WO2019111892A1 - Composé, composition de cristaux liquides, et élément d'affichage à cristaux liquides - Google Patents

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

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WO2019111892A1
WO2019111892A1 PCT/JP2018/044555 JP2018044555W WO2019111892A1 WO 2019111892 A1 WO2019111892 A1 WO 2019111892A1 JP 2018044555 W JP2018044555 W JP 2018044555W WO 2019111892 A1 WO2019111892 A1 WO 2019111892A1
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replaced
diyl
carbons
hydrogen
ring
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田中　裕之
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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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/16—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon double bonds, e.g. stilbenes
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
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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
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells

Definitions

  • the present invention relates to a compound, a liquid crystal composition and a liquid crystal display device. More specifically, a compound having both a polar group such as -OH group and a plurality of polymerizable groups such as methacryloyloxy, a liquid crystal composition containing this compound and having positive or negative dielectric anisotropy, and this composition or The present invention relates to a liquid crystal display element including a part of the cured product.
  • the liquid crystal display elements are classified based on the operation mode of liquid crystal molecules: PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS ( It can be classified into modes such as in-plane switching (VA), vertical alignment (VA), fringe field switching (FFS), and field-induced photo-reactive alignment (FPA). Also, based on the driving method of the element, it can be classified into PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into thin film transistor (TFT), metal insulator metal (MIM), etc.
  • PC phase change
  • TN twisted nematic
  • STN super twisted nematic
  • ECB electrically controlled birefringence
  • OCB optical compensated bend
  • IPS It can be classified into modes such as in-plane switching (VA), vertical alignment (VA), fringe field switching (FFS),
  • TFTs can be classified into amorphous silicon and polycrystal silicon. The latter are classified into high temperature type and low temperature type according to the manufacturing process.
  • the classification based on light source can be classified into a reflection type using natural light, a transmission type using back light, and a semi-transmission type using both natural light and back light.
  • the liquid crystal composition having a nematic phase has appropriate properties. By improving the properties of this composition, an AM element having good properties can be obtained.
  • the relationship between the properties of the composition and the properties of the AM device is summarized in Table 1 below.
  • the characteristics of the composition are further described based on commercially available AM devices.
  • the temperature range of the nematic phase (the temperature range exhibiting the nematic phase) relates to the usable temperature range of the device.
  • the preferred upper temperature limit of the nematic phase is about 70 ° C. or higher, and the preferred lower temperature limit of the nematic phase is about -10 ° C. or lower.
  • the viscosity of the composition is related to the response time of the device. Short response times are preferred for displaying motion pictures on the device. Even shorter response times of 1 millisecond are desirable. Therefore, the viscosity of the composition is preferably low, and more preferably low even at low temperatures.
  • the optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large or small optical anisotropy, ie a suitable optical anisotropy, is required.
  • the product ( ⁇ n ⁇ d) of the optical anisotropy ( ⁇ n) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio.
  • the appropriate product value depends on the type of operating mode. This value is about 0.45 ⁇ m for devices of modes such as TN. This value is in the range of about 0.30 ⁇ m to about 0.40 ⁇ m in the VA mode device and in the range of about 0.20 ⁇ m to about 0.30 ⁇ m in the IPS mode or FFS mode device.
  • compositions with large optical anisotropy are preferred for small cell gap devices.
  • the large dielectric anisotropy in the composition contributes to low threshold voltage, low power consumption and high contrast ratio in the device. Therefore, positive or negative large dielectric anisotropy is preferred.
  • the large resistivity in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a large specific resistance at an initial stage not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable. After long time use, a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable.
  • the stability of the composition to ultraviolet light and heat is related to the lifetime of the device. When this stability is high, the lifetime of the device is long. Such characteristics are preferable for an AM element used for a liquid crystal projector, a liquid crystal television or the like.
  • a liquid crystal composition containing a polymer is used.
  • a composition to which a small amount of a polymerizable compound is added is injected into the device.
  • polymerizable compounds having a plurality of polymerizable groups are generally used.
  • the composition is irradiated with ultraviolet light.
  • the polymerizable compound polymerizes to form a polymer network in the composition.
  • the polymer can control the alignment of liquid crystal molecules, so that the response time of the device is shortened and the image sticking is improved.
  • Such an effect of the polymer can be expected in devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
  • a mode is proposed in which a polar compound is added to a liquid crystal composition to align liquid crystal molecules.
  • a composition to which a small amount of polar compound and a small amount of polymerizable compound are added is injected into the device.
  • the polymerizable compound polymerizable compounds having a plurality of polymerizable groups are generally used.
  • the liquid crystal molecules are oriented by the action of the polar compound.
  • the composition is irradiated with ultraviolet light.
  • the polymerizable compound is polymerized to stabilize the alignment of liquid crystal molecules.
  • the polar compound and the polymer make it possible to control the alignment of liquid crystal molecules, so that the response time of the device is shortened and the image sticking is improved.
  • the step of forming the alignment film is unnecessary. Since there is no alignment film, the interaction between the alignment film and the composition does not lower the electrical resistance of the device.
  • Such an effect by the combination of a polar compound and a polymer can be expected to an element having modes such as TN, ECB, OCB, IPS, VA, FFS, FPA.
  • Patent Document 1 describes a polymerizable compound (S-1) having a plurality of polar groups and a plurality of polymerizable groups.
  • One embodiment of the present invention is a compound having at least one of high chemical stability, high ability to align liquid crystal molecules, high polymerization reactivity by ultraviolet irradiation, and high solubility in a liquid crystal composition.
  • One embodiment of the present invention comprises this compound, and the high upper limit temperature of the nematic phase, the low lower limit temperature of the nematic phase, the low viscosity, the appropriate optical anisotropy, the positive or negative large dielectric anisotropy, the large
  • a liquid crystal composition satisfying at least one of properties such as specific resistance, high stability to ultraviolet light, high stability to heat, a large elastic constant, and a large voltage holding ratio when used in a liquid crystal display element.
  • One embodiment of the present invention is characterized by wide temperature range where the device can be used, short response time, high transmittance, large voltage holding ratio, low threshold voltage, large contrast ratio, long lifetime, good vertical orientation, etc.
  • a liquid crystal display device comprising at least one of
  • One embodiment of the present invention is a liquid crystal display device comprising a compound represented by the formula (1), a liquid crystal composition containing this compound, and a polymer obtained by polymerizing at least a part of this composition and / or this composition. About.
  • Ring A 1 and ring A 2 are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4 -Cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2 , 5-diyl, 1,3-dioxan
  • At least one of chemically high stability, high ability to align liquid crystal molecules, high polymerization reactivity by ultraviolet irradiation, and large voltage holding ratio when used in a liquid crystal display device It is possible to provide a compound having a high solubility in a liquid crystal composition. According to one embodiment of the present invention, comprising this compound, and high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, low viscosity, suitable optical anisotropy, positive or negative large dielectric anisotropy It is possible to provide a liquid crystal composition satisfying at least one of the properties such as large resistivity, high stability to ultraviolet light, high stability to heat, and a large elastic constant.
  • a wide temperature range in which the device can be used short response time, high transmittance, large voltage holding ratio, low threshold voltage, large contrast ratio, long lifetime, good vertical alignment, etc.
  • a liquid crystal display device having at least one of the following characteristics can be provided.
  • liquid crystal compound liquid crystal composition
  • liquid crystal display element liquid crystal display element
  • compound liquid crystal phase
  • element liquid crystal display element
  • Liquid crystalline compound is a compound having a liquid crystal phase such as a nematic phase or smectic phase, and has no liquid crystal phase, but controls physical properties of the composition such as upper limit temperature, lower limit temperature, viscosity, dielectric anisotropy, etc.
  • a generic term for compounds added for the purpose of This compound usually has a 6-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and the molecular structure is rod like.
  • the "polymerizable compound” is a compound to be added for the purpose of forming a polymer in the composition.
  • the liquid crystal compound having an alkenyl is not a polymerizable compound in that sense.
  • the “polar group” interacts non-covalently with a substrate surface such as glass (or metal oxide), etc., and the following —OH, —NH 2 , —OR 3 , —N (R 3 ) 2 , —COOH A group such as —SH or —Si (R 3 ) 3 .
  • the “polar compound” assists the alignment of liquid crystal molecules by interaction of polar groups with the substrate surface and the like.
  • “Liquid crystal display element” is a generic term for liquid crystal display panels and liquid crystal display modules.
  • the liquid crystal composition is usually prepared by mixing a plurality of liquid crystal compounds.
  • a polymerizable compound for the purpose of further adjusting the physical properties, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer, a dye, and an extinction
  • Additives such as foaming agents are added as needed.
