WO2018150954A1 - Élément d'affichage à cristaux liquides, et composition de cristaux liquides - Google Patents

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

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WO2018150954A1
WO2018150954A1 PCT/JP2018/004042 JP2018004042W WO2018150954A1 WO 2018150954 A1 WO2018150954 A1 WO 2018150954A1 JP 2018004042 W JP2018004042 W JP 2018004042W WO 2018150954 A1 WO2018150954 A1 WO 2018150954A1
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formula
liquid crystal
diyl
carbons
hydrogen
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PCT/JP2018/004042
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English (en)
Japanese (ja)
Inventor
平井　吉治
史尚 近藤
和寛 荻田
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Jnc株式会社
Jnc石油化学株式会社
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Priority to CN201880008316.1A priority Critical patent/CN110226119B/zh
Priority to JP2018568129A priority patent/JPWO2018150954A1/ja
Publication of WO2018150954A1 publication Critical patent/WO2018150954A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/46—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing esters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

  • the present invention relates to a liquid crystal display element and a liquid crystal composition containing a liquid crystal composition having a negative dielectric anisotropy.
  • the present invention relates to a liquid crystal display element using a liquid crystal composition containing an alignment monomer and capable of achieving alignment of liquid crystal molecules without using an alignment film such as polyimide by the action of this compound.
  • the classification based on the operation mode of the liquid crystal molecules is as follows: PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS. (In-plane switching), VA (vertical alignment), FFS (fringe field switching), FPA (field-induced photo-reactive alignment) mode.
  • the classification based on the element drive system is PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into TFT (thin film insulator), MIM (metal film insulator), and the like. TFTs are classified into amorphous silicon and polycrystalline silicon. The latter is classified into a high temperature type and a low temperature type according to the manufacturing process.
  • the classification based on the light source includes a reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both natural light and backlight.
  • the liquid crystal display element contains a liquid crystal composition having a nematic phase.
  • This composition has suitable properties. By improving the characteristics of the composition, an AM device having good characteristics can be obtained. The relationship between the two characteristics is summarized in Table 1 below. The characteristics of the composition will be further described based on a commercially available AM device.
  • the temperature range of the nematic phase is related to the temperature range in which the device can be used.
  • a preferred upper limit temperature of the nematic phase is about 70 ° C. or more, and a preferred lower limit temperature of the nematic phase is about ⁇ 10 ° C. or less.
  • the viscosity of the composition is related to the response time of the device. A short response time is preferred for displaying moving images on the device. A shorter response time is desirable even at 1 millisecond. Therefore, a small viscosity in the composition is preferred. A small viscosity at low temperatures is even more preferred.
  • the optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large optical anisotropy or a small optical anisotropy, ie an appropriate optical anisotropy is required.
  • the product ( ⁇ n ⁇ d) of the optical anisotropy ( ⁇ n) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio.
  • the appropriate product value depends on the type of operation mode. This value is in the range of about 0.30 ⁇ m to about 0.40 ⁇ m for the VA mode element and in the range of about 0.20 ⁇ m to about 0.30 ⁇ m for the IPS mode or FFS mode element.
  • a composition having a large optical anisotropy is preferable for a device having a small cell gap.
  • a large dielectric anisotropy in the composition contributes to a low threshold voltage, a small power consumption and a large contrast ratio in the device. Therefore, a large dielectric anisotropy is preferable.
  • a large specific resistance in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a large specific resistance in the initial stage is preferable.
  • a composition having a large specific resistance after being used for a long time is preferred.
  • the stability of the composition to ultraviolet light and heat is related to the lifetime of the device. When this stability is high, the lifetime of the device is long. Such characteristics are preferable for an AM device used for a liquid crystal monitor, a liquid crystal television, and the like.
  • a composition having a positive dielectric anisotropy is used for an AM device having a TN mode.
  • a composition having a negative dielectric anisotropy is used in an AM device having a VA mode.
  • a composition having a positive or negative dielectric anisotropy is used in an AM device having an IPS mode or an FFS mode.
  • a composition having a positive or negative dielectric anisotropy is used in an AM device having an IPS mode or an FFS mode.
  • a composition having a positive or negative dielectric anisotropy is used in a polymer-supported alignment (PSA) type liquid crystal display element.
  • PSA polymer-supported alignment
  • the polymerizable compound polymerizes to form a polymer network in the composition.
  • the alignment of liquid crystal molecules can be controlled by the polymer, the response time of the device is shortened, and image burn-in is improved.
  • Such an effect of the polymer can be expected for a device having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
  • Patent Document 1 There is a method for controlling the alignment of liquid crystals using a low molecular compound having a cinnamate group or polyvinyl cinnamate, a low molecular compound having a chalcone structure, a low molecular compound having an azobenzene structure, or a dendrimer instead of an alignment film such as polyimide. It has been reported (Patent Document 1). In the method of Patent Document 1, first, the low molecular compound or polymer is dissolved in the liquid crystal composition as an additive. Next, a thin film made of a low molecular compound or a polymer is formed on the substrate by phase-separating the additive.
