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WO2017216996A1 - 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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Publication number
WO2017216996A1
WO2017216996A1 PCT/JP2017/002170 JP2017002170W WO2017216996A1 WO 2017216996 A1 WO2017216996 A1 WO 2017216996A1 JP 2017002170 W JP2017002170 W JP 2017002170W WO 2017216996 A1 WO2017216996 A1 WO 2017216996A1
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Prior art keywords
carbons
liquid crystal
fluorine
hydrogen
replaced
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English (en)
Japanese (ja)
Inventor
将之 齋藤
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JNC Corp
JNC Petrochemical Corp
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JNC Corp
JNC Petrochemical Corp
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Priority to JP2018523289A priority Critical patent/JP6766873B2/ja
Priority to TW106117903A priority patent/TW201809227A/zh
Publication of WO2017216996A1 publication Critical patent/WO2017216996A1/fr
Anticipated expiration legal-status Critical
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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
    • C09K19/08—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
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/16—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon double bonds, e.g. stilbenes
    • C—CHEMISTRY; METALLURGY
    • 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
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • 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 having a positive dielectric anisotropy, a liquid crystal display device containing the composition, and the like.
  • the present invention relates to a liquid crystal composition containing a polar compound having a polymerizable group (or this polymer) and capable of achieving vertical alignment of liquid crystal molecules by the action of this compound, and a liquid crystal display device.
  • 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 relationships in these properties are 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.
  • the elastic constant of the composition is related to the contrast of the device. In order to increase the contrast in the device, a large elastic constant in the composition is more preferable.
  • 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. In an element having a mode such as TN, this value is about 0.45 ⁇ m. In this case, 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 in the initial stage is preferable.
  • a composition having a large specific resistance after being used for a long time is preferred.
  • the stability of the composition to ultraviolet light or 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 polymer-supported alignment (PSA) type liquid crystal display element In a general-purpose liquid crystal display element, vertical alignment of liquid crystal molecules is achieved by a specific polyimide alignment film.
  • PSA polymer-supported alignment
  • a polymer is combined with an alignment film.
  • 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 alignment of liquid crystal molecules can be controlled by the polymer, 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 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.
  • a composition having positive or negative dielectric anisotropy is used in a device having no alignment film.
  • Compositions having positive dielectric anisotropy are disclosed in the following Patent Documents 1 to 4 and the like. In this invention, the polar compound (or this polymer) which has a polymeric group was combined with the liquid crystalline compound, and this composition was used for the liquid crystal display element which does not have an alignment film.
  • One object of the present invention is to provide a liquid crystal composition containing a polar compound having a polymerizable group (or this polymer), wherein the polar compound has high compatibility with the liquid crystal compound. .
  • Another object is to provide a liquid crystal composition capable of achieving vertical alignment of liquid crystal molecules by the action of a polymer generated from the polar compound.
  • Other objectives are: high maximum temperature of nematic phase, low minimum temperature of nematic phase, small viscosity, suitable optical anisotropy, positively large dielectric anisotropy, large specific resistance, high stability against ultraviolet rays, high heat resistance
  • Another object is to provide a liquid crystal composition having an appropriate balance between at least two of these properties. Another object is a liquid crystal display device containing such a composition. Another object is to provide 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 was selected from at least one compound selected from the group of compounds represented by formula (1) as the first component, and from a group of polar compounds represented by formula (2) as the first additive
  • a liquid crystal composition containing at least one compound and having positive dielectric anisotropy, and a liquid crystal display device containing the composition was selected from at least one compound selected from the group of compounds represented by formula (1) as the first component, and from a group of polar compounds represented by formula (2) as the first additive
  • a liquid crystal composition containing at least one compound and having positive dielectric anisotropy, and a liquid crystal display device containing the composition.
  • R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons;
  • ring A and ring B are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine -2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl;
  • Ring C and Ring E are independently cyclohexyl, cyclohexenyl, phenyl, 1- Naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl, or pyridin-2-yl
  • R 2 is a group represented by —OH, —OR 0 , —NH 2 , —NHR 0 , or —N (R 0 ) 2 , wherein R 0 is hydrogen or alkyl having 1 to 12 carbons; Yes; M 4 and M 5 are independently hydrogen, fluorine, alkyl of 1 to 5 carbons, or alkyl of 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine.
  • One advantage of the present invention is to provide a liquid crystal composition containing a polar compound having a polymerizable group (or a polymer thereof), wherein the polar compound has high compatibility with the liquid crystal compound. .
  • Another advantage is to provide a liquid crystal composition in which vertical alignment of liquid crystal molecules can be achieved by the action of a polymer generated from the polar compound.