  • the proportion (content) of the liquid crystal compound in the liquid crystal composition is represented by weight percentage (% by weight) based on the weight of the liquid crystal composition not including the additive, even when the additive is added.
  • the proportion (addition amount) of the additive in the liquid crystal composition is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition without the additive. That is, the proportions of the liquid crystal compound and the additive are calculated based on the total weight of the liquid crystal compound. Parts per million by weight (ppm) may be used.
  • the proportions of the polymerization initiator and the polymerization inhibitor in the liquid crystal composition are exceptionally expressed based on the weight of the polymerizable compound.
  • the “clearing point” is the transition temperature of the liquid crystal phase to the isotropic phase in the liquid crystal compound.
  • the “lower limit temperature of the liquid crystal phase” is a transition temperature of a solid-liquid crystal phase (eg, smectic phase, nematic phase) in a liquid crystal compound.
  • the “upper limit temperature of the nematic phase” is a transition temperature of the nematic phase-isotropic phase in the mixture of the liquid crystal compound and the base liquid crystal or the liquid crystal composition, and may be abbreviated as the “upper limit temperature”.
  • the “lower limit temperature of the nematic phase” may be abbreviated as the “lower limit temperature”.
  • the expressions "increase dielectric anisotropy” and “large dielectric anisotropy” mean that the absolute value of the value increases or is large.
  • the voltage holding ratio is large means that the device has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit at the initial stage, and even after using the device for a long time, not only the room temperature but also the upper limit temperature. It means that it has a large voltage holding ratio even at temperatures close to.
  • the characteristics of the composition or element may be examined before and after the aging test (including the accelerated aging test).
  • the expression "high solubility in liquid crystal composition” means that the solubility is high in any of the composition containing the liquid crystal compound at normal temperature, but as the composition, in the following examples, It can be based on the composition used to assess solubility.
  • the compound represented by Formula (1) may be abbreviated as "compound (1).”
  • the compound (1) means one compound represented by the formula (1), a mixture of two compounds, or a mixture of three or more compounds. This rule also applies to at least one compound etc. selected from the group of compounds represented by formula (2). Symbols such as A 1 , B 1 and C 1 surrounded by a hexagon correspond to ring A 1 , ring B 1 and ring C 1 and the like, respectively.
  • the hexagon represents a six-membered ring such as a cyclohexane ring or a benzene ring or a fused ring such as a naphthalene ring.
  • any hydrogen on the ring may be replaced by a group such as -Sp 1 -P 1 .
  • the subscripts such as f, g, h etc indicate the number of substituted groups. When the subscript is 0, there is no such replacement.
  • the ring A and the ring C are independently X, Y or Z”, “separately” is used because the subject is plural. When the subject is "ring A”, “independent” is not used because the subject is singular.
  • the symbol of the terminal group R 11 is used for a plurality of compounds, but the groups represented by R 11 in these compounds may be the same or different.
  • R 11 of Compound (2) when R 11 of Compound (2) is ethyl, R 11 of compound (3) may be ethyl, it may be other groups, such as propyl.
  • This rule also applies to other symbols.
  • compound (8) when i is 2, two rings D 1 are present. Two groups represented by two rings D 1 in this compound may be identical or different. When i is greater than 2, it also applies to any two rings D 1 . This rule also applies to other symbols.
  • the expression "at least one 'A'” means that the number of 'A' is arbitrary.
  • the expression “at least one 'A' may be replaced by 'B'” is replaced by one 'A' by 'B' in the case of 'A' itself which is not replaced by 'B' In this case, the case where two or more 'A's are replaced by' B 'is included, and in these, the position of' A 'replaced by' B 'is arbitrary.
  • the rule that the substitution position is optional also applies to the expression "at least one 'A' has been replaced by 'B'".
  • At least one A may be replaced by B, C or D
  • B, C or D means that if A is not substituted then at least one A is replaced by C if at least one A is replaced by B And when at least one A is replaced by D, it is meant to include the case where more than one A is replaced by at least two of B, C, D.
  • R 11 and R 12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — is replaced by —O— Also, in these groups, the expression “at least one hydrogen may be replaced by fluorine” may be used. In this expression, “in these groups” may be interpreted literally. In this expression, “these groups” mean alkyl, alkenyl, alkoxy, alkenyloxy and the like. That is, “these groups” represent all of the groups described earlier than the term “in these groups”. This common sense interpretation applies to other terms as well.
  • Halogen means fluorine, chlorine, bromine or iodine. Preferred halogens are fluorine or chlorine. A further preferred halogen is fluorine.
  • the alkyl is linear or branched and does not include cyclic alkyl. Linear alkyls are generally preferred over branched alkyls. The same is true for end groups such as alkoxy and alkenyl.
  • the configuration of 1,4-cyclohexylene is preferably trans rather than cis in order to raise the upper limit temperature of the nematic phase.
  • 2-fluoro-1,4-phenylene means the following two divalent groups.
  • fluorine may be leftward (L) or rightward (R). This rule also applies to asymmetric asymmetric divalent groups generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl.
  • One embodiment of the present invention includes the following items and the like.
  • Item 1 The compound represented by Formula (1).
  • Ring A 1 and ring A 2 are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4 -Cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2 , 5-diyl, 1,3-dioxan
  • the compound according to Item 1, wherein OCF 2 —, —CH 2 O—, —OCH 2 —, or —CF CF—.
  • Ring A 1 and ring A 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, and in these rings, at least one hydrogen is fluorine, chlorine, carbon number 1 10 alkyl, alkenyl of 2 to 10 carbons, alkoxy of 1 to 9 carbons, or alkenyloxy of 2 to 9 carbons, and in these groups, at least one hydrogen is fluorine or chlorine
  • the compound according to Item 1 or 2 which may be replaced by
  • Item 4. The compound according to any one of Items 1 to 3, which is represented by any one of formulas (1-1) to (1-4).
  • R 1 is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 14 carbons, or alkenyloxy having 2 to 14 carbons, and in these groups, at least one hydrogen is , May be replaced by fluorine;
  • Ring A 1 , ring A 2 , ring A 3 and ring A 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, Tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl, in which ring at least one hydrogen is fluorine, alkyl having 1 to 10 carbons, 2 to 10 carbons Of C 1 to C 9 alkoxy or C 2 to C 9 alkenyloxy, and in these groups, at least one hydrogen may be replaced by fluorine;
  • Z 1 , Z 2 and Z 3 independently represent a single
  • Item 5 The compound according to any one of Items 1 to 4, which is represented by any one of Formulas (1-5) to (1-7).
  • R 1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkoxy having 1 to 9 carbons;
  • Ring A 1 , ring A 2 , ring A 3 and ring A 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, Tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl, in which ring at least one hydrogen is fluorine, alkyl having 1 to 5 carbons, 2 to 5 carbons Or alkenyl of 1 to 4 carbon atoms;
  • Sp 1 , Sp 2 , Sp 3 , and Sp 4 are
  • Item 6. The compound according to any one of items 1 to 5, represented by any one of formulas (1-8) to (1-16):
  • R 1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkoxy having 1 to 9 carbons;
  • Z 1 and Z 2 are independently a single bond or-(CH 2 ) 2- ;
  • Sp 1 , Sp 2 and Sp 3 are independently a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one —CH 2 — may be replaced by —O—;
  • Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons, or 1 to 4 carbons Is alkoxy;
  • Z 1 is a single bond
  • Sp 2 and Sp 3 are -CH 2-
  • Y 1 and Y 2 are hydrogen
  • Sp 1 is not -CH 2- .
  • Item 7. The compound according to any one of items 1 to 6, which is represented by any one of formulas (1-17) to (1-23).
  • R 1 is alkyl having 1 to 10 carbons; Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 are independently hydrogen, fluorine, methyl or ethyl; Sp 1 is a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one —CH 2 — may be replaced by —O—; In formula (1-18), When Y 1 and Y 2 are hydrogen, Sp 1 is not —CH 2 —.
  • Item 8 A liquid crystal composition containing at least one of the compounds according to any one of items 1 to 7.
  • Item 9 The liquid crystal composition according to item 8, containing at least one compound selected from the group of compounds represented by formulas (2) to (4).
  • R 11 and R 12 independently represent alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one of —CH 2 — is replaced by —O— Well, in these groups at least one hydrogen may be replaced by fluorine;
  • Ring B 1 , ring B 2 , ring B 3 and ring B 4 are each independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene, or pyrimidine-2,5-diyl;
  • Item 10 The liquid crystal composition according to item 8 or 9, containing at least one compound selected from the group of compounds represented by formulas (5) to (7).