  • the substrate is irradiated with linearly polarized light at a temperature higher than the upper limit temperature of the liquid crystal composition.
  • a low molecular compound or polymer is dimerized or isomerized by this linearly polarized light, the molecules are arranged in a certain direction.
  • a device in a horizontal alignment mode such as IPS or FFS and a device in a vertical alignment mode such as VA can be manufactured.
  • VA vertical alignment mode
  • it is important that the low molecular weight compound or polymer is easily dissolved at a temperature higher than the upper limit temperature of the liquid crystal composition and is easily phase-separated from the liquid crystal composition when the temperature is returned to room temperature.
  • a dendrimer having azobenzene as a partial structure is dissolved as an additive in a liquid crystal composition.
  • a thin film of the compound is formed on the substrate by phase-separating the compound.
  • the liquid crystal composition is aligned perpendicular to the substrate.
  • linearly polarized light is irradiated without heating the substrate.
  • the dendrimer is dimerized or isomerized by this linearly polarized light, the molecules are arranged in a direction horizontal to the substrate.
  • a device in a horizontal alignment mode such as IPS or FFS can be manufactured.
  • Patent Documents 4 to 6 disclose a combination of a liquid crystal compound having negative dielectric anisotropy and a polymerizable compound having a polar group.
  • the polymerizable compound having a polar group contained in the liquid crystal medium controls the alignment of the liquid crystal vertically. Even using the method described here, it was difficult to control the orientation of the liquid crystal compound horizontally. Further, there is no suggestion or description that the polymerizable compound having a polar group can control the horizontal alignment of the liquid crystal compound by polarized light irradiation.
  • the problem to be solved by the present invention is to control the alignment of liquid crystal molecules of a liquid crystal display element having no alignment film by using an alignment monomer having no color, and an alignment monomer having no color is good. It is to provide a liquid crystal composition exhibiting good compatibility.
  • liquid crystal composition having a negative dielectric anisotropy containing an alignment monomer having a cinnamate group or a chalcone group and a hydroxyl group as a first additive.
  • liquid crystal composition containing the alignment monomer of the present invention By using the liquid crystal composition containing the alignment monomer of the present invention, an alignment film forming step is unnecessary, and a liquid crystal display element with reduced manufacturing costs can be obtained. In addition, a liquid crystal composition having negative dielectric anisotropy that is compatible with the alignment monomer can be obtained.
  • liquid crystal composition and “liquid crystal display element” may be abbreviated as “composition” and “element”, respectively.
  • “Liquid crystal display element” is a general term for liquid crystal display panels and liquid crystal display modules.
  • “Liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and a liquid crystal phase, but has a composition for the purpose of adjusting characteristics such as temperature range, viscosity, and dielectric anisotropy of the nematic phase. It is a general term for compounds mixed with products.
  • This compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-like.
  • the “polymerizable compound” is a compound added for the purpose of forming a polymer in the composition.
  • a liquid crystalline compound having alkenyl is not polymerizable in that sense.
  • the liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are added to this composition as necessary. .
  • the ratio of the liquid crystal compound is expressed as a weight percentage (% by weight) with respect to the total amount of the liquid crystal compound even when an additive is added.
  • the ratio of the additive is expressed as a percentage by weight (% by weight) when the total amount of the liquid crystal compounds is 100 parts by weight. That is, the ratio of the liquid crystal compound or additive is calculated based on the total weight of the liquid crystal compound. Weight parts per million (ppm) may be used.
  • the ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.
  • the maximum temperature of the nematic phase may be abbreviated as “the maximum temperature”.
  • “Lower limit temperature of nematic phase” may be abbreviated as “lower limit temperature”.
  • High specific resistance means that the composition has a large specific resistance in the initial stage and a large specific resistance after long-term use.
  • “High voltage holding ratio” means that the device has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and a large voltage not only at room temperature but also at a temperature close to the upper limit temperature after long-term use. It means having a retention rate.
  • An aging test may be used to examine the properties of the composition or device.
  • increasing dielectric anisotropy means that when the composition has a positive dielectric anisotropy, the value increases positively, and the composition having a negative dielectric anisotropy When it is a thing, it means that the value increases negatively.
  • the compound represented by the formula (1) may be abbreviated as “compound (1)”. At least one compound selected from the group of compounds represented by formula (1) may be abbreviated as “compound (1)”. “Compound (1)” means one compound represented by formula (1), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas.
  • the expression “at least one‘ A ’” means that the number of ‘A’ is arbitrary.
  • the expression “at least one 'A' may be replaced by 'B'” means that when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is 2 Even when there are more than two, their positions can be selected without restriction. This rule also applies to the expression “at least one 'A' is replaced by 'B'".
