronics and Information Technology Industries Association
  • nematic phase (NI; ° C.): A sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when a part of the sample changed from a nematic phase to an isotropic liquid.
  • the upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”.
  • T C Minimum temperature of nematic phase
  • a sample having a nematic phase is placed in a glass bottle and placed in a freezer at 0 ° C., ⁇ 10 ° C., ⁇ 20 ° C., ⁇ 30 ° C. and ⁇ 40 ° C. for 10 days After storage, the liquid crystal phase was observed. For example, when the sample remained in a nematic phase at ⁇ 20 ° C. and changed to a crystalline or smectic phase at ⁇ 30 ° C., the TC was described as ⁇ 20 ° C.
  • the lower limit temperature of the nematic phase may be abbreviated as “lower limit temperature”.
  • Viscosity Bulk viscosity; ⁇ ; measured at 20 ° C .; mPa ⁇ s: An E-type viscometer manufactured by Tokyo Keiki Co., Ltd. was used for the measurement.
  • Viscosity (rotational viscosity; ⁇ 1; measured at 25 ° C .; mPa ⁇ s): The measurement was performed according to the method described in M. ⁇ Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). I followed. A sample was injected into a VA device having a distance (cell gap) between two glass substrates of 20 ⁇ m. This element was applied stepwise in increments of 1 volt within a 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 (peak current) and peak time (peak time) of the transient current (transient current) generated by this application were measured. These measurements and M.I.
  • the value of rotational viscosity was obtained from the paper by Tsuji Imai et al.
  • the dielectric anisotropy necessary for this calculation was measured by the method described in measurement (6).
  • the dielectric constants ( ⁇ and ⁇ ) were measured as follows. 1) Measurement of dielectric constant ( ⁇ ): An ethanol (20 mL) solution of octadecyltriethoxysilane (0.16 mL) was applied to a well-cleaned glass substrate. The glass substrate was rotated with a spinner and then heated at 150 ° C. for 1 hour. A sample was put in a VA element in which the distance between two glass substrates (cell gap) was 4 ⁇ m, and the element was sealed with an adhesive that was cured with ultraviolet rays.
  • Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant ( ⁇ ) in the major axis direction of the liquid crystal molecules was measured.
  • 2) Measurement of dielectric constant ( ⁇ ) A polyimide solution was applied to a well-cleaned glass substrate. After baking this glass substrate, the obtained alignment film was rubbed. A sample was injected into 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 the device, and after 2 seconds, the dielectric constant ( ⁇ ) in the minor axis direction of the liquid crystal molecules was measured.
  • Threshold voltage (Vth; measured at 25 ° C .; V): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement.
  • the light source was a halogen lamp.
  • a sample is placed in a normally black mode VA element in which the distance between two glass substrates (cell gap) is 4 ⁇ m and the rubbing direction is anti-parallel, and an adhesive that cures the element with ultraviolet rays is used. And sealed.
  • the voltage (60 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 20V by 0.02V.
  • 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 reached the maximum and the transmittance was 0% when the light amount was the minimum.
  • the threshold voltage was expressed as a voltage when the transmittance reached 10%.
  • VHR-1 Voltage holding ratio
  • the TN device used for the measurement had a polyimide alignment film, and the distance between two glass substrates (cell gap) was 5 ⁇ m. . This element was sealed with an adhesive that was cured by ultraviolet rays after the sample was injected.
  • the TN device was charged by applying a pulse voltage (60 microseconds at 5 V).
  • the decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined.
  • Area B was the area when it was not attenuated.
  • the voltage holding ratio was expressed as a percentage of area A with respect to area B.
  • VHR-2 Voltage holding ratio (VHR-2; measured at 80 ° C .;%): The voltage holding ratio was measured in the same procedure as above except that it was measured at 80 ° C. instead of 25 ° C. The obtained value was expressed as VHR-2.
  • VHR-3 Voltage holding ratio
  • the TN device used for the measurement had a polyimide alignment film, and the cell gap was 5 ⁇ m.
  • a sample was injected into this element and irradiated with light for 20 minutes.
  • the light source was an ultra high pressure mercury lamp USH-500D (manufactured by USHIO), and the distance between the element and the light source was 20 cm.
  • a decaying voltage was measured for 16.7 milliseconds.
  • a composition having a large VHR-3 has a large stability to ultraviolet light.