  • Another advantage is the high maximum temperature of the nematic phase, the low minimum temperature of the nematic phase, small viscosity, suitable optical anisotropy, positively large dielectric anisotropy, large specific resistance, high stability against ultraviolet rays, high heat resistance
  • Another advantage is to provide a liquid crystal composition having an appropriate balance between at least two of these properties. Another advantage is a liquid crystal display device containing such a composition. Another advantage is to provide 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 to form a polymer in the composition.
  • a liquid crystalline compound having alkenyl is not polymerizable in that sense.
  • 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 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 in the initial stage and a large specific resistance after being used for a long time.
  • “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. It means having a retention rate.
  • characteristics may be evaluated by a aging test (including an accelerated deterioration test).
  • 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 the 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'".
  • An expression such as “at least one —CH 2 — may be replaced by —O—” may be used.
  • —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—. This is because this replacement produces unstable —O—O—CH 2 — (peroxide). 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.
  • the symbol of the terminal group R 1 is used for a plurality of compounds.
  • two groups represented by two arbitrary R 1 may be the same or different.
  • R 1 of the compound (1-1) is ethyl and R 1 of the compound (1-2) is ethyl.
  • R 1 of compound (1-1) is ethyl and R 1 of compound (1-2) is propyl.
  • This rule also applies to symbols such as other end groups.
  • the subscript 'a' is 2
  • there are two rings A 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 the subscript 'a' is greater than 2. This rule also applies to other symbols.
  • 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.
  • the diagonal line across one side of the hexagon represents that any hydrogen on the ring may be replaced with a group such as —Sp 1 —P 1 .
  • a subscript such as 'e' indicates the number of groups replaced. When the subscript 'e' is 0, there is no such replacement. When the subscript 'e' is 2 or more, there are a plurality of -Sp 1 -P 1 on the ring C.
  • the plurality of groups represented by —Sp 1 —P 1 may be the same or different.
  • ring A and ring B are independently X, Y, or Z”, since there are plural subjects, “independently” is used. In the case of “ring D is X, Y, or Z”, “independently” is not used because the subject is singular.
  • Ring D is used in multiple expressions, the rule “may be the same or different” applies to “Ring D”. 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. As the configuration of 1,4-cyclohexylene, trans is preferable to cis for increasing the maximum temperature.
  • the present invention includes the following items.
  • R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons
  • ring A and ring B are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine -2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl
  • Ring C and Ring E are independently cyclohexyl, cyclohexenyl, phenyl, 1- Nap
  • R 2 is a group represented by —OH, —OR 0 , —NH 2 , —NHR 0 , or —N (R 0 ) 2 , wherein R 0 is hydrogen or alkyl having 1 to 12 carbons; Yes; M 4 and M 5 are independently hydrogen, fluorine, alkyl of 1 to 5 carbons, or alkyl of 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine.
  • ring C and ring E are independently cyclohexyl, phenyl, 1-naphthyl, or 2-naphthyl, and in these rings, at least one hydrogen is fluorine, chlorine Alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen May be substituted with alkenyl having 2 to 12 carbon atoms replaced by fluorine or chlorine; ring D may be 1,4-cyclohexylene, 1,4-phenylene, naphthalene-1,2-diyl, or naphthalene- 2,6-diyl, and in these rings, at least one hydrogen is fluorine, chlorine, C 1-12 alkyl 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkyl having 1 to 12 carbon
  • Item 3. The liquid crystal composition according to item 1 or 2, containing at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-14) as a first component.
  • R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , X 9 , X 10 , X 11 , X 12 , X 13 , and X 14 are independently hydrogen or fluorine
  • Y 1 is fluorine, chlorine, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine, alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine, or at least 1 Alkenyloxy having 2 to 12 carbon atoms in which one hydrogen is replaced by fluorine or chlorine.
  • Item 4. The liquid crystal according to any one of items 1 to 3, wherein the first additive is at least one compound selected from the group of polar compounds represented by formulas (2-1) to (2-13): Composition.
  • R 2 is a group represented by —OH, —OR 0 , —NH 2 , —NHR 0 , or —N (R 0 ) 2 ;
  • R 0 is hydrogen or alkyl having 1 to 12 carbons
  • R 3 is hydrogen, fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 2 to 12 carbons Alkenyl, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine
  • Z 3 and Z 4 independently is a single bond or alkylene having 1 to 10 carbon atoms, in the alkylene, at least one of -CH 2
  • Item 5 The proportion of the first component is in the range of 5% to 55% by weight and the proportion of the first additive is in the range of 0.05% to 10% by weight based on the weight of the liquid crystal composition. 5. The liquid crystal composition according to any one of items 1 to 4.
  • Item 6. The liquid crystal composition according to any one of items 1 to 5, comprising at least one compound selected from the group of compounds represented by formula (3) as the second component.
  • R 4 and R 5 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 F and ring G are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5 -Difluoro-1,4-phenylene;
  • Z 5 is a single bond, -CH 2 CH 2- , -CH 2 O-, -OCH 2- , -COO-, or -OCO-; 1, 2, or 3.
