WO2020003599A1 - Composé polaire polymérisable, composition de cristaux liquides, et élément d'affichage à cristaux liquides - Google Patents

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

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Publication number
WO2020003599A1
WO2020003599A1 PCT/JP2019/006485 JP2019006485W WO2020003599A1 WO 2020003599 A1 WO2020003599 A1 WO 2020003599A1 JP 2019006485 W JP2019006485 W JP 2019006485W WO 2020003599 A1 WO2020003599 A1 WO 2020003599A1
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carbons
replaced
hydrogen
independently
compound
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Japanese (ja)
Inventor
田中　裕之
稲垣　順一
智広 矢野
匡一 矢野
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JNC Corp
JNC Petrochemical Corp
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JNC Corp
JNC Petrochemical Corp
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Priority to CN201980040468.4A priority Critical patent/CN112334441B/zh
Priority to JP2020527189A priority patent/JP7248025B2/ja
Publication of WO2020003599A1 publication Critical patent/WO2020003599A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
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    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D309/06—Radicals substituted by oxygen atoms
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
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    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/16—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon double bonds, e.g. stilbenes
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
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    • 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
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    • 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
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    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
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    • C09K19/00—Liquid crystal materials
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    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • 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 polymerizable polar compound, a liquid crystal composition and a liquid crystal display device. More specifically, a compound having both a polymerizable group such as methacryloyloxy and a polymerizable group such as acryloyloxy substituted by a polar group such as —OH group, including this compound, and having a positive or negative dielectric anisotropy.
  • the present invention relates to a negative liquid crystal composition and a liquid crystal display device including the composition or a partially cured product thereof.
  • a liquid crystal display device When a liquid crystal display device is classified based on the operation mode of liquid crystal molecules, PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), and IPS ( It can be classified into modes such as in-plane switching (VA), vertical alignment (VA), fringe field switching (FFS), and field-induced photo-reactive alignment (FPA). Further, based on the driving method of the elements, they can be classified into PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, and the like, and AM is classified into thin film transistor (TFT), metal insulator metal (MIM), and the like.
  • PC phase change
  • TN twisted nematic
  • STN super twisted nematic
  • ECB electrically controlled birefringence
  • OCB optical compensated bend
  • IPS It can be classified into modes such as in-plane switching (VA),
  • TFTs can be classified into amorphous silicon and amorphous 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 can be classified into 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 composition having a nematic phase has appropriate characteristics. By improving the characteristics of this composition, an AM device having good characteristics can be obtained. Table 1 below summarizes the relationship between the characteristics of the composition and the characteristics of the AM device.
  • the temperature range of the nematic phase (the temperature range exhibiting the nematic phase) is related to the temperature range in which the device can be used.
  • the preferred upper limit temperature of the nematic phase is about 70 ° C. or higher, and the preferred lower limit temperature of the nematic phase is about ⁇ 10 ° C. or lower.
  • the viscosity of the composition is related to the response time of the device. A short response time is preferable for displaying a moving image on the element. Shorter response times are desirable, even at 1 millisecond. Accordingly, the viscosity of the composition is preferably low, and more preferably low even at low temperatures.
  • the optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, large optical anisotropy or small optical anisotropy, that is, 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 product value depends on the type of operating mode. This value is about 0.45 ⁇ m for a device in a mode such as TN. This value ranges from about 0.30 ⁇ m to about 0.40 ⁇ m for the VA mode device, and from about 0.20 ⁇ m to about 0.30 ⁇ m for the IPS mode or FFS mode device.
  • a composition having a large optical anisotropy is preferable for a device having a small cell gap.
  • the large dielectric anisotropy of the composition contributes to a low threshold voltage, a small power consumption and a large contrast ratio of the device. Therefore, a large positive or negative 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 at the initial stage not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable.
  • compositions having a large specific resistance not only at room temperature but also at a temperature close to the maximum temperature of the nematic phase is preferable.
  • the stability of the composition to ultraviolet light and heat is related to the lifetime of the device. When this stability is high, the lifetime of the device is long. Such characteristics are preferable for an AM device used for a liquid crystal projector, a liquid crystal television, and the like.
  • a liquid crystal composition containing a polymer is used.
  • a composition to which a small amount of a polymerizable compound is added is injected into a device.
  • a polymerizable compound having a plurality of polymerizable groups is generally used.
  • the composition is irradiated with ultraviolet rays while applying a voltage between the substrates holding the element.
  • the polymerizable compound polymerizes to form a polymer network in the composition.
  • the orientation of the liquid crystal molecules can be controlled by the polymer, so that the response time of the device is shortened and the image sticking is improved.
  • Such an effect of the polymer can be expected for a device having a mode such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
  • a liquid crystal display element having no alignment film a mode in which a polar compound is added to a liquid crystal composition to align liquid crystal molecules has been proposed.
  • a composition to which a small amount of a polar compound and a small amount of a polymerizable compound are added is injected into a device.
  • the polymerizable compound a polymerizable compound having a plurality of polymerizable groups is generally used.
  • the liquid crystal molecules are aligned by the action of the polar compound.
  • the composition is irradiated with ultraviolet rays while applying a voltage between the substrates holding the element.
  • 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 polar compound and the polymer, so that the response time of the device is shortened and image sticking is improved.
  • a step of forming an alignment film is unnecessary. Since there is no alignment film, the electric resistance of the device does not decrease due to the interaction between the alignment film and the composition.
  • Such an effect due to the combination of the polar compound and the polymer can be expected for a device having a mode such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
  • Patent Document 1 describes polymerizable compounds (S-1) and (S-2) having both methacryloyloxy and a polymerizable group substituted with -OH.
  • the first object of the present invention is to provide at least one of chemically high stability, high ability to align liquid crystal molecules, high polymerization reactivity by ultraviolet irradiation, high solubility in a liquid crystal composition, and liquid crystal display.
  • An object of the present invention is to provide a compound having a large voltage holding ratio when used in a device.
  • the second problem involves this compound, and has a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, low viscosity, appropriate optical anisotropy, large positive or negative dielectric anisotropy, large specific resistance
  • Another object of the present invention is to provide a liquid crystal composition that satisfies at least one of characteristics such as high stability to ultraviolet light, high stability to heat, and a large elastic constant.
  • the third problem is that the device can be used in at least a wide temperature range, a short response time, a high transmittance, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, a long lifetime, and a good vertical alignment.
  • An object is to provide a liquid crystal display device having one.
  • the present invention relates to a compound represented by the formula (1), a liquid crystal composition containing the compound, and a liquid crystal display device containing the composition and / or a polymer obtained by polymerizing at least a part of the composition.
  • Ring A 1 and ring A 2 are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4 -Cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2 , 5-diyl, 1,3-dioxane-2,5-
  • a first advantage of the present invention is that it has at least one of high chemical stability, high polymerization reactivity by ultraviolet irradiation, high ability to align liquid crystal molecules, high solubility in a liquid crystal composition, and liquid crystal display.
  • An object of the present invention is to provide a compound having a large voltage holding ratio when used in a device.
  • the second advantage is that this compound contains this compound and has a high upper temperature limit of the nematic phase, a lower lower temperature limit of the nematic phase, low viscosity, appropriate optical anisotropy, positive or negative large dielectric anisotropy, and large specific resistance.
  • Another object of the present invention is to provide a liquid crystal composition that satisfies at least one of characteristics such as high stability to ultraviolet light, high stability to heat, and a large elastic constant.
  • the third advantage is that the device can be used in at least a wide temperature range, short response time, high transmittance, large voltage holding ratio, low threshold voltage, large contrast ratio, long lifetime, good vertical alignment, etc.
  • An object is to provide a liquid crystal display device having one.
  • liquid crystal compound is a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and has no liquid crystal phase, but controls physical properties of the composition such as an upper limit temperature, a lower limit temperature, a viscosity, and a dielectric anisotropy.
  • Polymerizable compound is a compound added for the purpose of forming a polymer in the composition.
  • the liquid crystal compound having alkenyl is not a polymerizable compound in that sense.
  • the “polar compound” assists the alignment of the liquid crystal molecules by the interaction of the polar group with the substrate surface or the like.
  • Liquid crystal display element is a generic term for liquid crystal display panels and liquid crystal display modules.
  • the liquid crystal composition is usually prepared by mixing a plurality of liquid crystal compounds.
  • the composition contains a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a dye, and Additives such as foaming agents are added as needed.
  • the ratio (content) of the liquid crystal compound in the liquid crystal composition is represented by a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive, even when an additive is added.
  • the ratio (addition amount) of the additive in the liquid crystal composition is represented by a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive.