  • R 13 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—, and in these groups, At least one hydrogen may be replaced by fluorine;
  • X 11 is fluorine, chlorine, -OCF 3 , -OCHF 2 , -CF 3 , -CHF 2 , -CH 2 F, -OCF 2 CHF 2 , or -OCF 2 CHFCF 3 ;
  • Ring C 1 , ring C 2 and ring C 3 are independently 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl Pyrimidine-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine;
  • Z 14, Z 15, and Z 16 are independently a
  • Item 11 The liquid crystal composition according to any one of items 8 to 10, containing at least one compound selected from the group of compounds represented by formula (8).
  • R 14 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—, and in these groups, At least one hydrogen may be replaced by fluorine;
  • X 12 is -C ⁇ N or -C ⁇ C-C ⁇ N;
  • Ring D 1 is 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or at least 1
  • Z 17 represents a single bond, -COO-, -OCO-, -CH 2 O-, -OCH 2- , -CF 2 O-, -OCF 2- , -CH 2 CH 2- , or -C ⁇ C- And L 13 and L
  • Item 12. The liquid crystal composition according to any one of items 8 to 11, containing at least one compound selected from the group of compounds represented by formulas (11) to (19).
  • R 15, R 16, and R 17 are independently alkenyl alkyl carbon atoms or 2 to 10 of 1 to 10 carbon atoms, in the alkyl and alkenyl, at least one of -CH 2 - by -O- Which may be replaced, in these groups at least one hydrogen may be replaced by fluorine, and R 17 may be hydrogen or fluorine;
  • Ring E 1 , ring E 2 , ring E 3 and ring E 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl Decahydronaphthalene-2,6-diyl, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine;
  • Ring E 5 and ring E 6 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl
  • Item 13 The liquid crystal composition according to any one of items 8 to 12, containing at least one polymerizable compound represented by formula (20) other than the compound represented by formula (1).
  • Ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl or pyridine -2-yl, in these rings, at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 1 carbon having at least one hydrogen replaced with halogen May be replaced by 12 alkyls; Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl
  • Item 14 The liquid crystal according to item 13, wherein P 11 , P 12 and P 13 are independently a group selected from the group of polymerizable groups represented by formula (P-1) to formula (P-5) Composition.
  • M 11 , M 12 and M 13 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen.
  • Item 15 Item 13 or 14, wherein the polymerizable compound represented by Formula (20) is at least one compound selected from the group of polymerizable compounds represented by Formula (20-1) to Formula (20-7) The liquid crystal composition as described in.
  • L 31 , L 32 , L 33 , L 34 , L 35 , L 36 , L 37 and L 38 are independently hydrogen, fluorine or methyl;
  • P 11 , P 12 and P 13 are independently a group selected from the group of polymerizable groups represented by Formula (P-1) to Formula (P-3).
  • M 11 , M 12 and M 13 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen.
  • Ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl or pyridine -2-yl, in these rings, at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 1 carbon having at least one hydrogen replaced with halogen May be replaced by 12 alkyls; Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl
  • Item 17 At least one selected from the group consisting of the liquid crystal composition according to any one of items 8 to 16, and at least a part of the liquid crystal composition according to any one of items 8 to 16 polymerized. Liquid crystal display element contained.
  • One embodiment of the present invention also includes the following items.
  • A At least two of additives such as a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer, a pigment, and an antifoamer
  • additives such as a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer, a pigment, and an antifoamer
  • B A polymerizable composition prepared by adding a polymerizable compound different from the compound (1) and the compound (20) to the liquid crystal composition described above.
  • C A polymerizable composition prepared by adding the compound (1) and the compound (20) to the liquid crystal composition described above.
  • D A liquid crystal composite prepared by polymerizing the polymerizable composition.
  • the compound (1) is characterized by having a mesogenic moiety composed of at least one ring, one polar group, and two or more polymerizable groups. Further, a spacer moiety (below Sp 1 ) bonded to a ring is branched to have a polymerizable group and a polar group on at least one side, and at least one polymerizable group on the other side, in particular, a polymerizable group characterized in that via a spacer part (below Sp 4) capped ethoxy group is attached to.
  • the compound (1) is useful because polar groups interact non-covalently with a substrate surface such as glass (or metal oxide).
  • One of the uses is an additive for a liquid crystal composition used in a liquid crystal display device, and in this use, the compound (1) is added for the purpose of controlling the alignment of liquid crystal molecules. It is preferable that such an additive is chemically stable under the condition sealed in a device, has a high ability to orient liquid crystal molecules, and has a high solubility in a liquid crystal composition, and that the additive When using for a liquid crystal display element, it is preferable that a liquid crystal display element with a large voltage holding ratio can be obtained.
  • the compound (1) fulfills such properties to a considerable extent, and the solubility in liquid crystal compositions is extremely high, which can not be achieved by the conventional compounds, and by using the compound (1), the conventional compounds A device excellent in orientation and long-term stability can be easily obtained as compared with the case of using.
  • the compound (1) will be described. Preferred examples of the symbols such as R 1 , A 1 and Sp 1 in compound (1) also apply to subformulas of compound (1), for example, formula (1-1) and the like.
  • the properties can be arbitrarily adjusted by appropriately combining the types of these groups.
  • the compound (1) may contain isotopes such as 2 H (deuterium) and 13 C in an amount larger than the natural abundance ratio because there is no significant difference in the properties of the compounds.
  • R 1 is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 14 carbons, or alkenyloxy having 2 to 14 carbons, and in these groups, at least one hydrogen May be replaced by fluorine. More preferable R 1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 9 carbons. Particularly preferred R 1 is alkyl having 1 to 10 carbons.
  • R 1 is alkyl having 1 to 15 carbons or alkoxy having 1 to 14 carbons tend to have high chemical stability.
  • Compounds in which R 1 is alkyl having 1 to 15 carbons, alkenyls having 2 to 15 carbons, or alkenyloxys having 2 to 14 carbons tend to have high solubility in liquid crystal compositions.
  • Compounds in which R 1 is alkyl having 1 to 15 carbon atoms tend to have high ability to align liquid crystal molecules.
  • Ring A 1 and ring A 2 are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4 -Cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2 , 5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl in which at least one hydrogen is fluorine, chlorine , Alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyloxy having 2 to 9 carbons. In these groups, at least
  • Preferred ring A 1 and ring A 2 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1, 3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl in which at least one hydrogen is fluorine, chlorine, 1 to 10 carbon atoms Alkyl, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyloxy having 2 to 9 carbons, and in these groups, at least one hydrogen is replaced by fluorine or chlorine It may be done.
  • More preferred ring A 1 and ring A 2 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl in which at least one hydrogen is fluorine, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons in these rings Or alkenyloxy having 2 to 9 carbon atoms, and in these groups, at least one hydrogen may be replaced by fluorine.
  • ring A 1 and ring A 2 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl in which at least one hydrogen is fluorine, alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons, or 1 to 4 carbons. It may be replaced by alkoxy.
  • Particularly preferable ring A 1 and ring A 2 are 1,4-cyclohexylene, 1,4-phenylene, 2-substituted, 3-substituted, or 2- and 3-substituted 1,4-phenylene, and the substituents Is preferably hydrogen, fluorine, alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons, or alkoxy having 1 to 4 carbons, and more preferably hydrogen, fluorine, methyl or ethyl .
  • Ring A 1 and ring A 2 are independently 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-phenylene, or at least one hydrogen is replaced by fluorine 1 , 4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with alkyl having 1 to 5 carbon atoms, decahydronaphthalene-2,6-diyl, or tetrahydropyran-2,5-diyl , Chemical stability tends to be high.
  • Ring A 1 and Ring A 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine, at least Compounds in which one hydrogen is 1,4-phenylene in which one hydrogen is replaced by alkyl having 1 to 5 carbons or 1,4-phenylene in which at least one hydrogen is replaced by alkenyl having 2 to 5 carbons have a liquid crystal composition There is a tendency for the solubility to be large.
  • Ring A 1 and Ring A 2 are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by alkyl having 1 to 2 carbon atoms; And the ability to align liquid crystal molecules tends to be high.
  • Ring A 1 and Ring A 2 are independently 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by alkyl having 1 to 5 carbon atoms, at least one hydrogen has 1 to 4 carbon atoms
  • Compounds that are alkoxy-substituted 1,4-phenylene, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl tend to be highly polymerizable by ultraviolet irradiation. It is in.
  • a is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 1, 2 or 3 and particularly preferably 1 or 2. It is.
  • Compounds in which a is 0 tend to have high solubility in liquid crystal compositions.
  • Compounds in which a is 3 or 4 tend to have high ability to align liquid crystal molecules.