  • Item 7. The liquid crystal composition according to any one of items 1 to 6, comprising at least one compound selected from the group of compounds represented by formulas (3-1) to (3-13) as a second component: object.
  • R 4 and R 5 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 8 The liquid crystal composition according to item 6 or 7, wherein the ratio of the second component is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition.
  • Item 9 The liquid crystal composition according to any one of items 1 to 8, comprising at least one compound selected from the group of compounds represented by formula (4) as a third component.
  • R 6 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons;
  • Ring I is 1,4-cyclohexylene, 1,4 -Phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane -2,5-diyl, or tetrahydropyran-2,5-diyl;
  • Z 6 is a single bond, —CH 2 CH 2 —, —COO—, or —OCO—;
  • X 15 and X 16 are independently hydrogen or fluorine;
  • Y 2 is fluorine, chlorine
  • Item 10 The liquid crystal composition according to any one of items 1 to 9, comprising at least one compound selected from the group of compounds represented by formulas (4-1) to (4-16) as a third component: object.
  • R 6 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons.
  • Item 11 The liquid crystal composition according to item 9 or 10, wherein the ratio of the third component is in the range of 5% by weight to 50% by weight based on the weight of the liquid crystal composition.
  • Item 12. The liquid crystal composition according to any one of items 1 to 11, comprising at least one compound selected from the group of compounds represented by formula (5) as a fourth component.
  • R 7 and R 8 are independently 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.
  • Ring J and Ring L are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine Or tetrahydropyran-2,5-diyl;
  • ring K is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5 - methyl-1,4-phenylene, it is a 3,4,5-trifluoro-2,6-diyl or 7,8-difluoro-chroman-2,6-diyl,;
  • Z 7 Oyo Z 8 are independently a single bond, -CH 2 CH 2 -, - CH 2 O -, - OCH 2 -, - COO-, or a -OCO-;
  • j is 1, 2 or 3,
  • K is 0 or 1 and the sum of j and
  • Item 13 The liquid crystal composition according to any one of items 1 to 12, comprising at least one compound selected from the group of compounds represented by formulas (5-1) to (5-22) as a fourth component: object.
  • R 7 and R 8 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or It is alkenyloxy having 2 to 12 carbon atoms.
  • Item 14 The liquid crystal composition according to item 12 or 13, wherein the ratio of the fourth component is in the range of 3% by weight to 40% by weight based on the weight of the liquid crystal composition.
  • Item 15. The liquid crystal composition according to any one of items 1 to 14, containing at least one compound selected from the group of polymerizable compounds 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 independently selected from the group of polymerizable groups represented by Formula (P-1) to Formula (P-5) Item 16.
  • 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 17. The item according to any one of Items 1 to 16, comprising at least one compound selected from the group of polymerizable compounds represented by Formula (6-1) to Formula (6-28) as the second additive.
  • Liquid crystal composition In the formulas (6-1) to (6-28), P 4 , P 5 , and P 6 are each independently a polymerizable group represented by the formula (P-1) to the formula (P-3).
  • Sp 10, Sp 11, and Sp 12 are independently a single bond or alkylene having 1 to 10 carbon atoms, in the alkylene, at least one of -CH 2 -, -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 18 The liquid crystal composition according to any one of items 15 to 17, 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 19 A liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 18.
  • Item 20 The liquid crystal display element according to item 19, wherein the operation mode of the liquid crystal display element is an IPS mode, a TN mode, an FFS mode, or an FPA mode, and the driving method of the liquid crystal display element is an active matrix method.
  • Item 21 A polymer-supported alignment type liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 14, wherein the first additive contained in the liquid crystal composition is polymerized.
  • Item 22 A liquid crystal display element of polymer-supported alignment type, comprising the liquid crystal composition according to any one of items 15 to 18, wherein the first additive and the second additive contained in the liquid crystal composition are polymerized. .
  • Item 23 Item 15. A liquid crystal display device having no alignment film, comprising the liquid crystal composition according to any one of items 1 to 14, wherein the first additive contained in the liquid crystal composition is polymerized.
  • Item 24 Item 19. A liquid crystal display element having no alignment film, comprising the liquid crystal composition according to any one of items 15 to 18, wherein the first additive and the second additive contained in the liquid crystal composition are polymerized.
  • Item 25 Use of the liquid crystal composition according to any one of items 1 to 18 in a liquid crystal display device.
  • Item 26 Item 19. Use of the liquid crystal composition according to any one of items 1 to 18 in a polymer supported alignment type liquid crystal display element.
  • Item 27 Use of the liquid crystal composition according to any one of items 1 to 18 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, and light is applied to the composition in a state where a voltage is applied to polymerize a polar compound having a polymerizable group contained in the composition.