  • the ratio of the liquid crystal compound or the additive is calculated based on the total weight of the liquid crystal compound. Parts per million by weight (ppm) may be used. The ratios of the polymerization initiator and the polymerization inhibitor in the liquid crystal composition are exceptionally expressed based on the weight of the polymerizable compound.
  • “Clearing point” is a transition temperature between a liquid crystal phase and an isotropic phase in a liquid crystal compound.
  • the “minimum temperature of the liquid crystal phase” is a transition temperature of a solid-liquid crystal phase (a smectic phase, a nematic phase, etc.) in the liquid crystalline compound.
  • the “maximum temperature of the nematic phase” is a transition temperature between a nematic phase and an isotropic phase in a mixture of a liquid crystal compound and a mother liquid crystal or a liquid crystal composition, and may be abbreviated as “maximum temperature”.
  • the “minimum temperature of the nematic phase” may be abbreviated as “minimum temperature”.
  • Expressions such as “increase the dielectric anisotropy” and “large dielectric anisotropy” mean that the absolute value of the value increases or increases.
  • “Large voltage holding ratio” means that the device has a large voltage holding ratio not only at room temperature in the initial stage but also at a temperature close to the upper limit temperature, and even after using the device for a long time, not only at room temperature but also at the upper limit temperature. Has a large voltage holding ratio even at a temperature close to.
  • the characteristics of the composition and the device may be examined before and after the aging test (including the accelerated deterioration test).
  • the expression “highly soluble in a liquid crystal composition” means that the solubility is high for any of the compositions containing a liquid crystal compound at room temperature.
  • the composition used to evaluate the solubility can be the criterion.
  • the compound represented by the formula (1) may be abbreviated as “compound (1)”.
  • Compound (1) means one compound represented by formula (1), a mixture of two compounds, or a mixture of three or more compounds. This rule is also applied to at least one compound selected from the group of compounds represented by the formula (2). Symbols such as A 1 , B 1 , C 1 and the like surrounded by a hexagon correspond to ring A 1 , ring B 1 , ring C 1 and the like, respectively.
  • the hexagon represents a six-membered ring such as a cyclohexane ring or a benzene ring or a condensed ring such as a naphthalene ring.
  • a straight line that crosses one side of this hexagon indicates that any hydrogen on the ring may be replaced by a group such as -Sp 1 -P 1 .
  • Subscripts such as f, g, and h indicate the number of replaced groups. When the subscript is 0, there is no such replacement.
  • ring A and ring C are independently X, Y, or Z
  • “independently” is used because the subject has a plurality.
  • “independent” is not used because the subject is singular.
  • the symbol of the terminal group R 11 is used for a plurality of compounds, but the groups represented by R 11 in these compounds may be the same or different.
  • R 11 of Compound (2) when R 11 of Compound (2) is ethyl, R 11 of compound (3) may be ethyl, it may be other groups, such as propyl.
  • This rule applies to other symbols.
  • i when i is 2, two rings D 1 are present.
  • the two groups represented by two rings D 1 in the compound may be the same or different.
  • i is greater than 2 also apply to any two rings D 1. This rule applies to other symbols.
  • the expression "at least one 'A'” means that the number of 'A' is arbitrary.
  • the expression "at least one 'A' may be replaced by 'B'” means that in the case of 'A' itself which is not replaced by 'B', one 'A' is replaced by 'B'. In this case, the case where two or more 'A' are replaced with 'B' is included, and in these, the position of 'A' replaced with 'B' is arbitrary. The rule that the replacement position is optional also applies to the expression “at least one 'A' has been replaced by 'B'”.
  • R 11 and R 12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, wherein at least one —CH 2 — is replaced with —O— And in these groups, at least one hydrogen may be replaced by fluorine.
  • “in these groups” may be interpreted literally.
  • “these groups” mean alkyl, alkenyl, alkoxy, alkenyloxy and the like. That is, “these groups” represent all of the groups described before the term “in these groups”. This commonsense interpretation applies to other terms.
  • Halogen means fluorine, chlorine, bromine, or iodine. Preferred halogens are fluorine or chlorine. A more preferred halogen is fluorine.
  • alkyl is linear or branched and does not include cyclic alkyl. Linear alkyls are generally preferred over branched alkyls. The same applies to terminal groups such as alkoxy and alkenyl.
  • trans is preferable to cis in order to increase the maximum temperature of the nematic phase.
  • 2-Fluoro-1,4-phenylene means the following two divalent groups.
  • fluorine may be leftward (L) or rightward (R). This rule also applies to left-right asymmetric divalent groups generated by removing two hydrogens from a ring, such as tetrahydropyran-2,5-diyl.
  • the present invention includes the following items.
  • Ring A 1 and ring A 2 are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4 -Cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2 , 5-diyl, 1,3
  • Ring A 1 and ring A 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, and in these rings, at least one hydrogen atom is fluorine, chlorine or a carbon atom having 1 to 4 carbon atoms.
  • Item 4. The compound according to any one of items 1 to 3, represented by any one of the formulas (1-1) to (1-4).
  • R 1 is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 14 carbons or alkenyloxy having 2 to 14 carbons.
  • At least one hydrogen is , May be replaced by fluorine;
  • Ring A 1 , ring A 2 , ring A 3 , and ring A 4 are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, Tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl, in which at least one hydrogen atom is fluorine, alkyl having 1 to 10 carbons, 2 to 10 carbons Alkenyl, alkoxy having 1 to 9 carbons, or alkenyloxy having 2 to 9 carbons, and in these groups, at least one hydrogen may be replaced by fluorine;
  • M 1 , M 2 , M 3 , M 4 , M 5 , and M 6 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or 1 to 5 carbons in which at least one hydrogen is replaced by fluorine.
  • 5 is alkyl;
  • R 2 and R 3 are each independently hydrogen, alkyl having 1 to 7 carbons, alkoxy having 1 to 6 carbons, or alkoxyalkyl having 1 to 6 carbons.
  • R 4 is a group selected from groups represented by formulas (1-a), (1-b), and (1-c);
  • One hydrogen may be replaced by fluorine or chlorine;
  • R 5 is hydrogen, alkyl having 1 to 7 carbons, alkoxy having 1 to 6 carbons, or alkoxyalkyl having 1 to 6 carbons;
  • X 1 is independently -OH, -NH 2 , -CO
  • Item 5. The compound according to any one of items 1 to 4, represented by any one of formulas (1-5) to (1-7).
  • R 1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkoxy having 1 to 9 carbons;
  • Ring A 1 , ring A 2 , ring A 3 , and ring A 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, Tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl, in which at least one hydrogen atom is fluorine, alkyl having 1 to 5 carbon atoms, 2 to 5 carbon atoms.
  • R 4 is a group selected from groups represented by formulas (1-a-1) and (1-b-1);
  • Sp 5 and Sp 6 are each independently a single bond or an alkylene having 1 to 10 carbon atoms, in which at least one —CH 2 — may be replaced by —O—;
  • R 5 is hydrogen or alkyl having 1 to 7 carbons.
  • Item 6. The compound according to any one of items 1 to 5, represented by any one of formulas (1-8) to (1-37).
  • Ring A 1 , ring A 2 , and ring A 3 are each independently 1,4-cyclohexylene or 1,4-phenylene, in which at least one hydrogen atom is fluorine, 1 to 5 carbon atoms. May be replaced by an alkyl of R 1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkoxy having 1 to 9 carbons; Z 1 and Z 2 are independently a single bond or — (CH 2 ) 2 —; Sp 1 , Sp 2 , Sp 3 , and Sp 4 are each independently a single bond or an alkylene having 1 to 5 carbon atoms, in which at least one —CH 2 — is replaced by —O—. Well; R 5 is hydrogen or alkyl having 1 to 5 carbons.
  • Item 7. The compound according to any one of items 1 to 6, represented by any one of formulas (1-38) to (1-49).
  • R 1 is alkyl having 1 to 10 carbons
  • Z 1 and Z 2 are independently a single bond or — (CH 2 ) 2 —
  • Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , and Y 6 are independently hydrogen, fluorine, methyl, or ethyl
  • Sp 1 and Sp 4 are independently a single bond or an alkylene having 1 to 5 carbon atoms, in which at least one —CH 2 — may be replaced by —O—
  • R 5 is hydrogen, methyl, or ethyl.
  • Item 8 The compound according to any one of claims 1 to 6, which is represented by any one of formulas (1-50) to (1-55).