  • VHR-3 is preferably 90% or more, and more preferably 95% or more.
  • VHR-4 Voltage holding ratio
  • the TN device injected with the sample was heated in a constant temperature bath at 80 ° C. for 500 hours, and then the voltage holding ratio was measured to determine the stability against heat. Evaluated. In the measurement of VHR-4, a voltage decaying for 16.7 milliseconds was measured. A composition having a large VHR-4 has a large stability to heat.
  • an ultraviolet curing multimetal lamp M04-L41 manufactured by Eye Graphics Co., Ltd. was used for irradiation with ultraviolet rays.
  • a rectangular wave 120 Hz 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 the maximum, and the transmittance was 0% when the light amount was the minimum.
  • the maximum voltage of the rectangular wave was set so that the transmittance was 90%.
  • the minimum voltage of the rectangular wave was set to 2.5 V at which the transmittance was 0%.
  • the response time was expressed as the time required to change the transmittance from 10% to 90% (rise time; millisecond).
  • Elastic constant (K11: spray elastic constant, K33: bend elastic constant; measured at 25 ° C .; pN):
  • an EC-1 type elastic constant measuring instrument manufactured by Toyo Corporation was used. Using. A sample was injected into a vertical alignment element in which the distance between two glass substrates (cell gap) was 20 ⁇ m. A 20 to 0 volt charge was applied to the device, and the capacitance and applied voltage were measured. Fitting the measured values of capacitance (C) and applied voltage (V) using “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun), formulas (2.98) and (2.101) on page 75 The value of the elastic constant was obtained from the formula (2.100).
  • Pretilt angle (degrees): A spectroscopic ellipsometer M-2000U (manufactured by J. A. Woollam Co., Inc.) was used to measure the pretilt angle.
  • compositions examples are shown below.
  • the component compounds were represented by symbols based on the definitions in Table 3 below.
  • Table 3 the configuration regarding 1,4-cyclohexylene is trans.
  • the number in parentheses after the symbol represents the chemical formula to which the compound belongs.
  • the symbol ( ⁇ ) means other liquid crystal compounds.
  • the ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive.
  • Example 1 of device A composition containing a polar compound was injected into an element having no raw material alignment film. After irradiating with ultraviolet rays, the vertical alignment of liquid crystal molecules in this device was examined. First, the raw materials will be explained.
  • the raw materials are compositions (M1) to (M16), polar compounds (PC-1) to (PC-33), and polymerizable compounds (RM-1) to (RM-11), which are listed in this order.
  • Example 1 of vertical alignment of liquid crystal molecules The polar compound (PC-1) was added to the composition (M1) at a ratio of 5% by weight and the polymerizable compound (RM-1) was added at a ratio of 0.5% by weight. This mixture was injected into a device having an alignment film having a gap (cell gap) of 4.0 ⁇ m between two glass substrates on a hot stage at 100 ° C.
  • the polymerizable compound was polymerized by irradiating this element with ultraviolet rays (28J) using an ultra-high pressure mercury lamp USH-250-BY (manufactured by USHIO).
  • This element was set in a polarizing microscope in which a polarizer and an analyzer were arranged so as to be orthogonal, and the element was irradiated with light from below, and the presence or absence of light leakage was observed.
  • the vertical alignment was judged as “good”.
  • light passing through the element was observed, it was indicated as “defective”.
  • Examples 2 to 33 and Comparative Example 1 A device having no alignment film was manufactured using a mixture of the composition, the polar compound, and the polymerizable compound. The presence or absence of light leakage was observed in the same manner as in Example 1. The results are summarized in Table 4. In Comparative Example 1, no polymerizable compound was added for comparison.
  • the liquid crystal composition of the present invention can control the alignment of liquid crystal molecules in an element having no alignment film.
  • a liquid crystal display element containing this composition has characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime, and thus can be used for a liquid crystal projector, a liquid crystal television, and the like. .