  • (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 more.
  • the present invention includes the following items.
  • (C) The above composition comprising at least two compounds selected from the above polar compound (2).
  • (D) The above composition further containing a polar compound different from the above polar compound (2).
  • F An AM device containing the above composition.
  • (I) The above composition is used as a composition having a nematic phase.
  • (J) A composition prepared by adding an optically active compound to the above composition is used as an optically active 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 further contains other liquid crystal compounds, additives and the like in addition to the liquid crystal compounds selected from the compound (1), the compound (3), the compound (4), and the compound (5). Also good.
  • the “other liquid crystal compound” is a liquid crystal compound different from the compound (1), the compound (3), the compound (4), and the compound (5). 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 (3), compound (4), and compound (5). “Substantially” means that the composition B may contain an additive but does not contain any 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.
  • Compound (1) increases the dielectric anisotropy.
  • Compound (3) increases the maximum temperature or decreases the viscosity.
  • Compound (4) increases the dielectric anisotropy and decreases the minimum temperature.
  • Compound (5) increases the dielectric constant in the minor axis direction.
  • Compound (5) is added for the purpose of adjusting the elastic constant of the composition and adjusting the voltage-transmittance curve of the device.
  • Compound (2) is adsorbed on the substrate surface by the action of the polar group and controls the alignment of liquid crystal molecules. In order to obtain the desired effect, it is essential that the compound (2) has high compatibility with the liquid crystal compound.
  • Compound (2) has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-shaped, which is optimal for this purpose.
  • the compound (6) is added for the purpose of further adaptation to the polymer-supported orientation type device.
  • Compound (2) or compound (6) gives a polymer by polymerization. This polymer stabilizes the orientation of the liquid crystal molecules, thereby shortening the response time of the device and improving image burn-in.
  • the polymer of the compound (2) is effective.
  • a polymer of compound (6) is also effective.
  • the combination of compound (2) and compound (6) is more effective. A synergistic effect can be expected by this combination. In this combination, better long-term stability can be expected than compound (2) alone.
  • a desirable ratio of compound (1) is approximately 5% by weight or more for increasing the dielectric anisotropy, and approximately 55% by weight or less for decreasing the minimum temperature or decreasing the viscosity.
  • a more desirable ratio is in the range of approximately 5% by weight to approximately 45% by weight.
  • a particularly preferred ratio is in the range of approximately 10% by weight to approximately 35% by weight.
  • a desirable ratio of the compound (2) 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.
  • a desirable ratio of compound (3) is approximately 10% by weight or more for increasing the maximum temperature or decreasing the viscosity, and approximately 90% by weight or less for increasing the dielectric anisotropy.
  • a more desirable ratio is in the range of approximately 15% by weight to approximately 85% by weight.
  • a particularly desirable ratio is in the range of approximately 20% by weight to approximately 80% by weight.
  • a desirable ratio of the compound (4) is approximately 5% by weight or more for increasing the dielectric anisotropy, and approximately 50% by weight or less for decreasing the minimum temperature.
  • a more desirable ratio is in the range of approximately 5% by weight to approximately 40% by weight.
  • a particularly desirable ratio is in the range of approximately 5% by weight to approximately 30% by weight.
  • a desirable ratio of compound (5) is approximately 3% by weight or more for increasing the dielectric constant in the minor axis direction, and approximately 40% by weight or less for decreasing the minimum temperature.
  • a more desirable ratio is in the range of approximately 5% by weight to approximately 35% by weight.
  • a particularly preferred ratio is in the range of approximately 10% by weight to approximately 35% by weight.
  • a desirable ratio of compound (6) is about 0.03% by weight or more for improving long-term reliability of the device, and about 10% by weight or less for preventing display failure of the device.
  • 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 alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons It is. Desirable R 1 is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat. R 4 and R 5 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. To 12 alkenyl. Desirable R 4 or R 5 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 6 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons. Desirable R 6 is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat.
  • R 7 and R 8 are independently 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 7 or R 8 is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat, and alkoxy having 1 to 12 carbons for increasing the dielectric anisotropy.
  • 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 B are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro. 1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl.
  • Preferred ring A or ring B is 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,6-difluoro-1,4-phenylene for increasing the optical anisotropy.
  • Ring F and ring G are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. Desirable ring F or ring G is 1,4-cyclohexylene for decreasing the viscosity, and 1,4-phenylene for increasing the optical anisotropy.
  • Ring I is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene Pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl.
  • Preferred ring I is 1,4-phenylene or 2-fluoro-1,4-phenylene for increasing the optical anisotropy.
  • Ring J and Ring L are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, or Tetrahydropyran-2,5-diyl.
  • Preferred ring J or ring L is 1,4-cyclohexylene for decreasing the viscosity, tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and increasing the optical anisotropy. 1,4-phenylene.