  • R 1 is alkyl having 1 to 10 carbons
  • Z 1 and Z 2 are independently a single bond or — (CH 2 ) 2 —
  • Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , and Y 6 are independently hydrogen, fluorine, methyl, or ethyl
  • Sp 1 and Sp 4 are each independently a single bond or an alkylene having 1 to 5 carbon atoms, in which at least one —CH 2 — may be replaced by —O—.
  • Item 9 A liquid crystal composition containing at least one compound according to any one of items 1 to 8.
  • Item 10 The liquid crystal composition according to item 9, comprising at least one compound selected from the group of compounds represented by formulas (2) to (4).
  • R 11 and R 12 are each independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons. In the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—.
  • Ring B 1 , ring B 2 , ring B 3 , and ring B 4 are each independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene or pyrimidine-2,5-diyl;
  • Item 11 The liquid crystal composition according to item 9 or 10, comprising at least one compound selected from the group of compounds represented by formulas (5) to (7).
  • R 13 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons.
  • at least one —CH 2 — may be replaced by —O—, and in these groups, At least one hydrogen may be replaced by fluorine;
  • X 11 is fluorine, chlorine, —OCF 3 , —OCHF 2 , —CF 3 , —CHF 2 , —CH 2 F, —OCF 2 CHF 2 , or —OCF 2 CHFCF 3 ;
  • Ring C 1 , ring C 2 and ring C 3 are each independently 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl , Pyrimidine-2,5-diyl, or 1,4-phenylene in which at least one hydrogen has been replaced by fluorine;
  • Z 14 , Z 15
  • Item 12. The liquid crystal composition according to any one of items 9 to 11, comprising at least one compound selected from the group of compounds represented by formula (8).
  • R 14 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons.
  • at least one —CH 2 — may be replaced by —O—.
  • At least one hydrogen may be replaced by fluorine;
  • X 12 is —C ⁇ N or —C ⁇ C—C ⁇ N;
  • Ring D 1 is 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or at least one 1,4-phenylene in which two hydrogens have been replaced by fluorine;
  • Z 17 is a single bond, —COO—, —OCO—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —, or —C ⁇ C— Is;
  • Item 13 The liquid crystal composition according to any one of items 9 to 12, comprising at least one compound selected from the group of compounds represented by formulas (11) to (19).
  • R 15 , R 16 and R 17 are each independently an alkyl having 1 to 10 carbons or an alkenyl having 2 to 10 carbons, wherein at least one —CH 2 — is —O— May be replaced, in these groups at least one hydrogen may be replaced by fluorine, and R 17 may be hydrogen or fluorine;
  • Ring E 1 , ring E 2 , ring E 3 and ring E 4 are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl , Decahydronaphthalene-2,6-diyl, or 1,4-phenylene in which at least one hydrogen has been replaced by fluorine;
  • Ring E 5 and ring E 6 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydr
  • Item 14 The liquid crystal composition according to any one of items 9 to 13, comprising at least one polymerizable compound represented by the formula (20) other than the compound represented by the formula (1).
  • Ring F and Ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl, or pyridine -2-yl, in which at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 1 carbon having at least one hydrogen replaced by halogen.
  • Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene- 2,7-diyl, phenanthrene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, or
  • Item 15. The liquid crystal according to item 14, wherein P 11 , P 12 , and P 13 are each independently a group selected from the group of polymerizable groups represented by formulas (P-1) to (P-5). Composition.
  • M 11 , M 12 , and M 13 are each independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen.
  • Item 16 Item 14 or 15 wherein the polymerizable compound represented by the formula (20) is at least one compound selected from the group of polymerizable compounds represented by the formulas (20-1) to (20-7). 3. The liquid crystal composition according to item 1.
  • L 31 , L 32 , L 33 , L 34 , L 35 , L 36 , L 37 , and L 38 are independently hydrogen, fluorine, or methyl;
  • P 11 , P 12 and P 13 are independently a group selected from the group of polymerizable groups represented by the formulas (P-1) to (P-3);
  • M 11 , M 12 , and M 13 are each independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen.
  • Item 18 The liquid crystal composition according to any one of items 9 to 17, and at least one selected from the group consisting of a polymer obtained by polymerizing at least a part of the liquid crystal composition according to any one of items 9 to 17. Liquid crystal display element containing.
  • the present invention also includes the following items.
  • A at least two of additives such as a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a dye, and an antifoaming agent.
  • B A polymerizable composition prepared by adding a polymerizable compound different from the compound (1) or the compound (20) to the liquid crystal composition.
  • C A polymerizable composition prepared by adding the compound (1) and the compound (20) to the liquid crystal composition.
  • D A liquid crystal composite prepared by polymerizing the polymerizable composition.
  • E A polymer-supported alignment-type device containing the liquid crystal composite.
  • F A polymerizable composition prepared by adding the compound (1), the compound (20), and a polymerizable compound different from the compound (1) or the compound (20) to the liquid crystal composition is used.
  • a polymer-supported orientation-type device produced by the above method.
  • the compound (1) of the present invention has a mesogen moiety composed of at least one ring and has two polymerizable groups such as methacryloyloxy linked to the same carbon atom via a spacer; And acryloyloxy substituted with a polar group such as —OH.
  • Compound (1) is useful because the polar group interacts non-covalently with the substrate surface such as glass (or metal oxide).
  • One of the uses is an additive for a liquid crystal composition used in a liquid crystal display device. In this use, the compound (1) is added for the purpose of controlling the alignment of liquid crystal molecules.
  • Such an additive is chemically stable under the conditions sealed in the device, has a high ability to align liquid crystal molecules, has a large voltage holding ratio when used in a liquid crystal display device, and has an effect on the liquid crystal composition. Is preferably large. Since the compound (1) has two polymerizable groups such as methacryloyloxy linked to the same carbon atom via a spacer, a high-quality polymer network having high symmetry can be formed when polymerized. In addition, a voltage holding ratio when used in a liquid crystal display element is extremely large, and an element excellent in alignment and long-term stability can be easily obtained as compared with a case where a conventional compound is used.
  • Preferred examples of the compound (1) will be described. Preferred examples of symbols such as R 1 , A 1 and Sp 1 in the compound (1) also apply to the lower formulas of the compound (1), for example, the formula (1-1).
  • the properties of the compound (1) can be arbitrarily adjusted by appropriately combining the types of these groups. Since there is no great difference in the properties of the compounds, the compound (1) may contain isotopes such as 2 H (deuterium) and 13 C in an amount larger than the natural abundance.
  • Desirable R 1 is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 14 carbons, or alkenyloxy having 2 to 14 carbons. May be replaced by fluorine. More preferred R 1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 9 carbons. Particularly preferred R 1 is alkyl having 1 to 10 carbons.
  • R 1 is alkyl having 1 to 15 carbons or alkoxy having 1 to 14 carbons have high chemical stability.
  • Ring A 1 and ring A 2 are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4 -Cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2 , 5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in which at least one hydrogen atom is fluorine, chlorine Is substituted by alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons or alkenyloxy having 2 to 9 carbons Well
  • Preferred ring A 1 and ring A 2 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, and in these rings, at least one hydrogen atom is fluorine, chlorine, 1-10 carbon atoms.
  • alkyl alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyloxy having 2 to 9 carbons, and in these groups, at least one hydrogen is replaced by fluorine or chlorine. You may be.
  • More preferred ring A 1 and ring A 2 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl, in which at least one hydrogen atom is fluorine, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons Or alkenyloxy having 2 to 9 carbon atoms, and in these groups, at least one hydrogen may be replaced by fluorine.
  • More preferred ring A 1 and ring A 2 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl wherein at least one hydrogen atom is fluorine, alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons, or 1 to 4 carbons. It may be replaced by alkoxy.
  • Particularly preferred ring A 1 and ring A 2 are 1,4-cyclohexylene, 1,4-phenylene, 2-substituted, 3-substituted, or 2- and 3-substituted 1,4-phenylene, and the substituent Is preferably hydrogen, fluorine, alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons or alkoxy having 1 to 4 carbons, and more preferably hydrogen, fluorine, methyl or ethyl .
  • Ring A 1 and ring A 2 are independently 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-phenylene, 1 wherein at least one hydrogen is replaced by fluorine , 4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by alkyl having 1 to 5 carbon atoms, decahydronaphthalene-2,6-diyl, or tetrahydropyran-2,5-diyl, , High chemical stability.
  • Ring A 1 and ring A 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine, at least A compound in which one hydrogen is 1,4-phenylene in which alkyl having 1 to 5 carbons is replaced or 1,4-phenylene in which at least one hydrogen is replaced by alkenyl having 2 to 5 carbons is a liquid crystal composition. High solubility in substances.