  • Compounds in which a is 1 or 2 have high solubility in liquid crystal compositions, high ability to align liquid crystal molecules, and tend to have high polymerization reactivity due to ultraviolet irradiation.
  • a particularly preferred Z 1 which is a bond or-(CH 2 ) 2- is a single bond.
  • Sp 1 is a single bond or an alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one —CH 2 — may be replaced by —O—;
  • Sp 2 and Sp 3 are independently a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one —CH 2 — may be replaced by —O—, more preferably -CH 2- and Sp 4 is -CH 2- .
  • Sp 5 is alkylene having 2 to 10 carbons, and in this alkylene, at least one —CH 2 — may be replaced by —O—.
  • Preferred Sp 5 is alkylene having 2 to 7 carbon atoms, in which at least one —CH 2 — may be replaced by —O—.
  • Compounds in which Sp 5 is an alkylene having 2 to 7 carbon atoms have high chemical stability and tend to be more excellent in solubility in liquid crystal compositions.
  • Compounds in which Sp 5 is a group in which at least one —CH 2 — of C 2 to C 7 alkylene is replaced by —O— have a high solubility in liquid crystal compositions and tend to have high ability to align liquid crystal molecules. It is in.
  • Sp 5 is particularly preferably — (CH 2 ) 2 — from the viewpoint of being a compound which is more excellent due to the solubility in the liquid crystal composition.
  • M 1 , M 2 , M 3 and M 4 independently represent hydrogen, fluorine, chlorine, alkyl having 1 to 5 carbon atoms, or 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine
  • Preferred R 2 is hydrogen or alkyl having 1 to 5 carbons. More preferable R 2 is alkyl having 1 to 3 carbon atoms, from the viewpoint of being a compound which is more excellent in solubility in liquid crystal composition, high in chemical stability, and high in ability to align liquid crystal molecules, etc.
  • Preferred R 2 is methyl.
  • X 1 is —OH, —NH 2 , —OR 3 , —N (R 3 ) 2 , —COOH, —SH, or —Si (R 3 ) 3 .
  • preferable X 1 is —OH, —NH 2 or —SH, and particularly preferable X 1 is —OH.
  • Examples of preferable compound (1) are compounds (1-1) to (1-4) described in Item 4. Examples of more preferable compound (1) are compounds (1-5) to (1-7) described in item 5. Examples of further preferable compound (1) are compounds (1-8) to (1-16) described in Item 6. Examples of the most preferred compound (1) are compounds (1-17) to (1-23) described in Item 7.
  • Synthesis of Compound (1) A synthesis method of compound (1) will be described.
  • the compound (1) can be synthesized by appropriately combining the methods of synthetic organic chemistry.
  • the compounds that did not describe the synthesis method are “Organic Synthesis” (Organic Syntheses, John Wiley & Sons, Inc.), “Organic Reactions” (Organic Reactions, John Wiley & Sons, Inc.), “Comprehensive Organic” Synthesis can be carried out by the method described in the book such as “Comprehensive Organic Synthesis, Pergamon Press”, “New Experimental Chemistry Lecture” (Maruzen).
  • MSG 1 (or MSG 2 ) is a monovalent organic group having at least one ring.
  • the monovalent organic groups represented by a plurality of MSG 1 (or MSG 2 ) may be the same or different.
  • Compounds (1A) to (1G) correspond to compound (1) or an intermediate of compound (1).
  • ring A 1 and A 2 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-cyclohexenylene , 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl
  • Starting materials are commercially available with respect to rings such as 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, etc., or a synthetic method is well known .
  • Sp 4 is -CH 2-
  • Sp 5 is-(CH 2 ) 2-
  • M 1 , M 2 , M 3 and M 4 are hydrogen and X 1 is-
  • the compound (1-51) which is OH can be synthesized by the following method.
  • Compound (51) is reacted with formaldehyde in the presence of DABCO (1,4-diazabicyclo [2.2.2] octane) to give compound (52).
  • Compound (52) is reacted with trifluoromethanesulfonic anhydride (Tf 2 O) and triethylamine, and then reacted with ethylene glycol to give compound (53).
  • Tf 2 O trifluoromethanesulfonic anhydride
  • Compound (53) is reacted with 3,4-dihydro-2H-pyran in the presence of PPTS (pyridinium p-toluenesulfonate) to give compound (54).
  • Compound (54) is hydrolyzed with lithium hydroxide to give compound (55).
  • Diol (56) synthesized by a known method and compound (57) are reacted in the presence of triethylamine to obtain compound (58).
  • Compound (58) and Compound (55) are reacted in the presence of DCC and DMAP to obtain Compound (59), and then deprotected using PPTS to lead to Compound (1-51). it can.
  • Liquid Crystal Composition 3-1 Component Compound
  • the liquid crystal composition according to an embodiment of the present invention contains the compound (1) as a component A.
  • the compound (1) can control the alignment of liquid crystal molecules by noncovalent interaction with the substrate of the device. It is preferable that this composition contains the compound (1) as the component A, and further contains at least one liquid crystal compound selected from the following components B, C, D, and E.
  • Component B is selected from compounds (2) to (4).
  • Component C is selected from compounds (5) to (7) other than compounds (2) to (4).
  • Component D is a compound (8).
  • Component E is selected from compounds (11) to (19). This composition may contain other liquid crystal compounds different from the compounds (2) to (8) and (11) to (19).
  • compositions with appropriately selected components have high upper limit temperature, lower limit temperature, lower viscosity, suitable optical anisotropy (ie large optical anisotropy or small optical anisotropy), positive or negative large dielectric constant It has anisotropy, high specific resistance, stability to heat or ultraviolet light, and a suitable elastic constant (ie, a large elastic constant or a small elastic constant).
  • the compound (1) is added to the composition for the purpose of controlling the alignment of liquid crystal molecules.
  • the preferred ratio of the compound (1) to 100% by weight of the liquid crystal composition is 0.05% by weight or more from the viewpoint that liquid crystal molecules can be easily aligned, etc., and the display defect of the device can be further prevented. From the point of etc., it is preferable that it is 10 weight% or less. A more preferable ratio is in the range of 0.1% by weight to 7% by weight, and a further preferable ratio is in the range of 0.4% by weight to 5% by weight, and a particularly preferable ratio is 0.5% by weight to 5%. It is the range of weight%. These ratios also apply to the composition containing compound (20).
  • Component B is a compound in which the two end groups are alkyl or the like.
  • Component B has a small dielectric anisotropy.
  • Preferred examples of component B include compounds (2-1) to (2-11), compounds (3-1) to (3-19), and compounds (4-1) to (4-7). it can.
  • R 11 and R 12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl or alkenyl, at least one —CH 2 — is —O— In these groups, at least one hydrogen may be replaced by fluorine.
  • the component B is a compound close to neutrality because the absolute value of the dielectric anisotropy is small.
  • the compound (2) is mainly effective in reducing the viscosity or adjusting the optical anisotropy.
  • the compounds (3) and (4) are effective in extending the temperature range of the nematic phase or in adjusting the optical anisotropy by raising the upper limit temperature.
  • the content of Component B is preferably 30% by weight or more, more preferably 40% by weight or more, based on 100% by weight of the liquid crystal composition, and the upper limit thereof is not particularly limited, and is, for example, 99.95% by weight.
  • Component C is a compound having a fluorine, chlorine or fluorine-containing group at at least one end.
  • Component C has a large dielectric anisotropy.
  • Preferred examples of component C include compounds (5-1) to (5-16), compounds (6-1) to (6-116), and compounds (7-1) to (7-59). .
  • R 13 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O— In these groups, at least one hydrogen may be replaced by fluorine;
  • X 11 is fluorine, chlorine, -OCF 3 , -OCHF 2 , -CF 3 , -CHF 2 , -CH 2 F, -OCF 2 CHF 2 or -OCF 2 CHFCF 3
  • Component C has a positive dielectric anisotropy and is very good in stability to heat, light and the like, and thus is suitably used when preparing a composition for modes such as IPS, FFS and OCB. .
  • the content of component C with respect to 100% by weight of the liquid crystal composition is suitably in the range of 1% by weight to 99% by weight, and preferably Is in the range of 10% by weight to 97% by weight, more preferably in the range of 40% by weight to 95% by weight.
  • component C is added to a composition having a negative dielectric anisotropy, the content of component C is preferably 30% by weight or less based on 100% by weight of the liquid crystal composition.
  • Component D is a compound (8) in which one terminal group is —C ⁇ N or —C ⁇ C—C ⁇ N.
  • Component D has a cyano group and thus has a larger dielectric anisotropy positively.
  • compounds (8-1) to (8-64) can be mentioned.