  • Ring K 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 K is 2,3-difluoro-1,4-phenylene for increasing the dielectric anisotropy. Tetrahydropyran-2,5-diyl is Or And preferably It is.
  • Z 1 and Z 2 are independently a single bond, —CH 2 CH 2 —, —CH ⁇ CH—, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —CF 2 O—. , or -OCF 2 - is.
  • Desirable Z 1 or Z 2 is a single bond for decreasing the viscosity.
  • Z 5 is a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, or —OCO—.
  • Desirable Z 5 is a single bond for decreasing the viscosity.
  • Z 6 is a single bond, —CH 2 CH 2 —, —COO—, or —OCO—.
  • Z 6 is a single bond for decreasing the viscosity.
  • Z 7 and Z 8 are independently a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, or —OCO—.
  • Desirable Z 7 or Z 8 is a single bond for decreasing the viscosity, and —CH 2 O— or —OCH 2 — for increasing the dielectric anisotropy.
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , and X 16 are independent Hydrogen or fluorine. Desirable X 1 to X 15 or X 16 is fluorine for increasing the dielectric anisotropy.
  • Y 1 and Y 2 are independently fluorine, chlorine, alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine, and from 1 carbon atom in which at least one hydrogen is replaced with fluorine or chlorine.
  • Desirable Y 1 or Y 2 is fluorine for decreasing the minimum temperature.
  • a preferred example of alkyl in which at least one hydrogen is replaced by fluorine or chlorine is trifluoromethyl.
  • a preferred example of alkoxy in which at least one hydrogen is replaced by fluorine or chlorine is trifluoromethoxy.
  • alkenyloxy in which at least one hydrogen has been replaced by fluorine or chlorine is trifluorovinyloxy.
  • A is 1, 2, 3, or 4, b is 0, 1, 2, or 3, and the sum of a and b is 4 or less.
  • Preferred a is 2 or 3 for increasing the dielectric anisotropy. Desirable b is 0 or 1 for decreasing the minimum temperature.
  • h is 1, 2 or 3.
  • Preferred h is 1 for decreasing the viscosity, and 2 for decreasing the minimum temperature.
  • i is 1, 2, 3, or 4.
  • Preferred i is 2 or 3 for increasing the dielectric anisotropy.
  • j is 1, 2, or 3, k is 0 or 1, and the sum of j and k is 3 or less.
  • Preferred j is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.
  • Preferred k is 0 for decreasing the viscosity, and 1 for decreasing the minimum temperature.
  • R 2 is —OH, —OR 0 , —NH 2 , —NHR 0 , or —N (R 0 ) 2 a group represented, wherein R 0 is hydrogen or alkyl of 1 to 12 carbon atoms.
  • R 2 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 (nitrogen, oxygen) are particularly preferred. The compound having such a polar group is effective even at a low concentration.
  • the compound (2) is preferably stable to ultraviolet rays and heat. When compound (2) is added to the composition, it is preferable that this compound does not lower the voltage holding ratio of the device.
  • the compound (2) preferably has 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.
  • Ring C and Ring E 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, alkenyl having 2 to 12 carbons, or at least one hydrogen. May be substituted with 1 to 12 carbon alkyl substituted with fluorine or chlorine, or at least one hydrogen with 2 to 12 carbon alkenyl substituted with fluorine or chlorine.
  • Preferred ring C or ring E is cyclohexyl or phenyl.
  • Ring D 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,
  • Preferred ring D is 1,4-phenylene or 2-fluoro-1,4-phenylene.
  • Z 3 and Z 4 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 3 or Z 4 is a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, or —OCO—. Further preferred Z 3 or Z 4 is a single bond.
  • Sp 1 , Sp 2 , and Sp 3 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.
  • Preferred Sp 1 or Sp 2 is a C 1-10 alkylene in which a single bond and at least one —CH 2 — is replaced by —O—.
  • Sp 4 is a single bond or alkylene having 1 to 7 carbon atoms, in which at least one —CH 2 — may be replaced by —O—, —COO—, or —OCO—, One —CH 2 CH 2 — may be replaced with —CH ⁇ CH—, and in these groups, at least one hydrogen may be replaced with fluorine.
  • C is 0, 1, 2, 3, or 4; Preferred c is 0, 1, or 2.
  • e, f, and g are independently 0, 1, 2, 3, or 4, and the sum of e, f, and g is 2 or greater.
  • P 1 , P 2 , and P 3 are each independently a polymerizable group represented by the formula (PA).
  • M 4 and M 5 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine.
  • Preferred M 4 or M 5 is hydrogen or methyl for increasing the reactivity. More preferred M 4 or M 5 is hydrogen.
  • R 3 is hydrogen, fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, It is alkyl having 1 to 12 carbons in which one hydrogen is replaced with fluorine or chlorine, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine.