  • Ring A 1 and ring A 2 are independently 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by alkyl having 1 to 5 carbons, and at least one hydrogen is having 1 to 4 carbons
  • the compound which is 1,4-phenylene, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl substituted with alkoxy has high polymerization reactivity by ultraviolet irradiation.
  • a is 0, 1, 2, 3, or 4, preferably 0, 1, 2, or 3, more preferably 1, 2, or 3, particularly preferably 1 or 2.
  • the compound in which a is 0 has high solubility in the liquid crystal composition.
  • the compound in which a is 3 or 4 has a high ability to align liquid crystal molecules.
  • the compound in which a is 1 or 2 has a high solubility in a liquid crystal composition, a high ability to align liquid crystal molecules, and a high polymerization reactivity by ultraviolet irradiation.
  • Z 1 is a single bond
  • a compound in which Z 1 is a single bond, — (CH 2 ) 2 —, —CF 2 O—, or —OCF 2 — has high solubility in a liquid crystal composition.
  • Compounds in which Z 1 is a single bond or — (CH 2 ) 2 — have a high ability to align liquid crystal molecules.
  • Sp 1 , Sp 2 , Sp 3 , and Sp 4 are independently a single bond or an alkylene having 1 to 7 carbon atoms have high chemical stability.
  • Sp 1 , Sp 2 , Sp 3 , and Sp 4 are each independently an alkylene having 1 to 7 carbon atoms, or a group in which at least one —CH 2 — of alkylene having 1 to 7 carbon atoms is replaced by —O—. Is highly soluble in the liquid crystal composition.
  • Sp 1 and Sp 4 are independently a single bond or an alkylene having 1 to 5 carbon atoms, in which at least one —CH 2 — may be replaced by —O—;
  • Sp 2 and Sp 3 are a single bond or alkylene having 1 to 5 carbon atoms, in which at least one —CH 2 — may be replaced by —O—, and more preferably —CH 2 -.
  • M 1 , M 2 , M 3 , M 4 , M 5 , and M 6 are independently hydrogen, fluorine, chlorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced by fluorine or chlorine Alkyl having 1 to 5 carbon atoms, preferably hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced by fluorine, Hydrogen is more preferred from the viewpoint that the compound becomes particularly highly reactive.
  • R 2 and R 3 are each independently hydrogen, alkyl having 1 to 7 carbons, alkoxy having 1 to 6 carbons, or alkoxyalkyl having 1 to 6 carbons.
  • R 2 and R 3 are more preferably independently a carbon atom having 1 to 5 carbon atoms from the viewpoint of being superior in solubility in a liquid crystal composition, having high chemical stability, and being a compound having a high ability to align liquid crystal molecules.
  • Particularly preferred R 2 and R 3 are methyl.
  • R 4 is a group selected from the groups represented by formulas (1-a), (1-b), and (1-c). Desirable R 4 is a group represented by the formula (1-a) or the formula (1-b).
  • R 4 is a group represented by the formula (1-a)
  • the solubility in the liquid crystal composition is large, and the voltage holding ratio when used in a liquid crystal display device is large.
  • R 4 is a group represented by the formula (1-b) or the formula (1-c)
  • the ability to align liquid crystal molecules is high.
  • R 4 is a group represented by the formula (1-b)
  • the solubility in the liquid crystal composition is high and the ability to align liquid crystal molecules is high.
  • R 5 is hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or alkoxyalkyl having 1 to 9 carbons. Desirable R 5 is hydrogen, alkyl having 1 to 7 carbons, alkoxy having 1 to 6 carbons, or alkoxyalkyl having 1 to 6 carbons. More preferred R 5 is hydrogen or alkyl having 1 to 7 carbons. Particularly preferred R 5 is hydrogen or alkyl having 1 to 5 carbons.
  • Preferred X 1 is independently —OH, —NH 2 , —COOH, or —SH. Particularly preferred X 1 is —OH.
  • X 1 is independently —OH, —NH 2 , —COOH, or —SH, the ability to align liquid crystal molecules is high.
  • X 1 is —OH, the solubility in the liquid crystal composition is high, the ability to align liquid crystal molecules is high, and the voltage holding ratio when used in a liquid crystal display device is high.
  • Examples of preferred compound (1) are compounds (1-1) to (1-4) described in item 4. Examples of more preferred compound (1) are the compounds (1-5) to (1-7) described in item 5. More preferred examples of the compound (1) are the compounds (1-8) to (1-37) described in item 6. Examples of the most preferred compound (1) are the compounds (1-38) to (1-49) described in item 7.
  • MSG 1 (or MSG 2 ) is a monovalent organic group having at least one ring.
  • the monovalent organic groups represented by a plurality of MSG 1 (or MSG 2 ) may be the same or different.
  • Compounds (1A) to (1H) correspond to compound (1) or an intermediate of compound (1).
  • rings A 1 and A 2 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-cyclohexenylene 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl
  • rings such as 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl and the like, starting materials are commercially available or synthetic methods are well known. .
  • Sp 2 and Sp 3 are —CH 2 —, M 1 , M 2 , M 3 and M 4 are hydrogen, and R 4 is a group represented by the formula (1-a) Wherein Sp 5 is —CH 2 — and X 1 is —OH (1-51) can be synthesized by the following method.
  • the compound (51) is reacted with sodium hydride and the compound (52) to obtain a compound (53).
  • Compound (54) is obtained by reacting compound (53) with palladium hydroxide under a hydrogen atmosphere.
  • Compound (54) is reacted with 3,4-dihydro-2H-pyran and pyridinium p-toluenesulfonate (PPTS) to give compound (55).
  • PPTS 3,4-dihydro-2H-pyran and pyridinium p-toluenesulfonate
  • Compound (55) is reduced using lithium aluminum hydride to obtain compound (56).
  • Compound (56) is reacted with methacrylic acid chloride and triethylamine to obtain compound (57), and then deprotected using PPTS to obtain compound (58).
  • Compound (58) and compound (59) are reacted in the presence of DCC and DMAP to obtain compound (60), which is then deprotected using PPTS to lead to compound (1-51). it can.
  • Sp 2 and Sp 3 are —CH 2 —, M 1 , M 2 , M 3 and M 4 are hydrogen, and R 4 is a group represented by the formula (1-a) Wherein Sp 5 is — (CH 2 ) 2 —, X 1 is —OH, a compound (1-52) — (CH 2 ) 2 —, and X 1 is —OH. 52) can be synthesized by the following method.
  • Compound (1-51) can be converted to compound (1-52) by reacting the compound (1-51) with phosphorus tribromide to cause bromination and then reacting with formaldehyde in the presence of an indium catalyst.
  • Sp 2 and Sp 3 are —CH 2 —
  • M 1 , M 2 , M 3 and M 4 are hydrogen
  • R 4 is a group represented by the formula (1-a) Wherein Sp 5 is —CH 2 O (CH 2 ) a — and X 1 is —OH (1-53)
  • Sp 5 is —CH 2 O (CH 2 ) a —
  • X 1 is —OH
  • Compound (1-51) is reacted with trifluoromethanesulfonic anhydride (Tf 2 O) and triethylamine, and then reacted with a corresponding diol having a carbon number a (HO— (CH 2 ) a —OH). Can lead to compound (1-53).
  • Sp 2 and Sp 3 are —CH 2 —, M 1 , M 2 , M 3 and M 4 are hydrogen, and R 4 is a group represented by the formula (1-b) Wherein Sp 5 and Sp 6 are —CH 2 —, R 5 is hydrogen, and X 1 is —OH, and the compound (1-54) can be synthesized by the following method.
  • Compound (61) is iodinated with iodine, triphenylphosphine, and imidazole to obtain compound (62), and then reacted with compound (63) and sodium hydride, paraformaldehyde and potassium carbonate sequentially to obtain compound (64).
  • the compound (64) is hydrolyzed using lithium hydroxide to obtain a compound (65).
  • the compound (58) is reacted with the compound (65) in the presence of DCC and DMAP to obtain the compound (66), which is then deprotected using PPTS to lead to the compound (1-54). it can.
  • Liquid crystal composition 3-1 Component Compound
  • the liquid crystal composition of the present invention contains Compound (1) as Component A.
  • the compound (1) can control the alignment of liquid crystal molecules by noncovalent interaction with the substrate of the device.
  • This composition preferably contains the compound (1) as the component A, and further contains at least one liquid crystal compound selected from the following components B, C, D, and E.
  • Component B is compounds (2) to (4).
  • Component C is compounds (5) to (7).
  • Component D is compound (8).