  • R 14 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O— In these groups, at least one hydrogen may be replaced by fluorine; -X 12 is -C ⁇ N or -C ⁇ C-C ⁇ N.
  • Component D is mainly used when preparing a composition for a mode such as TN since the dielectric anisotropy is positive and the value thereof is large. By adding this component D, the dielectric anisotropy of the composition can be increased. Component D has the effect of widening the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. Component D is also useful for adjusting the voltage-transmittance curve of the device.
  • the content of component D with respect to 100% by weight of the liquid crystal composition is suitably in the range of 1% by weight to 99% by weight, and preferably Is in the range of 10% by weight to 97% by weight, more preferably in the range of 40% by weight to 95% by weight.
  • the content of component D is preferably 30% by weight or less based on 100% by weight of the liquid crystal composition.
  • Component E is selected from compounds (11) to (19).
  • Component E has a large negative dielectric anisotropy. These compounds have phenylene in which lateral position is substituted by two halogens (fluorine or chlorine) like 2,3-difluoro-1,4-phenylene.
  • Preferred examples of component E include compounds (11-1) to (11-9), compounds (12-1) to (12-19), compounds (13-1) and (13-2), and compounds (14-). 1) to (14-3), compounds (15-1) to (15-3), compounds (16-1) to (16-11), compounds (17-1) to (17-3), compounds 18-1) to (18-3) and the compound (19-1) can be mentioned.
  • R 15, R 16, and R 17 are independently alkenyl alkyl carbon atoms or 2 to 10 of 1 to 10 carbon atoms, in the alkyl and alkenyl, at least one -CH 2 - May be replaced by —O—, in these groups at least one hydrogen may be replaced by fluorine and R 17 may be hydrogen or fluorine.
  • Component E has a large negative dielectric anisotropy.
  • Component E is suitably used when preparing a composition for modes such as IPS, VA, PSA and the like.
  • the dielectric anisotropy of the composition increases negatively, but the viscosity increases. Therefore, as long as the required value of the threshold voltage of the device is satisfied, the content is preferably as small as possible.
  • the content of component E with respect to 100% by weight of the liquid crystal composition is preferably 40% by weight or more in order to achieve sufficient voltage driving.
  • the compound (11) is a bicyclic compound, it has an effect of lowering the viscosity, adjusting the optical anisotropy or increasing the dielectric anisotropy.
  • Compounds (12) and (13) are tricyclic compounds, and compound (14) is a tetracyclic compound. Therefore, the effects of increasing the maximum temperature, optical anisotropy, or dielectric anisotropy are obtained. is there.
  • Compounds (15) to (19) have the effect of increasing the dielectric anisotropy.
  • the content of the component E is preferably 40% by weight or more, more preferably 50% by weight, relative to 100% by weight of the liquid crystal composition. % To 95% by weight.
  • the content of component E is preferably 30% by weight or less based on 100% by weight of the liquid crystal composition.
  • liquid crystal composition satisfying at least one of the properties such as specific resistance, high stability to ultraviolet light, high stability to heat, and a large elastic constant.
  • the liquid crystal composition is prepared by a known method. For example, there is a method in which the components are mixed and dissolved with one another by heating.
  • additives may be added to the composition.
  • additives include polymerizable compounds other than the compound (1), polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dyes, antifoaming agents, etc. It is. Such additives are well known to those skilled in the art and are described in the literature.
  • the polymerizable compound is added in order to form a polymer in the liquid crystal composition.
  • a polymer can be produced
  • the compound (1) is immobilized in the state where its polar group interacts non-covalently with the substrate surface of the glass (or metal oxide).
  • the ability to control the alignment of liquid crystal molecules is further improved, and an appropriate pretilt is obtained, so that the response time is shortened.
  • Preferred examples of the polymerizable compound are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes), and vinyl ketones. Further preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. Further preferred examples also include compounds having both acryloyloxy and methacryloyloxy.
  • a particularly preferred example of the polymerizable compound includes the compound (20).
  • the compound (20) is a compound different from the compound (1).
  • the compound (1) has a polar group. On the other hand, it is preferable that a compound (20) does not have a polar group.
  • ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine- 2-yl or pyridin-2-yl in which at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is halogen It may be substituted by substituted C 1 to C 12 alkyl.
  • Preferred ring F and ring I are cyclohexyl, cyclohexenyl, phenyl, fluorophenyl, difluorophenyl, 1-naphthyl or 2-naphthyl. Further preferred ring F and ring I are cyclohexyl, cyclohexenyl or phenyl. Particularly preferred ring F and ring I are phenyl.
  • ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene- 1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2, 6-diyl, naphthalene-2,7-diyl, phenanthrene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or Pyridine-2,5-diyl
  • Preferred ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3 -Diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl Naphthalene-2,6-diyl and naphthalene-2,7-diyl.
  • More preferable ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene or 2-fluoro-1,4-phenylene.
  • Particularly preferred ring G is 1,4-phenylene or 2-fluoro-1,4-phenylene.
  • the most preferred ring G is 1,4-phenylene.
  • Preferred Z 22 and Z 23 are a single bond, -CH 2 CH 2- , -CH 2 O-, -OCH 2- , -COO-, or -OCO-. Further preferred Z 22 and Z 23 are single bonds.
  • P 11 , P 12 and P 13 are independently a polymerizable group.
  • Preferred P 11 to P 13 are groups selected from the group of polymerizable groups represented by formulas (P-1) to (P-5). Further preferable P 11 to P 13 are groups represented by Formula (P-1), Formula (P-2), or Formula (P-3). Particularly preferable P 11 to P 13 are groups represented by formula (P-1).
  • the wavy lines in formulas (P-1) to (P-5) indicate the binding site.
  • M 11 , M 12 and M 13 independently represent hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is replaced by halogen Alkyl having 1 to 5 carbon atoms.
  • Preferred M 11 , M 12 and M 13 are hydrogen or methyl to increase the reactivity.
  • Further preferred M 11 is hydrogen or methyl, and further preferred M 12 and M 13 are hydrogen.
  • Preferred Sp 11 , Sp 12 and Sp 13 are single bonds.
  • u is 0, 1 or 2.
  • Preferred u is 0 or 1.
  • f, g and h are independently 0, 1, 2, 3 or 4 and the sum of f, g and h is 1 or more.
  • Preferred f, g or h is 0, 1 or 2.
  • the preferred sum is 2, 3 or 4. More preferable sum is 2 or 3.
  • Preferred examples of the compound (20) are the compounds (20-1) to the compounds (20-7) described in item 15 and the following compounds (20-8) to (20-11). Further preferable examples are compound (20-1-1) to (20-1-5), compound (20-2-1) to (20-2-5), compound (20-4-1), compound ( 20-5-1), a compound (20-6-1), and a compound (20-7-1).
  • R 25 to R 31 are independently hydrogen or methyl;
  • R 32 , R 33 and R 34 are independently hydrogen or alkyl having 1 to 5 carbon atoms, R 32 , At least one of R 33 and R 34 is alkyl having 1 to 5 carbons;
  • v and x are independently 0 or 1;
  • t and u are independently an integer of 1 to 10 And t + v and x + u are each at most 10;
  • L 31 to L 36 are independently hydrogen or fluorine, and
  • L 37 and L 38 are independently hydrogen, fluorine or methyl.
  • the polymerizable compound in the composition can be rapidly polymerized by using a polymerization initiator such as a radical photopolymerization initiator.
  • a polymerization initiator such as a radical photopolymerization initiator.
  • the amount of the remaining polymerizable compound can be reduced by optimizing the reaction conditions in the polymerization.
  • photo radical polymerization initiators include TPO, 1173, and 4265 from Darocure series of BASF, and 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, from Irgacure series. 1850 and 2959 can be mentioned.
  • photo radical polymerization initiators include 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyl Dimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate mixture, benzophenone / methyltriethanolamine mixture It is.
  • polymerization After adding a photo radical polymerization initiator to the liquid crystal composition, polymerization can be performed by irradiating ultraviolet light in a state where an electric field is applied. However, unreacted polymerization initiator or decomposition products of the polymerization initiator may cause display defects such as image sticking to the device. In order to prevent this, photopolymerization may be carried out without adding a polymerization initiator.
  • the preferred wavelength of the light to be irradiated is in the range of 150 nm to 500 nm. A further preferred wavelength is in the range of 250 nm to 450 nm, and the most preferred wavelength is in the range of 300 nm to 400 nm.
  • a polymerization inhibitor When storing the polymerizable compound, a polymerization inhibitor may be added to prevent polymerization. When the polymerization compound contains a polymerization inhibitor, it is usually added to the composition without removing the polymerization inhibitor.
  • polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine.