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Abstract

L'invention concerne une composition de cristaux liquides dans laquelle l'alignement vertical des molécules de cristaux liquides peut être obtenu sous l'effet des actions d'un composé polaire et d'un polymère, et un élément d'affichage à cristaux liquides la contenant. La composition de cristaux liquides selon l'invention est une composition de cristaux liquides nématiques présentant une anisotropie diélectrique négative et contenant un composé cristallin liquide spécifique ayant une importante anisotropie diélectrique négative à titre de premier composant, un composé polaire à titre de premier additif, et un composé polymérisable à titre de second additif. La composition peut contenir un composé cristallin liquide spécifique ayant une température à limite haute élevée ou une faible viscosité à titre de deuxième composant et un composé cristallin liquide spécifique présentant une importante anisotropie négative à titre de troisième composant. Un élément d'affichage à cristaux liquides contenant ladite composition est en outre décrit.
PCT/JP2016/075972 2015-10-23 2016-09-05 Composition de cristaux liquides et élément d'affichage à cristaux liquides WO2017068875A1 (fr)

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WO2018221270A1 (fr) * 2017-05-31 2018-12-06 Jnc株式会社 Composition de cristaux liquides et élément d'affichage à cristaux liquides
WO2019003936A1 (fr) * 2017-06-26 2019-01-03 Dic株式会社 Auxiliaire d'alignement spontané pour composition à cristaux liquides
WO2019124153A1 (fr) * 2017-12-22 2019-06-27 Dic株式会社 Composition de cristaux liquides, et élément d'affichage à cristaux liquides
JPWO2018212059A1 (ja) * 2017-05-18 2019-06-27 Dic株式会社 液晶組成物及びそれを使用した液晶表示素子
CN110093166A (zh) * 2018-01-31 2019-08-06 北京八亿时空液晶科技股份有限公司 一种含有自配向化合物的液晶组合物及其应用
JPWO2019124095A1 (ja) * 2017-12-19 2019-12-19 Dic株式会社 液晶組成物及び液晶表示素子
CN111417700A (zh) * 2017-12-22 2020-07-14 Dic株式会社 聚合性液晶组合物及液晶显示元件以及聚合性化合物
US11697666B2 (en) 2021-04-16 2023-07-11 Gilead Sciences, Inc. Methods of preparing carbanucleosides using amides
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CN111205878B (zh) * 2018-11-22 2022-07-26 河北迈尔斯通电子材料有限公司 低粘度快速响应且低功耗负性液晶组合物及液晶显示器
JP7243170B2 (ja) * 2018-12-18 2023-03-22 Dic株式会社 液晶組成物及び液晶表示素子
CN111748355B (zh) * 2019-03-29 2023-05-02 石家庄诚志永华显示材料有限公司 一种液晶化合物、包含该液晶化合物的液晶组合物及液晶显示元器件
CN114196422B (zh) * 2020-09-17 2023-09-08 江苏和成显示科技有限公司 液晶组合物及其液晶显示器件

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JPWO2018212059A1 (ja) * 2017-05-18 2019-06-27 Dic株式会社 液晶組成物及びそれを使用した液晶表示素子
WO2018221270A1 (fr) * 2017-05-31 2018-12-06 Jnc株式会社 Composition de cristaux liquides et élément d'affichage à cristaux liquides
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WO2019003936A1 (fr) * 2017-06-26 2019-01-03 Dic株式会社 Auxiliaire d'alignement spontané pour composition à cristaux liquides
JPWO2019003936A1 (ja) * 2017-06-26 2019-07-04 Dic株式会社 液晶組成物用自発配向助剤
CN110651021B (zh) * 2017-06-26 2023-04-04 Dic株式会社 液晶组合物用自发取向助剂
JPWO2019124095A1 (ja) * 2017-12-19 2019-12-19 Dic株式会社 液晶組成物及び液晶表示素子
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WO2019124153A1 (fr) * 2017-12-22 2019-06-27 Dic株式会社 Composition de cristaux liquides, et élément d'affichage à cristaux liquides
CN111373019A (zh) * 2017-12-22 2020-07-03 Dic株式会社 液晶组合物及液晶显示元件
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JPWO2019124345A1 (ja) * 2017-12-22 2020-07-27 Dic株式会社 重合性液晶組成物及び液晶表示素子ならびに重合性化合物
CN111373019B (zh) * 2017-12-22 2023-10-03 Dic株式会社 液晶组合物及液晶显示元件
CN111417700B (zh) * 2017-12-22 2024-01-30 Dic株式会社 聚合性液晶组合物及液晶显示元件以及聚合性化合物
CN110093166A (zh) * 2018-01-31 2019-08-06 北京八亿时空液晶科技股份有限公司 一种含有自配向化合物的液晶组合物及其应用
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