  • Expressions such as “at least one —CH 2 — may be replaced by —O—” are used herein.
  • —CH 2 —CH 2 —CH 2 — may be converted to —O—CH 2 —O— by replacing non-adjacent —CH 2 — with —O—.
  • adjacent —CH 2 — is not replaced by —O—.
  • —O—O—CH 2 — (peroxide) is formed by this replacement. That is, this expression includes both “one —CH 2 — may be replaced with —O—” and “at least two non-adjacent —CH 2 — may be replaced with —O—”. means. This rule applies not only to replacement with —O— but also to replacement with a divalent group such as —CH ⁇ CH— or —COO—.
  • the symbol of the terminal group R 1 is used for a plurality of compounds.
  • two groups represented by two arbitrary R 1 may be the same or different.
  • R 1 of the compound (1-1) is ethyl and R 1 of the compound (1-2) is ethyl.
  • R 1 of compound (1-1) is ethyl and R 1 of compound (1-2) is propyl.
  • This rule also applies to symbols such as other end groups.
  • the subscript 'a' is 2
  • there are two rings A In this compound, the two rings represented by the two rings A may be the same or different.
  • This rule also applies to any two rings A when the subscript 'a' is greater than 2.
  • This rule also applies to symbols such as Z 1 and ring D.
  • Symbols such as A, B, C, and D surrounded by hexagons correspond to rings such as ring A, ring B, ring C, and ring D, respectively, and represent rings such as six-membered rings and condensed rings.
  • the diagonal line across one side of the hexagon represents that any hydrogen on the ring may be replaced with a group such as —Sp 1 —P 1 .
  • a subscript such as 'e' indicates the number of groups replaced. When the subscript 'e' is 0 (zero), there is no such replacement. When the subscript 'e' is 2 or more, a plurality of -Sp 1 -P 1 exists on the ring F.
  • the plurality of groups represented by -Sp 1 -P 1 may be the same or different.
  • 2-Fluoro-1,4-phenylene means the following two divalent groups.
  • fluorine may be leftward (L) or rightward (R).
  • This rule also applies to asymmetric divalent groups generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl.
  • This rule also applies to divalent linking groups such as carbonyloxy (—COO— or —OCO—).
  • the alkyl of the liquid crystal compound is linear or branched and does not include cyclic alkyl. Linear alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. As the configuration of 1,4-cyclohexylene, trans is preferable to cis for increasing the maximum temperature.
  • the present invention includes the following items.
  • a liquid crystal layer is sandwiched between a pair of substrates that are arranged opposite to each other and bonded through a sealant, Between the pair of substrates and the liquid crystal layer, an alignment control layer for controlling alignment of liquid crystal molecules,
  • the liquid crystal layer is made of a liquid crystal composition having negative dielectric anisotropy,
  • the liquid crystal composition includes a group of compounds represented by the formula (A-1), the formula (A-2), the formula (B-1), and the formula (B-2) as an alignment monomer as a first additive. Containing at least one compound selected from the group consisting of a liquid crystalline compound and
  • the alignment control layer is a liquid crystal display element comprising a polymer produced by polymerizing the first additive.
  • P 10 is independently a group selected from the groups represented by formula (Q-1) to formula (Q-5);
  • M 10 , M 20 , and M 30 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is fluorine or chlorine 1 to 5 alkyl substituted with
  • Sp 10 and Sp 11 are independently a single bond or alkylene having 1 to 12 carbon atoms, and at least one hydrogen of the alkylene may be replaced by fluorine, chlorine or formula (Q-6), and at least One —CH 2 — may be replaced by —O—, —CO—, —COO—, or —OCO—, and at least one —CH 2 —CH 2 — may be —CH ⁇ CH— or — May be replaced by C ⁇ C-;
  • M 11 , M 21 , and M 31 are independently hydrogen, fluorine, alphaCH— or — May be replaced by C ⁇ C-;
  • M 11 , M 21 , and M 31 are independently hydrogen, fluorine
  • Ring A 10 , Ring A 20 , Ring A 30 , Ring A 40 and Ring A 50 are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 4,4 ′ -Biphenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3 -Dioxane-2,
  • Z 10 is independently a single bond, —COO—, —OCO—, —CH ⁇ CH—COO—, —OCO—CH ⁇ CH—, — OCO—CH 2 CH 2 —, —CH 2 CH 2 —COO—, —C ⁇ C—COO—, —OCO—C ⁇ C—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —CONH—, —NHCO—, — (CH 2 ) 4 —, —CH 2 CH 2 —, —CF 2 CF 2 —, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C-;
  • Z 11 is —CH ⁇ CH—CO— or —CO—CH ⁇ CH—;
  • n 10 is an integer of 0
  • n 20 is an integer of 0 to 3.