  • the optically active compound has an effect of preventing reverse twist by inducing a helical structure to liquid crystal molecules to give a necessary twist angle.
  • the helical pitch can be adjusted by adding an optically active compound.
  • Two or more optically active compounds may be added in order to adjust the temperature dependency of the helical pitch.
  • the optically active compounds the following compounds (Op-1) to (Op-18) can be mentioned.
  • ring J is 1,4-cyclohexylene or 1,4-phenylene
  • R 28 is alkyl having 1 to 10 carbons.
  • the symbol * represents an asymmetric carbon.
  • an antioxidant is effective to maintain a large voltage holding ratio of the device.
  • the following compounds (AO-1) and (AO-2); Irganox 415, Irganox 565, Irganox 1010, Irganox 1035, Irganox 3114, and Irganox 1098 (trade name; manufactured by BASF) can be mentioned.
  • UV absorber is effective to prevent the lowering of the upper limit temperature of the device.
  • Preferred examples of UV absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like, and specific examples thereof include the following compounds (AO-3) and (AO-4); Tinuvin 329, Tinuvin P, Tinuvin 326, Tinuvin 326, Tinuvin 213, Tinuvin 400, There may be mentioned Tinuvin 328, and Tinuvin 99-2 (trade name; BASF AG); and 1,4-diazabicyclo [2.2.2] octane (DABCO).
  • light stabilizers such as sterically hindered amines is preferred to maintain high voltage holding of the device.
  • the following compounds AO-5), (AO-6), and (AO-7); Tinuvin 144, Tinuvin 765, and Tinuvin 770 DF (trade name; BASF Corporation); LA-77Y and LA- 77G (trade name; ADEKA company) can be mentioned.
  • heat stabilizer is also effective for maintaining a large voltage holding ratio of the device, and a preferred example is Irgafos 168 (trade name; BASF Corporation).
  • a dichroic dye such as an azo dye or an anthraquinone dye is added to the composition.
  • Defoamers are effective to prevent foaming.
  • Preferred examples of the antifoaming agent are dimethyl silicone oil, methylphenyl silicone oil and the like.
  • R 40 is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, -COOR 41 , or -CH 2 CH 2 COOR 41 , wherein R 41 is 1 carbon To 20 alkyl.
  • R 42 is alkyl having 1 to 20 carbons.
  • R 43 is hydrogen, methyl or O.
  • ring G 1 is 1,4-cyclohexylene or 1,4-phenylene; in compound (AO-7)
  • ring G 2 is a group in which at least one hydrogen of 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene is replaced by fluorine; compounds (AO-5) and (AO-7) In the above, z is 1, 2 or 3.
  • the liquid crystal composition has an operation mode such as PC, TN, STN, OCB or PSA and can be suitably used for a liquid crystal display element driven by an active matrix system.
  • This composition has an operation mode such as PC, TN, STN, OCB, VA, IPS, etc., and can also be suitably used for a liquid crystal display element driven by a passive matrix system.
  • These elements can be applied to any of reflective, transmissive and semi-transmissive types.
  • the composition is also suitable for a nematic curvilinear aligned phase (NCAP) device, in which the composition is microencapsulated.
  • NCAP nematic curvilinear aligned phase
  • This composition can also be used for polymer dispersed liquid crystal display (PDLCD) and polymer network liquid crystal display (PNLCD).
  • PDLCD polymer dispersed liquid crystal display
  • PLCD polymer network liquid crystal display
  • the ratio of the polymerizable compound is preferably 10% by weight or less with respect to 100% by weight of the liquid crystal composition, and a more preferable ratio is 0.1% by weight to 2% %, And more preferably 0.2% to 1.0% by weight.
  • the element in the PSA mode can be driven by a driving method such as an active matrix method or a passive matrix method. Such an element can be applied to any of reflective, transmissive, and semi-transmissive types.
  • a polymer contained in the composition aligns liquid crystal molecules.
  • Polar compounds help the liquid crystal molecules to align. That is, a polar compound can be used instead of the alignment film.
  • An example of a method of manufacturing such a device is as follows. An element having two substrates called an array substrate and a color filter substrate is prepared. This substrate does not have an alignment film. At least one of the substrates has an electrode layer. A liquid crystal compound is mixed to prepare a liquid crystal composition. To this composition is added compound (1), and, if necessary, other polymerizable compounds and polar compounds. Additives may be further added as needed. The composition is injected into the device. Light is irradiated in a state where a voltage is applied to this element. UV light is preferred. The polymerizable compound is polymerized by light irradiation. By this polymerization, a composition containing a polymer is formed, and a device having a PSA mode is produced.
  • polar compounds are arranged on the substrate as the polar groups interact with the substrate surface.
  • This polar compound aligns the liquid crystal molecules.
  • the interaction with the substrate surface becomes stronger and can be oriented at a low concentration.
  • the alignment of liquid crystal molecules is further promoted by the action of an electric field.
  • the polymerizable compound is also oriented according to this orientation. In this state, since the polymerizable compound is polymerized by ultraviolet light, a polymer maintaining this orientation is formed. The effect of the polymer is to additionally stabilize the orientation of the liquid crystal molecules, thus reducing the response time of the device. Since image sticking is a malfunction of liquid crystal molecules, the effect of the polymer is to simultaneously improve the sticking.
  • the compound (1) Since the compound (1) is polymerizable, it is consumed by polymerization. The compound (1) is also consumed by copolymerizing with other polymerizable compounds. Accordingly, the compound (1) has a polar group but is consumed, so that a liquid crystal display device having a large voltage holding ratio can be obtained. In addition, since the effects of both the polar compound and the polymerizable compound can be achieved with one compound by using the polar compound having the polymerizability, the polymerizable compound having no polar group is not required. is there.
  • the present invention will be described in more detail by way of examples (including synthesis examples and usage examples). The invention is not limited by these examples.
  • the invention also includes mixtures prepared by mixing at least two of the compositions of the Use Examples.
  • Example 1 Examples of Compound (1) Unless otherwise stated, reactions were carried out under a nitrogen atmosphere. Compound (1) was synthesized by the procedure shown in Example 1 and the like. The compound synthesized was identified by a method such as NMR analysis. The properties of the compound (1), the liquid crystal compound, the composition and the device were measured by the following methods.
  • NMR analysis For measurement, DRX-500 manufactured by Bruker Biospin Ltd. was used. In the measurement of 1 H-NMR, the sample was dissolved in a deuterated solvent such as CDCl 3, and the measurement was performed at room temperature under conditions of 500 MHz and 16 integrations. Tetramethylsilane was used as an internal standard. In the measurement of 19 F-NMR, CFCl 3 was used as an internal standard, and the measurement was performed under the condition of 24 times of integration. In the description of nuclear magnetic resonance spectrum, s is singlet, d is doublet, t is triplet, q is quartet, quin is quintet, sext is sextet, m is multiplet, br is broad.
  • a GC-2010 gas chromatograph manufactured by Shimadzu Corporation was used for measurement.
  • capillary columns DB-1 (length 60 m, inner diameter 0.25 mm, film thickness 0.25 ⁇ m) manufactured by Agilent Technologies Inc. were used.
  • Helium (1 ml / min) was used as a carrier gas.
  • the temperature of the sample vaporization chamber was set to 300 ° C.
  • the temperature of the detector (FID) portion was set to 300 ° C.
  • the sample was dissolved in acetone to prepare a 1% by weight solution, and 1 ⁇ l of the resulting solution was injected into the sample vaporization chamber.
  • a recorder a GC Solution system manufactured by Shimadzu Corporation was used.
  • HPLC analysis For measurement, Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used.
  • the column used was YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle diameter 5 ⁇ m) manufactured by YMC.
  • the eluate was used by appropriately mixing acetonitrile and water.
  • a detector a UV detector, an RI detector, a CORONA detector, etc. were used suitably. When a UV detector was used, the detection wavelength was 254 nm.
  • the sample was dissolved in acetonitrile to prepare a 0.1% by weight solution, and 1 ⁇ L of this solution was introduced into the sample chamber.
  • C-R7Aplus manufactured by Shimadzu Corporation was used.
  • Ultraviolet-visible spectroscopy For measurement, PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used. The detection wavelength was from 190 nm to 700 nm. The sample was dissolved in acetonitrile to prepare a solution of 0.01 mmol / L, and placed in a quartz cell (optical path length: 1 cm) for measurement.
  • Measurement sample When measuring the phase structure and transition temperature (clearing point, melting point, polymerization initiation temperature, etc.), the compound itself was used as a sample.