  • Component E is compounds (11) to (19). This composition may contain other liquid crystal compounds different from the compounds (2) to (8) and (11) to (19).
  • a composition with properly selected components has a high upper temperature limit, a lower lower temperature limit, a low viscosity, a suitable optical anisotropy (ie, large or small optical anisotropy), and a positive or negative large dielectric constant. It has anisotropy, large resistivity, stability to heat or ultraviolet light, and an appropriate elastic constant (ie, a large elastic constant or a small elastic constant).
  • Compound (1) is added to the composition for the purpose of controlling the alignment of liquid crystal molecules.
  • the preferable ratio of the compound (1) to 100% by weight of the liquid crystal composition is 0.05% by weight or more from the viewpoint that the liquid crystal molecules can be easily aligned, and the like, and display failure of the device can be further prevented.
  • the content is preferably 10% by weight or less.
  • a more desirable ratio is in the range of 0.1% to 7% by weight, and a particularly desirable ratio is in the range of 0.4% to 5% by weight.
  • Component B is a compound wherein the two terminal groups are alkyl or the like.
  • Component B has a small dielectric anisotropy.
  • Preferred examples of component B include compounds (2-1) to (2-11), compounds (3-1) to (3-19), and compounds (4-1) to (4-7). it can.
  • R 11 and R 12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH 2 — is —O— And at least one hydrogen may be replaced by fluorine.
  • Component B is a nearly neutral compound because the absolute value of the dielectric anisotropy is small.
  • the compound (2) is effective mainly for decreasing the viscosity or adjusting the optical anisotropy.
  • Compounds (3) and (4) have an effect of increasing the maximum temperature and thereby expanding the temperature range of the nematic phase, or an effect of adjusting the optical anisotropy.
  • the content of the component B increases, the dielectric anisotropy of the composition decreases, but the viscosity decreases. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the content of the component B is preferably higher.
  • the content of Component B is preferably at least 30% by weight, more preferably at least 40% by weight, based on 100% by weight of the liquid crystal composition, and the upper limit thereof is not particularly limited, but is, for example, 99.95% by weight.
  • Component C is a compound having fluorine, chlorine or a fluorine-containing group at at least one terminal.
  • Component C has a very large dielectric anisotropy.
  • Preferred examples of Component C include compounds (5-1) to (5-16), compounds (6-1) to (6-116), and compounds (7-1) to (7-59).
  • R 13 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons. In the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—.
  • At least one hydrogen may be replaced by fluorine;
  • X 11 is fluorine, chlorine, —OCF 3 , —OCHF 2 , —CF 3 , —CHF 2 , —CH 2 F, —OCF 2 CHF 2 , or —OCF 2 CHFCF 3 .
  • Component C has a positive dielectric anisotropy and has very good stability to heat, light, and the like, and is therefore suitably used when preparing a composition for a mode such as IPS, FFS, and OCB. .
  • the content of Component C with respect to 100% by weight of the liquid crystal composition is suitably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, and more preferably in the range of 40% by weight to 95% by weight. Range.
  • the content of Component C is preferably 30% by weight or less based on 100% by weight of the liquid crystal composition.
  • Component D is a compound (8) in which one terminal group is -C ⁇ N or -C ⁇ CC-N.
  • Component D has a more positive dielectric anisotropy because it has a cyano group.
  • Preferred examples of the component D include the compounds (8-1) to (8-64).
  • R 14 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons. In the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—. , At least one hydrogen may be replaced by fluorine; -X 12 is -C ⁇ N or -C ⁇ C-C ⁇ N.
  • Component D has a positive dielectric anisotropy and a large value, and thus is mainly used when preparing a composition for a mode such as TN. By adding this component D, the dielectric anisotropy of the composition can be increased.
  • Component D has the effect of expanding the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy.
  • Component D is also useful for adjusting the voltage-transmittance curve of the device.
  • the content of the component D with respect to 100% by weight of the liquid crystal composition is suitably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, more preferably 40% by weight to 95% by weight. Range.
  • the content of component D is preferably 30% by weight or less based on 100% by weight of the liquid crystal composition.
  • Component E is compounds (11) to (19).
  • Component E has a large negative dielectric anisotropy. These compounds have phenylene in which the lateral position is substituted with two halogens (fluorine or chlorine), such as 2,3-difluoro-1,4-phenylene.
  • Preferred examples of the component E include compounds (11-1) to (11-9), compounds (12-1) to (12-19), compounds (13-1) and (13-2), and a compound (14- 1) to (14-3), compounds (15-1) to (15-3), compounds (16-1) to (16-11), compounds (17-1) to (17-3), compound ( 18-1) to (18-3) and the compound (19-1).
  • R 15 , R 16 , and R 17 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — May be replaced by —O—, in these groups at least one hydrogen may be replaced by fluorine, and R 17 may be hydrogen or fluorine.
  • Component E has a large negative dielectric anisotropy.
  • Component E is suitably used when preparing a composition for a mode such as IPS, VA, and PSA.
  • the content of the component E is increased, the dielectric anisotropy of the composition is negatively increased, but the viscosity is increased. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the content is preferably small.
  • the dielectric anisotropy is about ⁇ 5
  • the content of the component E with respect to 100% by weight of the liquid crystal composition is preferably 40% by weight or more for sufficient voltage driving.
  • compound (11) is a bicyclic compound, and therefore has an effect of reducing viscosity, adjusting optical anisotropy, or increasing dielectric anisotropy. Since the compounds (12) and (13) are tricyclic compounds and the compound (14) is a tetracyclic compound, the effect of increasing the maximum temperature, increasing the optical anisotropy, or increasing the dielectric anisotropy is obtained. is there. Compounds (15) to (19) have the effect of increasing the dielectric anisotropy.
  • the content of the component E is preferably 40% by weight or more, more preferably 50% by weight to 95% by weight, based on 100% by weight of the liquid crystal composition.
  • the content of the component E is preferably 30% by weight or less based on 100% by weight of the liquid crystal composition.
  • a high maximum temperature, a low minimum temperature, a small viscosity, an appropriate optical anisotropy, a positive or negative large dielectric anisotropy, a large A liquid crystal composition that satisfies at least one of characteristics such as specific resistance, high stability to ultraviolet light, high stability to heat, and a large elastic constant can be prepared.
  • the liquid crystal composition is prepared by a known method. For example, there is a method in which the above components are mixed and dissolved by heating.
  • additives may be added to the composition.
  • additives include polymerizable compounds other than compound (1), polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dyes, defoamers, etc. It is. Such additives are well known to those skilled in the art and have been described in the literature.
  • the polymerizable compound is added for the purpose of forming a polymer in the liquid crystal composition.
  • a polymer can be generated by irradiating ultraviolet rays with a voltage applied between the electrodes to polymerize the compound (1).
  • the compound (1) is immobilized in a state where its polar group interacts non-covalently with the glass (or metal oxide) substrate surface. Thereby, the ability to control the alignment of the liquid crystal molecules is further improved, and an appropriate pretilt is obtained, so that the response time is shortened.
  • Preferred examples of the polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), and vinyl ketone. Further preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. Further preferred examples include compounds having both acryloyloxy and methacryloyloxy. Particularly preferred examples of the polymerizable compound include the compound (20).
  • Compound (20) is a compound different from compound (1). Compound (1) has a polar group. On the other hand, compound (20) preferably does not have a polar group.
  • Ring F and Ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidine- 2-yl or pyridin-2-yl, and in these rings, at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is halogen. It may be substituted by substituted alkyl having 1 to 12 carbons.
  • Preferred ring F or ring I is cyclohexyl, cyclohexenyl, phenyl, fluorophenyl, difluorophenyl, 1-naphthyl, or 2-naphthyl. More preferred ring F or ring I is cyclohexyl, cyclohexenyl, or phenyl. Particularly preferred ring F or ring I is phenyl.
  • ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene- 1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2, 6-diyl, naphthalene-2,7-diyl, phenanthrene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or Pyridine-2,5-diyl
  • Preferred ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3 -Diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl , Naphthalene-2,6-diyl and naphthalene-2,7-diyl.
  • More preferred ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, or 2-fluoro-1,4-phenylene. Particularly preferred ring G is 1,4-phenylene or 2-fluoro-1,4-phenylene. Most preferred ring G is 1,4-phenylene.
  • Desirable Z 7 or Z 8 is a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, or —OCO—. More preferred Z 22 or Z 23 is a single bond.
  • P 11 , P 12 , and P 13 are independently a polymerizable group.