  • P 10 is independently of formula (Q-1);
  • M 10 is independently hydrogen, fluorine, methyl, or trifluoromethyl;
  • M 20 and M 30 are hydrogen;
  • Sp 10 and Sp 11 are independently a single bond or alkylene having 2 to 12 carbon atoms, and at least one hydrogen of the alkylene may be replaced by fluorine, chlorine or formula (Q-6), and at least One —CH 2 — may be replaced by —O—, —CO—, —COO—, or —OCO—, and at least one —CH 2 —CH 2 — may be —CH ⁇ CH— or — May be replaced by C ⁇ C-;
  • M 11 is independently hydrogen, fluorine, methyl, or trifluoromethyl;
  • M 21 and M 31 are hydrogen;
  • Sp 41 is independently a single bond or alkylene having 1 to 12 carbons, and at least one hydrogen of the alkylene may be replaced by fluorine, and at
  • n 20 is an integer from 0 to 3.
  • P 10 is independently of formula (Q-1);
  • M 10 is independently hydrogen, methyl or fluorine;
  • M 20 and M 30 are hydrogen;
  • Sp 10 and Sp 11 are each independently a single bond or alkylene having 2 to 12 carbon atoms, and at least one hydrogen of the alkylene may be replaced by formula (Q-6), and at least one —CH 2 — may be replaced by —O—, —CO—, —COO—, or —OCO—, wherein at least one —CH 2 —CH 2 — is —CH ⁇ CH— or —C ⁇ C— May be replaced by;
  • Z 10 is independently a single bond, —COO—, —OCO—, —CH ⁇ CH—COO—, —OCO—CH ⁇ CH—, — OCO—CH 2 CH 2 —, —CH 2 CH 2 —COO—, —C ⁇ C—COO
  • n 10 is an integer of 0 to 2;
  • R 20 is hydrogen, fluorine, hydroxy, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
  • Sp 20 and Sp 21 are each independently a single bond or alkylene having 1 to 12 carbons, and at least one —CH 2 — of the alkylene may be replaced by —O—;
  • n 20 is an integer from 0 to 3, Item 3.
  • the liquid crystal display element according to item 1 or 2.
  • Item 4. The liquid crystal according to any one of Items 1 to 3, wherein the proportion of the alignment monomer is in the range of 0.1% by weight to 10% by weight when the total amount of the liquid crystal compounds is 100 parts by weight. Display element.
  • Item 5 The liquid crystal display element according to any one of items 1 to 4, wherein the liquid crystal composition contains at least one compound selected from the group of compounds represented by formula (1) as a first component.
  • R 1 and R 2 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons.
  • Ring A and Ring C are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine Or tetrahydropyran-2,5-diyl;
  • ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5 - methyl-1,4-phenylene, it is a 3,4,5-trifluoro-2,6-diyl or 7,8-difluoro-chroman-2,6-diyl,;
  • Z 1 Oyo Z 2 is independently a single bond, ethylene, carbonyloxy or methyleneoxy,;
  • a is 1, 2, or 3,, b is 0 or 1, and the sum is 3 of a and b It is as follows.
  • Item 6. The liquid crystal composition according to any one of items 1 to 5, wherein the liquid crystal composition contains as a first component at least one compound selected from the group of compounds represented by formulas (1-1) to (1-22): The liquid crystal display element as described.
  • R 1 and R 2 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or It is alkenyloxy having 2 to 12 carbon atoms.
  • Item 7. The liquid crystal display device according to item 5 or 6, wherein in the liquid crystal composition, the ratio of the first component is in the range of 10% by weight to 90% by weight with respect to the total amount of the liquid crystal compound.
  • Item 8. The liquid crystal display device according to any one of items 1 to 7, wherein the liquid crystal composition further contains at least one compound selected from the group of compounds represented by formula (2) as the second component.
  • R 3 and R 4 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least one hydrogen is replaced by fluorine or chlorine Or alkyl having 1 to 12 carbon atoms or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine;
  • Ring D and Ring E are each independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene;
  • Z 3 is a single bond, ethylene, carbonyloxy, or methyleneoxy;
  • the liquid crystal composition further comprises at least one compound selected from the group of compounds represented by formulas (2-1) to (2-13) as the second component: A liquid crystal display element according to 1.
  • R 3 and R 4 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, It is alkyl having 1 to 12 carbons in which one hydrogen is replaced with fluorine or chlorine, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine.
  • Item 10 The liquid crystal display device according to item 8 or 9, wherein in the liquid crystal composition, the ratio of the second component is in the range of 10% by weight to 90% by weight with respect to the total amount of the liquid crystal compound.
  • Item 11 The liquid crystal display device according to any one of items 1 to 10, wherein the liquid crystal composition further contains at least one compound selected from the group of polymerizable compounds represented by formula (3) as the second additive.
  • 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, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen.
  • ring G may be 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1, 2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1, -Diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5- Diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5- Diyl, 1,3-dioxane-2,5-
  • P 1 , P 2 , and P 3 are groups independently selected from the group of polymerizable groups represented by the formulas (P-1) to (P-5). 11.