  • Measurement method The measurement of the characteristics was performed by the following method. Many of these are described in the JEITA standard (JEITA ED-2521B) deliberated and enacted by the Japan Electronics and Information Technology Industries Association (JEITA), or a modified method thereof. there were. A thin film transistor (TFT) was not attached to the TN device used for the measurement.
  • JEITA Japan Electronics and Information Technology Industries Association
  • Phase structure The sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarization microscope (model: FP-52 hot stage manufactured by Mettler). While heating this sample at a rate of 3 ° C./min, the phase state and its change were observed with a polarization microscope to identify the type of phase.
  • a polarization microscope model: FP-52 hot stage manufactured by Mettler
  • Transition temperature (° C)
  • a scanning calorimeter manufactured by Perkin Elmer, a Diamond DSC system, or a high-sensitivity differential scanning calorimeter manufactured by Hitachi High-Tech Science Co., Ltd., X-DSC7000 was used.
  • the temperature of the sample was raised and lowered at a rate of 3 ° C./min, and the transition point was determined by extrapolating the start point of the endothermic peak or exothermic peak associated with the phase change of the sample.
  • the melting point of the compound and the polymerization initiation temperature were also measured using this apparatus.
  • the temperature at which a compound transitions from a solid to a liquid crystal phase such as a smectic phase or a nematic phase may be abbreviated as "the lower limit temperature of the liquid crystal phase”.
  • the temperature at which a compound transitions from liquid crystal phase to liquid may be abbreviated as the "clearing point”.
  • the crystal is designated C.
  • the smectic phase is represented by S and the nematic phase is represented by N.
  • a smectic A phase, a smectic B phase, a smectic C phase, or a smectic F phase can be distinguished among the smectic phases, they are represented as S A , S B , S C or S F , respectively.
  • the liquid (isotropic) was designated as I.
  • the transition temperature is expressed as, for example, "C 50.0 N 100.0 I". This indicates that the transition temperature from crystal to nematic phase is 50.0 ° C., and the transition temperature from nematic phase to liquid is 100.0 ° C.
  • T NI or NI Maximum temperature of nematic phase
  • the sample was placed on the hot plate of a melting point apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when part of the sample changed from the nematic phase to the isotropic liquid.
  • the upper limit temperature of the nematic phase may be abbreviated as "upper limit temperature”.
  • TNI When the sample is a mixture of compound (1) and mother liquid crystals, it is indicated by the symbol TNI .
  • TNI When the sample is a mixture of compound (1) and a compound such as component B, C or D, it is indicated by the symbol NI.
  • Viscosity Bulk viscosity; ;; measured at 20 ° C .; mPa ⁇ s
  • an E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used.
  • the measurement method of characteristics may be different between the sample with positive dielectric anisotropy and the sample with negative dielectric anisotropy.
  • the measuring methods when the dielectric anisotropy is positive are described in the items (8a) to (12a).
  • the terms (8b) to (12b) are described.
  • Viscosity Rotational viscosity; ⁇ 1; measured at 25 ° C .; mPa ⁇ s) Positive dielectric anisotropy: The measurement was according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). The sample was placed in a TN device having a twist angle of 0 degree and a distance between two glass substrates (cell gap) of 5 ⁇ m. A voltage was applied to this element in steps of 0.5 V in the range of 16 V to 19.5 V. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds).
  • the peak current and peak time of transient current generated by this application were measured. These measurements and M.
  • the rotational viscosity was obtained from the paper of Imai et al., Calculation formula (8) on page 40. The value of dielectric anisotropy required for this calculation was determined by the method described below using the device for which this rotational viscosity was measured.
  • Viscosity Rotational viscosity; ⁇ 1; measured at 25 ° C .; mPa ⁇ s
  • Negative dielectric anisotropy Measurement was according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 20 ⁇ m. A voltage was applied to the device stepwise in steps of 1 volt in the range of 39 to 50 volts. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds).
  • the dielectric constants ( ⁇ and ⁇ ) were measured as follows. 1) Measurement of dielectric constant ( ⁇ ): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a well-cleaned glass substrate. The glass substrate was rotated by a spinner and then heated at 150 ° C. for 1 hour. A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 4 ⁇ m, and this device was sealed with an adhesive cured with ultraviolet light.
  • Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant ( ⁇ ) in the major axis direction of liquid crystal molecules was measured.
  • 2) Measurement of dielectric constant ( ⁇ ) A polyimide solution was applied to a well-cleaned glass substrate. After firing the glass substrate, the obtained alignment film was rubbed. The sample was placed in a TN device in which the distance between two glass substrates (cell gap) was 9 ⁇ m and the twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant ( ⁇ ) in the minor axis direction of liquid crystal molecules was measured.
  • Threshold voltage (Vth; measured at 25 ° C .; V) Positive dielectric anisotropy: For measurement, an LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. The sample was placed in a normally white mode TN device in which the distance between two glass substrates (cell gap) is 0.45 / ⁇ n ( ⁇ m) and the twist angle is 80 degrees. The voltage (32 Hz, rectangular wave) applied to this element was gradually increased by 0.02 V from 0 V to 10 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The threshold voltage was represented by the voltage at 90% transmittance.
  • Threshold voltage (Vth; measured at 25 ° C .; V) Negative dielectric anisotropy: For measurement, an LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. A sample is placed in a normally black mode VA device in which the distance between two glass substrates (cell gap) is 4 ⁇ m and the rubbing direction is antiparallel, and an adhesive for curing this device with ultraviolet light is used. Used and sealed. The voltage (60 Hz, rectangular wave) applied to this element was gradually increased by 0.02 V from 0 V to 20 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The threshold voltage was represented by the voltage at 10% transmittance.
  • the rise time ( ⁇ r: millisecond) is the time taken for the transmittance to change from 90% to 10%.
  • the fall time ( ⁇ f: milliseconds) is the time taken to change from 10% transmission to 90% transmission.
  • the response time is represented by the sum of the rise time and the fall time obtained in this manner.
  • a rectangular wave 60 Hz, 10 V, 0.5 seconds was applied to this element.
  • the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. It was considered that the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum.
  • the response time is represented by the time (fall time; milliseconds) taken to change from 90% transmittance to 10% transmittance.
  • Raw materials Solmix (registered trademark) A-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (IPA) (1.1%), and is sold by Nippon Alcohol Sales Co., Ltd. obtained.
  • Step 2 Compound (T-2) (6.18 g), 3,4-dihydro-2H-pyran (3.57 g), pyridinium p-toluenesulfonate (PPTS) (0.970 g), and dichloromethane (60. 6). 0 ml) was charged into the reactor and stirred at room temperature for 12 hours. The reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate.
  • PPTS pyridinium p-toluenesulfonate
  • Step 3 Compound (T-3) (9.15 g), THF (45.0 ml), and water (45.0 ml) were charged into a reactor and cooled to 0 ° C. Lithium hydroxide monohydrate (3.14 g) was added there, and it stirred for 7 hours, returning to room temperature. The reaction mixture was poured into water, 6N hydrochloric acid (15 ml) was slowly added to acidify, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to give compound (T-4) (5.07 g; 59%).
  • Step 4 Compound (T-5) (124 g), triethylamine (52.4 g), and THF (3100 ml) synthesized according to the method described in WO 2014/097952 were charged into a reactor and cooled to 0 ° C. .
  • the compound (T-6) (50.0 g) was slowly dropped there, and stirred at 50 ° C. for 3 hours.
  • the reaction mixture was poured into brine and the aqueous layer was extracted with t-butyl methyl ether.
  • the obtained organic layer was washed successively with water and brine, and dried over anhydrous magnesium sulfate.
  • Step 3 Lithium aluminum hydride (2.46 g) and THF (200 ml) were charged to the reactor and cooled to 0 ° C. A solution of compound (T-12) (34.8 g) in THF (150 ml) was slowly added thereto, and the mixture was stirred for 3 hours while returning to room temperature. The reaction mixture was poured into water, insolubles were filtered off, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by recrystallization from heptane to give compound (T-13) (18.3 g; 61%).
  • TsCl p-toluenesulfon
  • Step 8 Compound (T-19) (6.67 g; 88%) was obtained in the same manner as in the fifth step of Synthesis Example 1 using compound (T-18) (5.00 g) as a starting material.
  • Step 9 Using compound (T-19) (6.67 g) as a starting material, and according to the same method as step 6 of Synthesis Example 1, compound (1-2-6) (4.32 g; 75%) was obtained.
  • Step 3 Compound (T-22) (137 g), triphenylphosphine (115 g), and dichloromethane (850 ml) were charged into a reactor, and cooled to 0 ° C. Thereto, a solution of carbon tetrabromide (145 g) in THF (500 ml) was slowly added, and stirred for 12 hours while returning to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (heptane) to give compound (T-23) (132 g; 82%).