  • Desirable P 11 to P 13 are groups selected from the group of polymerizable groups represented by the formulas (P-1) to (P-5). More preferred P 11 to P 13 are groups represented by formula (P-1), formula (P-2), or formula (P-3). Particularly preferred P 11 to P 13 are groups represented by the formula (P-1).
  • the wavy lines in the formulas (P-1) to (P-5) indicate binding sites.
  • M 11 , M 12 , and M 13 are each independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced by halogen. Alkyl having 1 to 5 carbon atoms. Desirable M 11 , M 12 or M 13 is hydrogen or methyl for increasing reactivity. More preferred M 11 is hydrogen or methyl, and more preferred M 12 or M 13 is hydrogen.
  • u is 0, 1, or 2.
  • Preferred u is 0 or 1.
  • f, g, and h are each independently 0, 1, 2, 3, or 4, and the sum of f, g, and h is 1 or more.
  • Preferred f, g, or h is 1 or 2.
  • Preferred sums are 2, 3 or 4.
  • a more preferred sum is 2 or 3.
  • Preferred examples of the compound (20) include the compounds (20-1) to (20-7) and the compounds (20-8) to (20-11) described in item 15. More preferred examples are compounds (20-1-1) to (20-1-5), compounds (20-2-1) to (20-2-5), compound (20-4-1), compound (20-4-1) 20-5-1), compound (20-6-1) and compound (20-7-1).
  • R 31 is hydrogen or methyl
  • R 32, R 33, and R 34 are independently alkyl of 5 hydrogen or C 1 -C, R 32, At least one of R 33 and R 34 is alkyl having 1 to 5 carbons
  • v and x are each independently 0 or 1
  • t and u are each independently an integer of 1 to 10 There; t + v and x + u is at most 10, respectively
  • L 36 from L 31 are each independently hydrogen or fluorine
  • L 37 and L 38 are independently hydrogen, fluorine or methyl.
  • the polymerizable compound in the composition can be rapidly polymerized by using a polymerization initiator such as a photoradical polymerization initiator.
  • a polymerization initiator such as a photoradical polymerization initiator.
  • photo-radical polymerization initiators include TPO, 1173, and 4265 from the Darocure series of BASF, and 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800 from the Irgacure series. 1850, and 2959.
  • photoradical polymerization initiators include 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyl Dimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate, benzophenone / methyltriethanolamine mixture It is.
  • ⁇ Polymerization can be carried out by adding a photo-radical polymerization initiator to the liquid crystal composition and then irradiating the liquid crystal composition with ultraviolet light while applying an electric field.
  • unreacted polymerization initiators or decomposition products of the polymerization initiators may cause display defects such as image sticking on the device.
  • photopolymerization may be performed without adding a polymerization initiator.
  • the preferred wavelength of the irradiated light is in the range of 150 nm to 500 nm. More preferred wavelengths are in the range from 250 nm to 450 nm, and most preferred wavelengths are in the range from 300 nm to 400 nm.
  • 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 derivatives such as hydroquinone and methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, and phenothiazine.
  • the optically active compound has an effect of inducing a helical structure in liquid crystal molecules to give a necessary twist angle, thereby preventing reverse twist.
  • the helical pitch can be adjusted by adding an optically active compound.
  • Two or more optically active compounds may be added for the purpose of adjusting the temperature dependence of the helical pitch.
  • Preferred examples of the optically active compound include the following compounds (Op-1) to (Op-18).
  • ring J is 1,4-cyclohexylene or 1,4-phenylene
  • R 28 is alkyl having 1 to 10 carbons. * Indicates an asymmetric carbon.
  • Antioxidants are effective for maintaining a large voltage holding ratio.
  • Preferred examples of the antioxidant include the following compounds (AO-1) and (AO-2); Irganox 415, Irganox 565, Irganox 1010, Irganox 1035, Irganox 3114, and Irganox 1098 (trade name: BASF).
  • the UV absorber is effective for preventing the lowering of the maximum temperature.
  • Preferred examples of the ultraviolet absorber include a benzophenone derivative, a benzoate derivative, a triazole derivative, and the like, and specific examples thereof include the following compounds (AO-3) and (AO-4); Tinuvin 328 and Tinuvin 99-2 (trade name; BASF); and 1,4-diazabicyclo [2.2.2] octane (DABCO).
  • Light stabilizers such as sterically hindered amines are preferred to maintain large voltage holding ratios.
  • Preferred examples of the light stabilizer include the following compounds (AO-5), (AO-6), and (AO-7); Tinuvin 144, Tinuvin 765, and Tinuvin 770DF (trade name; BASF); LA-77Y and LA- 77G (trade name; ADEKA).
  • a heat stabilizer is also effective for maintaining a large voltage holding ratio, and a preferable example is Irgafos 168 (trade name; BASF).
  • a dichroic dye such as an azo dye or an anthraquinone dye is added to the composition in order to make the device compatible with a device of a GH (guest host) mode.
  • Defoamers are effective in preventing foaming.
  • Preferred examples of the antifoaming agent include dimethyl silicone oil, methyl phenyl silicone oil and the like.
  • R 40 is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, —COOR 41 , or —CH 2 CH 2 COOR 41 , wherein R 41 has 1 carbon atoms.
  • R 42 is alkyl having 1 to 20 carbons.
  • R 43 is hydrogen, methyl or O ⁇ be (oxygen radicals); in the compound (AO-7); ring G 1 is 1,4-cyclohexylene or 1,4-phenylene , ring G 2 is 1,4-cyclohexylene, it is 1,4-phenylene or 1,4 least one hydrogen is replaced by fluorine group phenylene; compound (AO-5) and (AO-7 )), Z is 1, 2, or 3.
  • the liquid crystal composition has operation modes such as PC, TN, STN, OCB, and PSA, and can be suitably used for a liquid crystal display device driven by an active matrix system.
  • This composition has an operation mode such as PC, TN, STN, OCB, VA, and IPS, and can be suitably used for a liquid crystal display element driven by a passive matrix system.
  • These elements can be applied to any of a reflection type, a transmission type, and a transflective type.
  • This composition is also suitable for an NCAP (nematic curvilinear aligned phase) element, in which the composition is microencapsulated.
  • This composition can be used for a polymer dispersed liquid crystal display (PDLCD) and a polymer network liquid crystal display (PNLCD). In these compositions, a large amount of a polymerizable compound is added.
  • the ratio of the polymerizable compound is preferably 10% by weight or less based on 100% by weight of the liquid crystal composition, and more preferably 0.1% by weight to 2% by weight. %, And a more desirable ratio is in the range of 0.2% to 1.0% by weight.
  • the element in the PSA mode can be driven by a driving method such as an active matrix method or a passive matrix method. Such an element can be applied to any of a reflection type, a transmission type, and a semi-transmission type.
  • the polymer contained in the composition aligns the liquid crystal molecules.
  • Polar compounds help the liquid crystal molecules to align. That is, the polar compound can be used instead of the alignment film.
  • An example of a method for manufacturing such an element is as follows. An element having two substrates called an array substrate and a color filter substrate is prepared. This substrate has no alignment film. At least one of the substrates has an electrode layer. A liquid crystal composition is prepared by mixing a liquid crystal compound. Compound (1) and, if necessary, other polymerizable compounds and polar compounds are added to this composition. If necessary, additives may be further added. This composition is injected into the device. Light irradiation is performed with a voltage applied to this element. Ultraviolet light is preferred. The polymerizable compound is polymerized by light irradiation. By this polymerization, a composition containing a polymer is produced, and an element having a PSA mode is manufactured.
  • the polar compounds are arranged on the substrate because the polar groups interact with the substrate surface.
  • This polar compound orients the liquid crystal molecules.
  • the interaction with the substrate surface becomes stronger and orientation can be performed at a low concentration.
  • the action of the electric field further promotes the alignment of the liquid crystal molecules.
  • the polymerizable compound is also oriented according to this orientation. In this state, the polymerizable compound is polymerized by ultraviolet rays, so that a polymer maintaining this orientation is generated. The effect of the polymer additionally stabilizes the orientation of the liquid crystal molecules, thereby shortening the response time of the device.
  • the present invention will be described in more detail with reference to Examples (including Synthesis Examples and Usage Examples). The invention is not limited by these examples.
  • the invention also includes a mixture prepared by mixing at least two of the compositions of the use examples.
  • NMR analysis For measurement, DRX-500 manufactured by Bruker Biospin was used. In 1 H-NMR measurement, a sample was dissolved in a deuterated solvent such as CDCl 3, and the measurement was performed at room temperature under the conditions of 500 MHz and 16 accumulations. Tetramethylsilane was used as an internal standard. The 19 F-NMR measurement was carried out using CFCl 3 as an internal standard with an integral count of 24.