  • a liquid crystal display device according to item 11.
  • M 1 , M 2 , and M 3 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is fluorine or chlorine 1-5 alkyl substituted with
  • Item 13 The liquid crystal composition according to any one of items 1 to 12, wherein the liquid crystal composition contains at least one compound selected from the group of polymerizable compounds represented by formulas (3-1) to (3-27) as a second additive.
  • P 4 , P 5 , and P 6 are each independently a polymerizable group represented by formula (P-1) to formula (P-3).
  • M 1 , M 2 , and M 3 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine.
  • Sp 1 , Sp 2 , and Sp 3 are each independently a single bond or alkylene having 1 to 10 carbons, in which at least one —CH 2 — is —O—, —COO—, —OCO—, or —OCOO— may be substituted, and at least one —CH 2 CH 2 — may be substituted with —CH ⁇ CH— or —C ⁇ C—, and in these groups, at least One hydrogen may be replaced with fluorine or chlorine.
  • Item 14 The liquid crystal composition according to any one of Items 11 to 13, wherein the ratio of the second additive is in the range of 0.03% by weight to 10% by weight when the total amount of the liquid crystal compounds is 100 parts by weight.
  • Item 15 The liquid crystal composition according to any one of items 1 to 14, which has a liquid crystal composition and an electrode between a pair of substrates, and which is irradiated with linearly polarized light, A liquid crystal display device in which one additive has reacted.
  • Item 16 The liquid crystal display element according to item 15, wherein the operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and the driving method of the liquid crystal display element is an active matrix method.
  • Item 17 The liquid crystal display element according to item 15, wherein the operation mode of the liquid crystal display element is an IPS mode or an FFS mode, and the driving method of the liquid crystal display element is an active matrix method.
  • Item 18 A polymer-supported alignment type liquid crystal display device comprising the liquid crystal composition in the liquid crystal display device according to any one of items 11 to 14, wherein a polymerizable compound in the liquid crystal composition is polymerized.
  • Item 19 Use of a liquid crystal composition in a liquid crystal display device according to any one of items 1 to 14 in a liquid crystal display device.
  • Item 20 Use of the liquid crystal composition in the liquid crystal display device according to any one of items 1 to 14 in a polymer supported alignment type liquid crystal display device.
  • Item 21 Control of orientation of compounds represented by formula (A-1), formula (A-2), formula (B-1), and formula (B-2) in the liquid crystal display device according to any one of items 1 to 3 Use as a layer-forming monomer.
  • Item 22 Item 15. A liquid crystal composition in a liquid crystal display element according to any one of items 1 to 14. *
  • the present invention includes the following items.
  • the above composition further containing at least one additive such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound. object.
  • An AM device containing the above composition.
  • a polymer-supported orientation (PSA) type AM device containing the above composition further containing a polymerizable compound.
  • a polymer-supported orientation (PSA) type AM device comprising the above-described composition, wherein the polymerizable compound in the composition is polymerized.
  • (E) A device containing the above composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA.
  • (F) A transmissive device containing the above composition.
  • (G) Use of the above composition as a composition having a nematic phase.
  • (H) Use as an optically active composition by adding an optically active compound to the above composition.
  • the alignment monomer having a cinnamate group or chalcone group and a hydroxyl group contained in the liquid crystal composition used in the liquid crystal display element of the present invention will be described.
  • This compound is the first additive. This compound absorbs ultraviolet rays and causes reactions such as dimerization and isomerization and a polymerization reaction.
  • P 10 is independently a group selected from the groups represented by formula (Q-1) to formula (Q-5);
  • M 10 , M 20 , and M 30 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is fluorine or chlorine 1 to 5 alkyl substituted with
  • Sp 10 and Sp 11 are independently a single bond or alkylene having 1 to 12 carbon atoms, and at least one hydrogen of the alkylene may be replaced by fluorine, chlorine or formula (Q-6), and at least One —CH 2 — may be replaced by —O—, —CO—, —COO—, or —OCO—, and at least one —CH 2 —CH 2 — may be —CH ⁇ CH— or — May be replaced by C ⁇ C-;
  • M 11 , M 21 , and M 31 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or 1 carbon in which at least one hydrogen is replaced by fluorine or chlorine.
  • Sp 41 is independently a single bond or alkylene having 1 to 12 carbons, and at least one hydrogen of the alkylene may be replaced by fluorine or chlorine, and at least one —CH 2 — is —O May be replaced by-, -CO-, -COO-, or -OCO-;
  • Ring A 10 , Ring A 20 , Ring A 30 , Ring A 40 and Ring A 50 are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 4,4 ′ -Biphenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl
  • Z 10 is independently a single bond, —COO—, —OCO—, —CH ⁇ CH—COO—, —OCO—CH ⁇ CH—, — OCO—CH 2 CH 2 —, —CH 2 CH 2 —COO—, —C ⁇ C—COO—, —OCO—C ⁇ C—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —CONH—, —NHCO—, — (CH 2 ) 4 —, —CH 2 CH 2 —, —CF 2 CF 2 —, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C-;
  • Z 11 is —CH ⁇ CH—CO— or —CO—CH ⁇ CH—;
  • n 10 is an integer of 0
  • n 20 is an integer of 0 to 3.