  • Preferred R 3 is alkyl having 1 to 12 carbons.
  • L 1 , L 2 , L 3 , L 4 , L 5 , and L 6 are independently hydrogen, fluorine, methyl, or ethyl.
  • Preferred L 1 to L 6 are hydrogen, fluorine, or methyl. More desirable L 1 to L 6 are hydrogen or fluorine.
  • P 4 , P 5 and P 6 are independently a polymerizable group different from the polymerizable group represented by the formula (PA).
  • This polymerizable group does not have a polar group such as —OH, —OR 0 , —NH 2 , —NHR 0 , or —N (R 0 ) 2 .
  • R 0 is hydrogen or alkyl having 1 to 12 carbons.
  • Preferred P 4 , P 5 , or P 6 is a group selected from the group of polymerizable 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 acryloyloxy (—OCO—CH ⁇ CH 2 ) or methacryloyloxy (—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 10 , Sp 11 , and Sp 12 are each independently a single bond or alkylene having 1 to 10 carbon atoms.
  • this alkylene at least one —CH 2 — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, and at least one —CH 2 CH 2 — may be —CH ⁇ CH— or —C ⁇ C— may be substituted, and in these groups at least one hydrogen may be substituted 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, 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. It may be replaced by alkyl having 1 to 12 carbon atoms replaced by fluorine or chlorine.
  • 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 11 and Z 12 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—, —CO—, —COO—, or —OCO— may be substituted, 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 ) —, in which at least one hydrogen may be replaced with fluorine or chlorine.
  • Preferred Z 11 or Z 12 is a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, or —OCO—. Further preferred Z 11 or Z 12 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 (1-14) according to Item 3.
  • at least one of the first components is compound (1-3), compound (1-4), compound (1-7), compound (1-9), compound (1-10), or compound (1-12) is preferred.
  • At least two of the first components are compound (1-3) and compound (1-4), compound (1-3) and compound (1-7), compound (1-3) and compound (1-10), The compound (1-7) and the compound (1-10), or a combination of the compound (1-9) and the compound (1-10) is preferable.
  • Desirable compounds (2) are the compounds (2-1) to (2-13) described in item 4.
  • at least one of the first additives is compound (2-1), compound (2-3), compound (2-5), compound (2-6), compound (2-7), compound (2-9), compound (2-10), or compound (2-11) is preferred.
  • At least two of the first additives are the compound (2-1) and the compound (2-5), the compound (2-3) and the compound (2-5), or the compound (2-10) and the compound (2-11). ) Is preferred.
  • Desirable compound (3) is the compound (3-1) to the compound (3-13) according to item 7.
  • at least one of the second components is compound (3-1), compound (3-3), compound (3-5), compound (4-6), compound (5-8), or compound (6-13) is preferred.
  • At least two of the second components are compound (3-1) and compound (3-3), compound (3-1) and compound (3-5), compound (3-1) and compound (3-8), Alternatively, a combination of the compound (3-3) and the compound (3-5) is preferable.
  • Desirable compound (4) is the compound (4-1) to the compound (4-16) described in item 10.
  • at least one of the third components is compound (4-4), compound (4-8), compound (4-9), compound (4-11), compound (4-12), compound ( 4-13) or a compound (4-16) is preferable.
  • At least two of the third components are compound (4-9) and compound (4-12), compound (4-11) and compound (4-12), compound (4-12) and compound (4-13), Alternatively, a combination of the compound (4-12) and the compound (4-16) is preferable.
  • Desirable compound (5) is the compound (5-1) to the compound (5-22) according to item 13.
  • at least one of the fourth components is the compound (5-1), the compound (5-3), the compound (5-4), the compound (5-6), the compound (5-8), or the compound (5-10) is preferred.
  • At least two of the fourth components are compound (5-1) and compound (5-6), compound (5-1) and compound (5-10), compound (5-3) and compound (5-8), The compound (5-4) and the compound (5-6), the compound (5-4) and the compound (5-8), or a combination of the compound (5-4) and the compound (5-10) is preferable.
  • Desirable compound (6) is the compound (6-1) to the compound (6-28) according to item 17. More desirable compounds (6) are the compound (6-1), the compound (6-2), the compound (6-3), the compound (6-4), the compound (6-5), the compound (6-6), Compound (6-7), Compound (6-18), Compound (6-20), Compound (6-23), Compound (6-24), Compound (6-25), and Compound (6-26) is there. Particularly preferred compounds (6) are the compound (6-2), the compound (6-3), the compound (6-4), and the compound (6-18).
  • 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 (2) and compound (6) are suitable for this purpose.
  • a polymerizable compound different from the compound (2) and the compound (6) may be added to the composition together with the compound (2) and the compound (6).
  • Preferred examples of such a polymerizable compound 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 (2) and 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.