  • Step 4 Compound (T-23) (132 g), triphenylphosphine (94.1 g), and toluene (2500 ml) were placed in a reactor, and heating to reflux was carried out at 110 ° C. for 15 hours. The reaction mixture was cooled to 0 ° C., and the precipitated crystals were collected by filtration to give compound (T-24) (178 g; 82%).
  • Step 5 Compound (T-24) (178 g) and THF (900 ml) were placed in a reactor and cooled to -30.degree. To this was added potassium t-butoxide (29.9 g), and the mixture was stirred at -30 ° C for 1 hour. Next, a solution of compound (T-25) (38.4 g) in THF (900 ml) was slowly added dropwise, and stirred for 12 hours while returning to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate.
  • Step 6 Using compound (T-26) (78.1 g) as a starting material, compound (T-27) (78.0 g; 99%) was obtained in the same manner as in the second step of Synthesis Example 2.
  • Step 7 The compound (T-27) (74.6 g), p-toluenesulfonic acid monohydrate (PTSA), toluene (800 ml) and methanol (800 ml) were placed in a reactor and stirred at room temperature for 12 hours did.
  • the reaction mixture was poured into saturated aqueous sodium hydrogen carbonate solution, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate.
  • the solution was concentrated under reduced pressure to give compound (T-28) (59.0 g, yield 87%).
  • Step 8 Compound (T-29) (6.44 g; 43%) was obtained in the same manner as in the seventh step of Synthesis Example 2 using compound (T-28) (12.9 g) as a starting material.
  • Step 9 Using compound (T-29) (22.0 g) as a starting material, compound (T-30) (24.6 g; 78%) was obtained in the same manner as in the fifth step of Synthesis Example 1.
  • Step 10 Compound (1-3-4) (19.5 g; 90%) was obtained by the same method as in Step 6 of Synthesis Example 1 using compound (T-30) (24.6 g) as a starting material.
  • compound (T-30) (24.6 g)
  • Step 3 Compound (T-33) (9.75 g; 54%) was obtained in the same manner as in the third step of Synthesis Example 1 using compound (T-32) (19.2 g) as a starting material.
  • Step 4 Using compound (T-18) (5.00 g) and compound (T-33) (4.72 g) as starting materials, compound (T-34) in the same manner as in the fifth step of Synthesis Example 1. Obtained (7.32 g; 90%).
  • Step 5 Using compound (T-34) (7.32 g) as a starting material, and according to a procedure similar to the sixth step of Synthesis Example 1, compound (1-2-16) (4.56 g; 71%) is obtained.
  • Step 3 Compound (T-37) (13.0 g; 91%) was obtained in the same manner as in the third step of Synthesis Example 1 using compound (T-36) (15.0 g) as a starting material.
  • Step 4 Using the compound (T-18) (5.00 g) and the compound (T-37) (4.23 g) as starting materials, the compound (T-38) is prepared in the same manner as in the fifth step of Synthesis Example 1. (6.84 g; 82%) were obtained.
  • Step 5 Using compound (T-38) (6.84 g) as a starting material, and according to a method similar to the sixth step of Synthesis Example 1, compound (1-2-17) (2.33 g; 39%) is obtained.
  • Comparative Example 1 As a comparison compound, the following compound (S-1) described in WO 2017/047177 was synthesized based on the description of the publication, and the characteristics thereof were measured.
  • composition (i) The proportions of the components of composition (i) are indicated in% by weight.
  • the compound (1-2-2), the compound (1-2-6), the compound (1-3-4), the compound (1-2-16), and the compound (I) per 100% by weight of the composition (i) 1-2-17), or a comparison compound (S-1) was added at a ratio of 0.1 wt% to 1.0 wt% shown in Table A to prepare a sample.
  • the sample was allowed to stand at 25 ° C. for 7 days and then visually observed.
  • the compound (1-2-2), the compound (1-2-6), the compound (1-3-4), the compound (1-2-16), and the compound (1-2-2) 17) maintained the nematic phase even when added to the mother liquid crystal (composition (i)) at 1.0% by weight, whereas the comparative compound (S-1) maintained 0.2% by weight for crystals. It precipitated.
  • These compounds are similar compounds in that they have a plurality of polymerizable groups, but their compatibility with the mother liquid crystals is largely different.
  • the compound (1-2-2), the compound (1-2-6), the compound (1-3-4), the compound, while the comparative compound (S-1) has a plurality of hydroxyl groups as a polar group.
  • the compound (1) can be said to be an excellent compound having a plurality of polymerizable groups and having practical compatibility.
  • Example 1 1-BB-3 (2-8) 5% 1-BB-5 (2-8) 8% 2-BTB-1 (2-10) 2% 3-HHB-1 (3-1) 6% 3-HHB-3 (3-1) 14% 3-HHB-O1 (3-1) 5% 3-HHB-F (6-1) 4% 2-HHB (F) -F (6-2) 7% 3-HHB (F) -F (6-2) 8% 5-HHB (F) -F (6-2) 8% 3-HHB (F, F) -F (6-3) 5% 3-HHEB-F (6-10) 4% 5-HHEB-F (6-10) 5% 2-HB-C (8-1) 5% 3-HB-C (8-1) 14%
  • the following compound (1-2-2) was added at a ratio of 1% by weight to 100% by weight of a composition containing these components.
  • the following compound (1-2-6) was added in a proportion of 0.5% by weight to 100% by weight of the composition containing these components.
  • the following compound (1-3-4) was added in a proportion of 2% by weight to 100% by weight of the composition containing these components.
  • the following compound (1-3-21) was added in a proportion of 5% by weight to 100% by weight of the composition containing these components.
  • V-HBB-2 (3-4) 12% 1O1-HBBH-4 (4-1) 5% 1O1-HBBH-5 (4-1) 4% 3-HHB (F, F) -F (6-3) 9% 3-H2HB (F, F) -F (6-15) 9% 4-H2HB (F, F) -F (6-15) 9% 5-H2HB (F, F) -F (6-15) 8% 3-HBB (F, F) -F (6-24) 11% 5-HBB (F, F) -F (6-24) 18% 3-H2BB (F, F) -F (6-27) 9% 5-HBBB (F, F) -F (7-6) 2% 3-HH2BB (F, F) -F (7-15) 2% 5-HHEBB-F (7-17) 2%
  • the following compound (1-3-66) was added at a ratio of 1.5% by weight to 100% by weight of a composition containing these components.
  • the following compound (1-3-62) was added in a proportion of 2% by weight to 100% by weight of the composition containing these components.
  • the following compound (1-3-88) was added at a ratio of 0.8% by weight to 100% by weight of a composition containing these components.
  • the following compound (1-2-2) was added in a proportion of 3% by weight to 100% by weight of the composition containing these components.
  • the following compound (1-2-6) was added in a proportion of 4% by weight to 100% by weight of the composition containing these components.
  • the following compound (1-3-4) was added in a proportion of 5% by weight to 100% by weight of the composition containing these components.
  • the following compound (1-3-21) was added at a ratio of 1.5% by weight to 100% by weight of a composition containing these components.
  • the liquid crystal composition containing the compound (1) can be used for display elements such as a liquid crystal projector and a liquid crystal television.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Liquid Crystal Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyridine Compounds (AREA)
  • Pyrane Compounds (AREA)
  • Liquid Crystal (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)

Abstract

La présente invention concerne un composé, une composition de cristaux liquides, et un élément d'affichage à cristaux liquides. Le composé est représenté par la formule (1). R1 représente l'hydrogène ou un alkyle qui peut être substitué ; les cycles A1 et A2 représentent chacun un cyclopropylène, cyclobutylène, cyclopentylène, cyclohexylène, cycloheptylène, cyclohexénylène, phénylène, naphtalènediyle, décahydronaphtalènediyle, tétrahydronaphtalènediyle, tétrahydropyrandiyle, dioxanediyle, pyrimidinediyle, ou pyridinediyle qui peut être substitué ; "a" est compris entre 0 et 4 ; Z1 est une liaison simple ou un alkylène qui peut être substitué ; Sp1 à Sp5 représentent chacun une liaison simple ou un alkylène qui peut être substitué ; M1 à M4 représentent chacun H, F, Cl, ou un alkyle qui peut être substitué ; R2 représente un atome d'hydrogène ou un alkyle en C1-C5 qui peut être substitué ; et X1 représente -OH, -NH2, -OR3, -N(R3)2, -COOH, -SH, ou -Si(R3)3.
PCT/JP2018/044555 2017-12-06 2018-12-04 Composé, composition de cristaux liquides, et élément d'affichage à cristaux liquides Ceased WO2019111892A1 (fr)

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