  • the alignment monomer having a cinnamate group or chalcone group and a hydroxyl group which is the first additive, undergoes photoisomerization from a trans isomer to a cis isomer and formation of a cyclobutane ring by dimerization when irradiated with ultraviolet rays. Further, it is considered that the first additive is easily adsorbed on the substrate interface side due to the interaction between the hydroxyl group and the substrate interface. Moreover, since it has a polymerizable group, it is fixed by polymerization. Using this property, a thin film capable of aligning liquid crystal molecules can be prepared. In order to prepare this thin film, linearly polarized light is suitable for the ultraviolet rays to be irradiated.
  • the first additive is added to the liquid crystal composition in the range of 0.1 to 10 parts by weight, and the composition is heated to dissolve the first additive.
  • This composition is injected into a device having no alignment film.
  • photoisomerization and dimerization are promoted by irradiating the linearly polarized light to the thin film made of the first additive adsorbed on the substrate interface side while heating the element.
  • the photoisomerized compound and the dimerized compound are arranged in a certain direction.
  • photopolymerization occurs, and the thin film is fixed on the substrate.
  • the formed thin film has a function as a liquid crystal alignment film.
  • composition used in the present invention will be described in the following order. First, the composition of the composition will be described. Second, the main characteristics of the component compounds and the main effects of the compounds on the composition and the device will be described. Third, the combination of components in the composition, the preferred ratio of the components, and the basis thereof will be described. Fourth, a preferred form of the component compound will be described. Fifth, preferred component compounds are shown. Sixth, additives that may be added to the composition will be described. Seventh, a method for synthesizing the component compounds will be described. Eighth, the use of the composition will be described. Ninth, a method for manufacturing an element will be described.
  • This composition contains a plurality of liquid crystal compounds.
  • the composition may contain additives. Additives include optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like.
  • This composition is classified into a composition A and a composition B from the viewpoint of a liquid crystal compound.
  • the composition A may further contain other liquid crystal compounds in addition to the liquid crystal compound selected from the compound (1) and the compound (2).
  • the “other liquid crystal compound” is a liquid crystal compound different from the compound (1) and the compound (2). Such compounds are mixed into the composition for the purpose of further adjusting the properties.
  • Composition B consists essentially of a liquid crystalline compound selected from compound (1) and compound (2).
  • the term “substantially” means that the composition may contain an additive but no other liquid crystal compound.
  • Composition B has fewer components than composition A. From the viewpoint of reducing the cost, the composition B is preferable to the composition A.
  • the composition A is preferable to the composition B from the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds.
  • the main characteristics of the component compounds and the main effects of the compounds on the composition and the device will be explained.
  • the main characteristics of the component compounds are summarized in Table 2 based on the effects of the present invention.
  • L means large or high
  • M means moderate
  • S means small or low.
  • L, M, and S are classifications based on qualitative comparison among the component compounds, and the symbol 0 (zero) means that the dielectric anisotropy is extremely small.
  • the main effects of the component compound on the properties of the composition are as follows.
  • An alignment monomer having a cinnamate group or chalcone group and a hydroxyl group is the first additive.
  • This compound is arranged in a certain direction at the molecular level when dimerization, isomerization and polymerization are carried out by polarized light. Therefore, the thin film formed from the first additive aligns liquid crystal molecules in the same manner as an alignment film such as polyimide.
  • Compound (1) as the first component increases the dielectric anisotropy and decreases the minimum temperature.
  • Compound (2) as the second component increases the maximum temperature or decreases the viscosity.
  • Compound (3), the second additive gives a polymer by polymerization, which shortens the response time of the device and improves image burn-in.
  • first additive + first component first additive + second component
  • first additive + first component + second component first additive + first component + second component
  • first additive + first component + first Two additives first additive + second component + second additive or first additive + first component + second component + second additive.
  • Further preferred combinations are: first additive + first component + second component or first additive + first component + second component + second additive.
  • a desirable ratio of the first additive is about 0.1 parts by weight or more when the total amount of the liquid crystal compounds is 100 parts by weight for aligning liquid crystal molecules, and about 1% for preventing display defects of the device. 10 parts by weight or less.
  • a more desirable ratio is in the range of approximately 0.3 part by weight to approximately 6 parts by weight.
  • a particularly preferred ratio is in the range of approximately 0.5 parts by weight to approximately 4 parts by weight.
  • a desirable ratio of the first component is approximately 10% by weight or more with respect to the total amount of the liquid crystal compounds for increasing the dielectric anisotropy, and approximately 90% by weight or less for decreasing the minimum temperature.