  • This polymerizable compound is polymerized by ultraviolet irradiation.
  • the polymerization may be carried out 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 this 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—.
  • 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 polymer-supported orientation type element is as follows.
  • An element having two substrates called an array substrate and a color filter substrate is prepared.
  • 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.
  • a device without an alignment film is manufactured from a substrate without an alignment film according to the procedure described in the previous paragraph.
  • the compound (2) is arranged on the substrate because the polar group interacts with the substrate surface.
  • the liquid crystal molecules are aligned according to this arrangement.
  • the alignment of liquid crystal molecules is further promoted.
  • the polymerizable group 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.
  • a solvent such as chloroform or hexane 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 put in a TN device having a twist angle of 0 ° and a distance (cell gap) between two glass substrates of 5 ⁇ m. A voltage was applied to this device in steps of 0.5 V in the range of 16 V to 19.5 V. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds).
  • the peak current (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).
  • 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 was put in a normally white mode TN device in which the distance between two glass substrates (cell gap) was 0.45 / ⁇ n ( ⁇ m) and the twist angle was 80 degrees.
  • the voltage (32 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 10V 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 90%.
  • 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 90% to 10% (fall time; millisecond).
  • Pretilt angle A spectroscopic ellipsometer M-2000U (manufactured by J.A. Woollam Co., Inc.) was used to measure the pretilt angle.
  • Step 1 Paraformaldehyde (60.0 g), 1,4-diazabicyclo [2.2.2] octane (DABCO; 56.0 g) and water (200 ml) were placed in the reactor and stirred at room temperature for 15 minutes. .
  • the reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate.
  • the combined organic layers were washed with water and dried over anhydrous magnesium sulfate.
  • Step 4 Compound (T-5) was synthesized according to a conventional method.
  • Compound (T-5) (7.5 g), tetrakis (triphenylphosphine) palladium 1.3 g), tetrabutylammonium bromide (TBAB; 1.5 g), potassium carbonate (6.4 g), 1-bromo-3, 5-dimethoxybenzene (5 g), toluene (200 ml), 2-propanol (IPA; 80 ml) and pure water (20 ml) were placed in the reactor and stirred at 90 ° C. The reaction mixture was poured into water and the aqueous layer was extracted with toluene.
  • DMAP N-dimethyl-4-a
  • Step 8 Compound (T-9) (8.3 g) and THF (100 ml) were placed in a reactor and cooled to 0 ° C. Tetrabutylammonium fluoride (TBAF; 2.9 g) was added dropwise and stirred for 3 hours while warming to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with water and dried over anhydrous magnesium sulfate.
  • TAF Tetrabutylammonium fluoride
  • 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 symbolized compound 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 were appropriately selected from the compositions (M1) to (M13), polar compounds (PC-1) to (PC-5), and polymerizable compounds (RM-1) to (RM-9).
  • the composition is as follows.
  • Composition (M7) 3-BB (F) B (F, F) XB (F, F) -F (1-10) 3% 4-BB (F) B (F, F) XB (F, F) -F (1-10) 5% 3-BB (F, F) XB (F) B (F, F) -F (1-12) 3% 5-BB (F) B (F, F) XB (F) B (F, F) -F (1-14) 4% 2-HH-5 (3-1) 8% 3-HH-V (3-1) 25% 3-HH-V1 (3-1) 7% 4-HH-V1 (3-1) 6% 5-HB-O2 (3-2) 5% 7-HB-1 (3-2) 5% VFF-HHB-O1 (3-5) 8% VFF-HHB-1 (3-5) 3% 3-HH2BB (F, F) -F (4) 3% 4-HH2BB (F, F) -F (4) 3% 3-HBB (F, F) -F (4-8) 5% 5-HBB (F, F) -
  • the first additives are polar compounds (PC-1) to (PC-5).
  • the second additive is a polymerizable compound (RM-1) to (RM-9).
  • 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. This mixture was injected on a hot stage at 100 ° C. into an element having no alignment film in which the distance between two glass substrates (cell gap) was 4.0 ⁇ m. The device was irradiated with ultraviolet rays (28J) using an ultra-high pressure mercury lamp USH-250-BY (manufactured by USHIO INC.) To polymerize the polar compound (PC-1). This element was set in a polarizing microscope in which a polarizer and an analyzer were arranged orthogonally, and the element was irradiated with light from below, and the presence or absence of light leakage was observed. When light did not pass through the device, the vertical alignment was judged as “good”. This is because it is presumed that the liquid crystal molecules are sufficiently aligned. When light passing through the element was observed, the orientation was expressed as “bad”.
  • Examples 2 to 13 A device having no alignment film was prepared using a mixture prepared by adding a polar compound having a polymerizable group to the composition. 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 Example 13, a polymerizable compound (RM-1) was also added at a ratio of 0.5% by weight.