  • s means singlet
  • d means doublet
  • t means triplet
  • q means quartet
  • quin means quintet
  • sext means sextet
  • m means multiplet
  • br means broad.
  • a GC-2010 gas chromatograph manufactured by Shimadzu Corporation was used for measurement.
  • a capillary column DB-1 (length 60 m, inner diameter 0.25 mm, film thickness 0.25 ⁇ m) manufactured by Agilent Technologies Inc. was used.
  • Helium (1 ml / min) was used as a carrier gas.
  • the temperature of the sample vaporization chamber was set at 300 ° C.
  • the temperature of the detector (FID) was set at 300 ° C.
  • the sample was dissolved in acetone to prepare a 1% by weight solution, and 1 ⁇ l of the obtained solution was injected into the sample vaporization chamber.
  • the recorder used was a GC Solution system manufactured by Shimadzu Corporation.
  • Ultraviolet-visible spectroscopic analysis PharmaSpec @ UV-1700 manufactured by Shimadzu Corporation was used for the measurement. The detection wavelength was from 190 nm to 700 nm. The sample was dissolved in acetonitrile to prepare a 0.01 mmol / L solution, and placed in a quartz cell (optical path length 1 cm) for measurement.
  • Measurement method The characteristics were measured by the following methods. Most of these are described in the JEITA standard (JEITA ED-2521B) established by the Japan Electronics and Information Technology Industries Association (JEITA; Japan Electronics and Information Technology Industries Association), or modified methods thereof. there were. No thin film transistor (TFT) was attached to the TN device used for the measurement.
  • JEITA Japan Electronics and Information Technology Industries Association
  • TFT thin film transistor
  • Phase structure A sample was placed on a hot plate (FP-52 type hot stage, manufactured by METTLER CORPORATION) of a melting point apparatus equipped with a polarizing microscope. While heating the sample at a rate of 3 ° C./min, the phase state and its change were observed with a polarizing microscope to identify the type of phase.
  • FP-52 type hot stage manufactured by METTLER CORPORATION
  • the temperature at which a compound transitions from a solid to a liquid crystal phase such as a smectic phase or a nematic phase may be abbreviated as “lower limit temperature of liquid crystal phase”.
  • the temperature at which a compound transitions from a liquid crystal phase to a liquid may be abbreviated as “clearing point”.
  • the crystals were designated C. When the types of crystals can be distinguished, they are represented as C 1 and C 2 , respectively.
  • the smectic phase was represented by S, and the nematic phase was represented by N.
  • a smectic A phase, a smectic B phase if can be distinguished in the smectic C phase, or a smectic F phase, respectively S A, S B, expressed as S C or S F,.
  • the liquid (isotropic) was designated I.
  • the transition temperature is represented, for example, as “C 50.0 N 100.0 I”. This indicates that the transition temperature from the crystal to the nematic phase is 50.0 ° C., and the transition temperature from the nematic phase to the liquid is 100.0 ° C.
  • T C Minimum Temperature of a Nematic Phase
  • Viscosity Bulk viscosity; ⁇ ; measured at 20 ° C .; mPa ⁇ s
  • an E-type viscometer manufactured by Tokyo Keiki Co., Ltd. was used.
  • the method of measuring characteristics may differ between a sample having a positive dielectric anisotropy and a sample having a negative dielectric anisotropy.
  • the measuring method when the dielectric anisotropy is positive is described in the sections (8a) to (12a).
  • Viscosity Rotational viscosity; ⁇ 1; measured at 25 ° C .; mPa ⁇ s) Positive dielectric anisotropy: The measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was placed in a TN device in which the twist angle was 0 degree and the distance (cell gap) between two glass substrates was 5 ⁇ m. A voltage was applied to the device in a stepwise manner at intervals of 0.5 V from 16 V to 19.5 V. After 0.2 seconds of no application, application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds).
  • a peak current and a peak time of a transient current generated by this application were measured. These measurements and M.P.
  • the rotational viscosity value was obtained from the calculation formula (8) on page 40 of Imai et al. The value of the dielectric anisotropy required for this calculation was determined by the method described below using the element whose rotational viscosity was measured.
  • Viscosity Rotational viscosity; ⁇ 1; measured at 25 ° C .; mPa ⁇ s
  • Negative dielectric anisotropy The measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was placed in a VA device in which a distance (cell gap) between two glass substrates was 20 ⁇ m. A voltage was applied to the device in steps of 1 volt in the range of 39 volts to 50 volts. After 0.2 seconds of no application, application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds).
  • a peak current and a peak time of a transient current generated by this application were measured. These measurements and M.P.
  • the rotational viscosity value was obtained from the calculation formula (8) on page 40 of Imai et al. As the dielectric anisotropy required for this calculation, the value measured in the following section on dielectric anisotropy was used.
  • the dielectric constants ( ⁇ and ⁇ ) were measured as follows. 1) Measurement of dielectric constant ( ⁇ ): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a well-cleaned glass substrate. After rotating the glass substrate with a spinner, it was heated at 150 ° C. for 1 hour. A sample was placed in a VA device in which the distance (cell gap) between two glass substrates was 4 ⁇ m, and the device was sealed with an adhesive that cured with ultraviolet light.
  • Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant ( ⁇ ) in the major axis direction of the liquid crystal molecules was measured.
  • 2) Measurement of dielectric constant ( ⁇ ) A polyimide solution was applied to a well-cleaned glass substrate. After firing this glass substrate, a rubbing treatment was performed on the obtained alignment film. A sample was put in a TN device in which a distance (cell gap) between two glass substrates was 9 ⁇ m and a twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant ( ⁇ () of the liquid crystal molecules in the minor axis direction was measured.
  • Threshold voltage (Vth; measured at 25 ° C .; V) Positive dielectric anisotropy: 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 placed 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 device was increased stepwise from 0 V to 10 V in steps of 0.02 V. At this time, the device was irradiated with light from a vertical direction, and the amount of light transmitted through the device was measured.
  • a voltage-transmittance curve was prepared in which the maximum amount of light was 100% transmittance, and the minimum amount of light was 0% transmittance.
  • the threshold voltage was represented by a voltage when the transmittance became 90%.
  • the device was irradiated with light from a vertical direction, and the amount of light transmitted through the device was measured.
  • a voltage-transmittance curve was prepared in which the maximum amount of light was 100% transmittance, and the minimum amount of light was 0% transmittance.
  • the threshold voltage was represented by a voltage when the transmittance became 10%.
  • the maximum light amount was considered to be 100% transmittance, and the minimum light amount was considered to be 0% transmittance.
  • the rise time ( ⁇ r: rise time; millisecond) is the time required for the transmittance to change from 90% to 10%.
  • the fall time ( ⁇ f: fall time; millisecond) is the time required for the transmittance to change from 10% to 90%.
  • the response time was represented by the sum of the rise time and the fall time thus obtained.
  • a rectangular wave 60 Hz, 10 V, 0.5 seconds was applied to the device.
  • the device was irradiated with light from a vertical direction, and the amount of light transmitted through the device was measured.
  • the maximum light amount was considered to be 100% transmittance, and the minimum light amount was considered to be 0% transmittance.
  • the response time was represented by the time required for the transmittance to change from 90% to 10% (fall time; millisecond).
  • the polymerizable compound was polymerized by irradiating ultraviolet rays using F40T10 / BL (peak wavelength: 369 nm), a black light manufactured by Eye Graphics Co., Ltd.
  • the device was charged at 60 ° C. by applying a pulse voltage (60 microseconds at 1 V).
  • the decaying voltage was measured for 1.67 seconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined.
  • the area B is an area when no attenuation occurs.
  • the voltage holding ratio was expressed as a percentage of the area A to the area B.
  • Raw Materials Solmix (registered trademark) A-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (IPA) (1.1%). obtained.
  • THP represents a tetrahydropyranyl group.
  • Step 2 Sodium hydride (21.8 g) and THF (800 ml) were put into a reactor, a THF (240 ml) solution of compound (T-24) (107 g) was slowly added dropwise, and the mixture was stirred for 1 hour. And cooled. A THF (360 ml) solution of the compound (T-23) (61.0 g) was slowly added dropwise thereto, and the mixture was heated to reflux at 55 ° C. for 6 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with brine and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure.
  • the resulting intermediate was placed in another reactor with paraformaldehyde (28.6 g), potassium carbonate (65.8 g), and water (610 ml) and stirred at 80 ° C. for 6 hours.