  • a more desirable ratio is in the range of approximately 20% by weight to approximately 85% by weight.
  • a particularly preferred ratio is in the range of approximately 30% by weight to approximately 85% by weight.
  • a desirable ratio of the second component is approximately 10% by weight or more based on the total amount of the liquid crystal compounds for decreasing the viscosity, and approximately 90% by weight or less for increasing the dielectric anisotropy.
  • a more desirable ratio is in the range of approximately 15% by weight to approximately 65% by weight.
  • a particularly preferred ratio is in the range of approximately 20% by weight to approximately 60% by weight.
  • the second additive may be added to the composition for the purpose of adapting to the polymer-supported orientation type device.
  • a desirable ratio of the additive is about 0.03 part by weight or more when the total amount of liquid crystalline compounds is 100 parts by weight for aligning liquid crystal molecules, and about 10 part for preventing display defects of the device. Less than parts by weight.
  • a more desirable ratio is in the range of approximately 0.1 parts by weight to approximately 2 parts by weight.
  • a particularly preferred ratio is in the range of approximately 0.2 parts by weight to approximately 1.0 parts by weight.
  • R 1 and R 2 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 to C 12 alkenyloxy. Desirable R 1 or R 2 is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat, and alkoxy having 1 to 12 carbons for increasing the dielectric anisotropy.
  • R 3 and R 4 are independently an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, an alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine 12 alkyls or alkenyls having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.
  • Desirable R 3 or R 4 is alkenyl having 2 to 12 carbons for decreasing the viscosity, and alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat.
  • R 1 to R 4 are alkyl, alkenyl, alkoxy or alkenyloxy, which are linear or branched and do not include a ring (structure). The straight chain (structure) is more preferable than the branch (structure).
  • Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More desirable alkyl is methyl, ethyl, propyl, butyl or pentyl for decreasing the viscosity.
  • Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. More desirable alkoxy is methoxy or ethoxy for decreasing the viscosity.
  • Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More desirable alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for decreasing the viscosity.
  • the preferred configuration of —CH ⁇ CH— in these alkenyls depends on the position of the double bond.
  • Trans is preferable in alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity.
  • Cis is preferred for alkenyl such as 2-butenyl, 2-pentenyl, and 2-hexenyl.
  • alkyl in which at least one hydrogen is replaced by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl. Or 8-fluorooctyl. Further preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl or 5-fluoropentyl for increasing the dielectric anisotropy.
  • alkenyl in which at least one hydrogen is replaced by fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro -4-pentenyl, or 6,6-difluoro-5-hexenyl. Further preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl for decreasing the viscosity.
  • Ring A and Ring C are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, or Tetrahydropyran-2,5-diyl.
  • Preferred ring A or ring C is 1,4-cyclohexylene for decreasing the viscosity, tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and for increasing the optical anisotropy.
  • Tetrahydropyran-2,5-diyl is Or And preferably It is.
  • Ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4, 5-trifluoronaphthalene-2,6-diyl or 7,8-difluorochroman-2,6-diyl.
  • Preferred ring B is 2,3-difluoro-1,4-phenylene for decreasing the viscosity, and 2-chloro-3-fluoro-1,4-phenylene for decreasing the optical anisotropy. In order to increase the anisotropy, 7,8-difluorochroman-2,6-diyl.
  • Ring D and ring E are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene.
  • Preferred ring D or ring E is 1,4-cyclohexylene for decreasing the viscosity or increasing the maximum temperature, and 1,4-phenylene for decreasing the minimum temperature.
  • trans is preferable to cis for increasing the maximum temperature.
  • Z 1 and Z 2 are independently a single bond, ethylene, carbonyloxy, or methyleneoxy. Desirable Z 1 or Z 2 is a single bond for decreasing the viscosity, ethylene for decreasing the minimum temperature, and methyleneoxy for increasing the dielectric anisotropy.
  • Z 3 is a single bond, ethylene, carbonyloxy, or methyleneoxy. Desirable Z 3 is a single bond for decreasing the viscosity, ethylene for decreasing the minimum temperature, and carbonyloxy for increasing the maximum temperature.
  • A is 1, 2, or 3, b is 0 or 1, and the sum of a and b is 3 or less.
  • Preferred a is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.
  • Preferred b is 0 for decreasing the viscosity, and 1 for decreasing the minimum temperature.
  • c is 1, 2 or 3.
  • Preferred c is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.
  • P 1 , P 2 , and P 3 are independently a polymerizable group.
  • Preferred P 1, P 2 or P 3 is a polymerizable group selected from the group of radicals represented by the formula (P-1) by the formula (P-5). More desirable P 1 , P 2 , or P 3 is a group represented by the formula (P-1), the formula (P-2), or the formula (P-3). Particularly preferred P 1 , P 2 , or P 3 is a group represented by formula (P-1) or formula (P-2). Most preferred P 1 , P 2 or P 3 is a group represented by the formula (P-1).