  • Example 13 As can be seen from Table 4, in Examples 1 to 13, the type of composition or polar compound was changed, but no light leakage was observed. This result shows that the vertical alignment is good even when the element does not have an alignment film, and the liquid crystal molecules are stably aligned. In Example 13, a polymerizable compound (RM-1) was further added, and similar results were obtained.
  • RM-1 polymerizable compound
  • the liquid crystal composition of the present invention can be used for a liquid crystal projector, a liquid crystal television and the like.

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  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
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  • Liquid Crystal (AREA)

Abstract

L'invention concerne : une composition de cristaux liquides qui permet d'obtenir un alignement vertical des molécules de cristaux liquides par l'action d'un polymère ; et un élément d'affichage à cristaux liquides qui contient cette composition. L'invention concerne une composition de cristaux liquides nématiques ayant une anisotropie diélectrique positive, qui contient, comme premier composant, un composé cristallin liquide spécifique ayant une grande anisotropie diélectrique positive, tout en contenant, en tant que premier additif, un composé polaire ayant un groupe polymérisable. Cette composition peut contenir, en tant que deuxième composant, un composé cristallin liquide spécifique qui a une température limite supérieure élevée ou une faible viscosité, en tant que troisième composant, un composé cristallin liquide spécifique qui a une anisotropie diélectrique positive, en tant que quatrième composant, un composé cristallin liquide spécifique qui a une anisotropie diélectrique négative, et en tant que second additif, un composé polymérisable. L'invention concerne en outre un élément d'affichage à cristaux liquides qui contient ladite composition.
PCT/JP2017/002170 2016-06-14 2017-01-23 Composition de cristaux liquides et élément d'affichage à cristaux liquides Ceased WO2017216996A1 (fr)

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CN108165279A (zh) * 2018-03-08 2018-06-15 京东方科技集团股份有限公司 一种液晶组合物及制备方法、显示面板、显示装置
JP2019189771A (ja) * 2018-04-26 2019-10-31 Jnc株式会社 液晶組成物および液晶表示素子
WO2019220673A1 (fr) * 2018-05-15 2019-11-21 Jnc株式会社 Composé, composition de cristaux liquides, et élément d'affichage à cristaux liquides
CN111258120A (zh) * 2018-11-30 2020-06-09 台湾捷恩智股份有限公司 液晶显示元件的半成品、液晶显示元件以及显示装置
WO2020158211A1 (fr) * 2019-02-01 2020-08-06 Jnc株式会社 Composite de cristaux liquides, élément de gradation de lumière à cristaux liquides, et fenêtre de gradation de lumière
WO2020184142A1 (fr) * 2019-03-14 2020-09-17 Jnc株式会社 Composés, composition de cristaux liquides, et élément d'affichage à cristaux liquides
CN112745861A (zh) * 2019-10-31 2021-05-04 捷恩智株式会社 液晶组合物、光学元件及液晶显示元件

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JP2015168826A (ja) * 2014-03-10 2015-09-28 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ ホメオトロピック配向を有する液晶媒体
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108165279A (zh) * 2018-03-08 2018-06-15 京东方科技集团股份有限公司 一种液晶组合物及制备方法、显示面板、显示装置
JP2019189771A (ja) * 2018-04-26 2019-10-31 Jnc株式会社 液晶組成物および液晶表示素子
WO2019220673A1 (fr) * 2018-05-15 2019-11-21 Jnc株式会社 Composé, composition de cristaux liquides, et élément d'affichage à cristaux liquides
CN111258120A (zh) * 2018-11-30 2020-06-09 台湾捷恩智股份有限公司 液晶显示元件的半成品、液晶显示元件以及显示装置
WO2020158211A1 (fr) * 2019-02-01 2020-08-06 Jnc株式会社 Composite de cristaux liquides, élément de gradation de lumière à cristaux liquides, et fenêtre de gradation de lumière
JPWO2020158211A1 (ja) * 2019-02-01 2021-12-02 Jnc株式会社 液晶複合体、液晶調光素子および調光窓
WO2020184142A1 (fr) * 2019-03-14 2020-09-17 Jnc株式会社 Composés, composition de cristaux liquides, et élément d'affichage à cristaux liquides
JPWO2020184142A1 (fr) * 2019-03-14 2020-09-17
CN113166035A (zh) * 2019-03-14 2021-07-23 捷恩智株式会社 化合物、液晶组合物及液晶显示元件
JP7597021B2 (ja) 2019-03-14 2024-12-10 Jnc株式会社 化合物、液晶組成物、および液晶表示素子
CN112745861A (zh) * 2019-10-31 2021-05-04 捷恩智株式会社 液晶组合物、光学元件及液晶显示元件
CN112745861B (zh) * 2019-10-31 2023-11-21 捷恩智株式会社 液晶组合物、光学元件及液晶显示元件

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