  • the aqueous layer was extracted with ethyl acetate, and the obtained organic layer was washed with water and dried over anhydrous magnesium sulfate.
  • Step 1 Using compound (T-20) (12.0 g) as a starting material, compound (T-28) (13.1 g; 82%) was obtained in the same manner as in Step 6 of Synthesis Example 1.
  • Step 2 Using compound (T-28) (13.1 g) as a raw material, compound (1-2-3) (10.1 g; 88%) was obtained in the same manner as in Step 7 of Synthesis Example 1. Was.
  • Step 2 Using compound (T-38) (2.57 g) as a starting material, compound (1-3-40) (1.70 g; 74%) was obtained in the same manner as in Step 7 of Synthesis Example 1. Was.
  • the proportions of the components of the composition (i) are indicated in% by weight.
  • Samples were prepared by adding each compound to the composition (i) at a ratio of 3.0% by weight. This sample was injected into a device having no alignment film in which the distance (cell gap) between two glass substrates was 3.5 ⁇ m. The device was irradiated with ultraviolet rays (20 J) using F40T10 / BL (peak wavelength: 355 nm) manufactured by Eye Graphics Co., Ltd. to polymerize the added compound. The device was charged at 60 ° C. by applying a pulse voltage (60 microseconds at 1 V). The decaying voltage was measured for 1.67 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined. The area B is an area when no attenuation occurs. The voltage holding ratio was expressed as a percentage of the area A to the area B.
  • Table 2 summarizes the voltage holding ratios of compounds (1-2-1) and (1-2-3) and comparative compounds (S-1) and (S-2).
  • the compound (1-2-1) or (1-2-3) was used, a higher voltage holding ratio was obtained than when the comparative compound (S-1) or (S-2) was used.
  • the compound of the present application has a plurality of polymerizable groups such as methacryloyl, and the polymerizable groups are connected to the same carbon atom via a spacer, so that a high-quality polymer network having high symmetry is formed. This is because a decrease in the voltage holding ratio was suppressed. Therefore, it can be said that the compounds (1-2-1) and (1-2-3) are excellent compounds having a large voltage holding ratio when used in a liquid crystal display device.
  • V-HBB-2 (3-4) 11% 1O1-HBBH-4 (4-1) 3% 1O1-HBBH-5 (4-1) 3% 3-HHB (F, F) -F (6-3) 9% 3-H2HB (F, F) -F (6-15) 9% 4-H2HB (F, F) -F (6-15) 8% 5-H2HB (F, F) -F (6-15) 8% 3-HBB (F, F) -F (6-24) 9% 5-HBB (F, F) -F (6-24) 21% 3-H2BB (F, F) -F (6-27) 10% 5-HHBB (F, F) -F (7-6) 3% 3-HH2BB (F, F) -F (7-15) 4% 5-HHEBB-F (7-17) 2%
  • the following compound (1-2-3) was added to the above composition at a ratio of 1% by weight.
  • V-HBB-2 (3-4) 11% 1O1-HBBH-4 (4-1) 3% 1O1-HBBH-5 (4-1) 3% 3-HHB (F, F) -F (6-3) 9% 3-H2HB (F, F) -F (6-15) 9% 4-H2HB (F, F) -F (6-15) 8% 5-H2HB (F, F) -F (6-15) 8% 3-HBB (F, F) -F (6-24) 9% 5-HBB (F, F) -F (6-24) 21% 3-H2BB (F, F) -F (6-27) 10% 5-HHBB (F, F) -F (7-6) 3% 3-HH2BB (F, F) -F (7-15) 4% 5-HHEBB-F (7-17) 2%
  • the following compound (1-3-4) was added to the above composition at a ratio of 5% by weight.
  • the following compound (1-3-40) was added to the above composition at a ratio of 1% by weight.
  • the following compound (1-2-37) was added to the above composition at a ratio of 3% by weight.
  • the liquid crystal composition containing the compound (1) can be used for a display device such as a liquid crystal projector and a liquid crystal television.

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

Abstract

L'invention concerne un composé polaire qui présente une stabilité chimique élevée, une haute capacité pour aligner des molécules de cristaux liquides, et une solubilité élevée dans une composition de cristaux liquides, et qui permet à des éléments d'affichage à cristaux liquides d'avoir un rapport de maintien de tension élevé. Le composé selon l'invention est représenté par la formule (1). R1 représente l'hydrogène ou un alkyle éventuellement substitué ; les cycles A1 et A2 représentent chacun un cyclohexylène éventuellement substitué, phénylène ou similaire ; a vaut de 0 à 4 ; Z1 représente une liaison simple ou un alkylène éventuellement substitué ; Sp1 à Sp4 représentent chacun une liaison simple ou un alkylène éventuellement substitué ; M1 à M4 représentent chacun H, F, Cl, ou un alkyle éventuellement substitué ; R2 et R3 représentent chacun l'hydrogène ou un alkyle éventuellement substitué ; R4 représente un groupe choisi parmi les groupes représentés par la formule (1-a), la formule (1-b), et la formule (1-c) ; Sp5 et Sp6 représentent chacun une liaison simple ou un alkylène éventuellement substitué ; R5 représente l'hydrogène ou un alkyle éventuellement substitué ; et X1 représente -OH, -NH2, -COOH, -SH, ou similaires.
PCT/JP2019/006485 2018-06-27 2019-02-21 Composé polaire polymérisable, composition de cristaux liquides, et élément d'affichage à cristaux liquides Ceased WO2020003599A1 (fr)

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WO2020080120A1 (fr) * 2018-10-15 2020-04-23 Jnc株式会社 Composé, composition de cristaux liquides, et élément d'affichage à cristaux liquides
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014117692A1 (fr) * 2013-02-01 2014-08-07 江苏和成显示科技股份有限公司 Composition de cristaux liquides de type alignement stable polymère et son utilisation
WO2017199514A1 (fr) * 2016-05-18 2017-11-23 Jnc株式会社 Élément d'affichage à cristaux liquides contenant un milieu à cristaux liquides qui contient un composé polaire de faible poids moléculaire pour alignement homogène d'un milieu à cristaux liquides
WO2017209161A1 (fr) * 2016-06-03 2017-12-07 Jnc株式会社 Composé polaire polymérisable, composition de cristaux liquides, et élément d'affichage à cristaux liquides
WO2018047850A1 (fr) * 2016-09-09 2018-03-15 Jnc株式会社 Composition de cristaux liquides et élément d'affichage à cristaux liquides
WO2018097093A1 (fr) * 2016-11-28 2018-05-31 Jnc株式会社 Procédé de fabrication d'un élément d'affichage à cristaux liquides sans film d'orientation

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4853897B2 (ja) * 2005-08-05 2012-01-11 Ｊｎｃ株式会社 ナフタレンを有する光学活性化合物、液晶組成物、液晶表示素子、成形体
JP5556991B2 (ja) * 2009-07-21 2014-07-23 Ｄｉｃ株式会社 重合性化合物及び当該化合物の製造中間体
US9073850B2 (en) * 2011-11-24 2015-07-07 Jnc Corporation Polymerizable compound
JP6493677B2 (ja) * 2015-07-17 2019-04-03 Jnc株式会社 極性化合物、液晶組成物および液晶表示素子
TWI744235B (zh) * 2015-09-15 2021-11-01 日商捷恩智股份有限公司 聚合性極性化合物、液晶組成物及液晶顯示元件

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014117692A1 (fr) * 2013-02-01 2014-08-07 江苏和成显示科技股份有限公司 Composition de cristaux liquides de type alignement stable polymère et son utilisation
WO2017199514A1 (fr) * 2016-05-18 2017-11-23 Jnc株式会社 Élément d'affichage à cristaux liquides contenant un milieu à cristaux liquides qui contient un composé polaire de faible poids moléculaire pour alignement homogène d'un milieu à cristaux liquides
WO2017209161A1 (fr) * 2016-06-03 2017-12-07 Jnc株式会社 Composé polaire polymérisable, composition de cristaux liquides, et élément d'affichage à cristaux liquides
WO2018047850A1 (fr) * 2016-09-09 2018-03-15 Jnc株式会社 Composition de cristaux liquides et élément d'affichage à cristaux liquides
WO2018097093A1 (fr) * 2016-11-28 2018-05-31 Jnc株式会社 Procédé de fabrication d'un élément d'affichage à cristaux liquides sans film d'orientation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE Registry CAS; 13 March 2018 (2018-03-13), retrieved from STN Database accession no. RN2190548-60-6 *
DATABASE Registry CAS; 7 March 2019 (2019-03-07), retrieved from STN Database accession no. RN2248009-14-3 *

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