  • a preferred group represented by the formula (P-1) is —OCO—CH ⁇ CH 2 or —OCO—C (CH 3 ) ⁇ CH 2 .
  • the wavy lines in the formulas (P-1) to (P-5) indicate the binding sites.
  • M 1 , M 2 , and M 3 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is fluorine or chlorine 1-5 alkyl substituted with Preferred M 1 , M 2 or M 3 is hydrogen or methyl for increasing the reactivity. More preferred M 1 is hydrogen or methyl, and more preferred M 2 or M 3 is hydrogen.
  • Preferred Sp 1 , Sp 2 , or Sp 3 is a single bond, —CH 2 —CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —CO—CH ⁇ CH—, Or —CH ⁇ CH—CO—. Further preferred Sp 1 , Sp 2 or Sp 3 is a single bond.
  • 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, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is replaced by fluorine or chlorine. Further, it may be substituted with alkyl having 1 to 12 carbons.
  • Preferred ring F or ring I is phenyl.
  • Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene -1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2 , 7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, At least one hydrogen is fluorine, chlorine,
  • Z 4 and Z 5 are each independently a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH 2 — is —O—, —CO—, —COO—, or — OCO— may be substituted, and at least one —CH 2 —CH 2 — may be —CH ⁇ CH—, —C (CH 3 ) ⁇ CH—, —CH ⁇ C (CH 3 ) —, or —C (CH 3 ) ⁇ C (CH 3 ) — may be replaced, and in these groups at least one hydrogen may be replaced with fluorine or chlorine.
  • Preferred Z 4 or Z 5 is a single bond, —CH 2 —CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, or —OCO—. Further preferred Z 4 or Z 5 is a single bond.
  • D is 0, 1, or 2.
  • Preferred d is 0 or 1.
  • e, f, and g are each independently 0, 1, 2, 3, or 4, and the sum of e, f, and g is 1 or more.
  • Preferred e, f, or g is 1 or 2.
  • the orientation monomer which is a preferred first additive, will be described.
  • the orientation monomer preferably has at least one polymerizable group and hydroxyl group.
  • the thin film (polymer) obtained by polymerizing an orientation monomer having one polymerizable group and at least one hydroxyl group is flexible, but has an intermolecular force between the hydroxyl group and the substrate. It is considered that there is little deformation in the temperature environment in which the liquid crystal display element is driven. Therefore, the effect of maintaining the orientation control force is expected.
  • an orientation monomer having two or more polymerizable groups and at least one hydroxyl group it is considered that the cross-linking density of the thin film obtained after polymerization is increased, resulting in a strong film.
  • a spacer may be introduced between the polymerizable group and the cyclic structure in order to increase the compatibility with the terminal chain of the liquid crystal compound.
  • the spacer is preferably linear or branched.
  • the length of the spacer is preferably 2 or more carbon atoms.
  • Specific examples of preferred orientation monomers are given below.
  • Preferred first additives are compound (A-1-1) to compound (A-1-9) and compound (B-1-1) to compound (B-1-8).
  • N and m in the compound (A-1-1) to the compound (B-1-8) are independently 2 to 6.
  • the orientation monomers may be used alone or in combination of two or more.
  • Desirable compound (1) is the compound (1-1) to the compound (1-22) according to item 6.
  • at least one of the first components is compound (1-1), compound (1-3), compound (1-4), compound (1-6), compound (1-8), or compound (1-10) is preferred.
  • At least two of the first components are compound (1-1) and compound (1-6), compound (1-1) and compound (1-10), compound (1-3) and compound (1-6), A compound (1-3) and a compound (1-10), a compound (1-4) and a compound (1-6), or a combination of a compound (1-4) and a compound (1-8) is preferable.
  • Desirable compound (2) is the compound (2-1) to the compound (2-13) according to item 9.
  • at least one of the second components is the compound (2-1), the compound (2-3), the compound (2-5), the compound (2-6), the compound (2-8), or the compound (2-9) is preferred.
  • At least two of the second components are compound (2-1) and compound (2-3), compound (2-1) and compound (2-5), or compound (2-1) and compound (2-6). A combination is preferred.
  • Desirable compound (3) is the compound (3-1) to the compound (3-27) according to item 13.
  • at least one of the additives is compound (3-1), compound (3-2), compound (3-3), compound (3-18), compound (3-24), or compound ( 3-25) is preferred.
  • At least two of the additives are compound (3-1) and compound (3-2), compound (3-1) and compound (3-18), compound (3-1) and compound (3-25), compound (3-2) and Compound (3-25), Compound (3-2) and Compound (3-26), Compound (3-18) and Compound (3-24), or Compound (3-25) and Compound A combination of (3-26) is preferable.
  • additives that may be added to the composition will be described.
  • Such additives are optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like.
  • An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules to give a twist angle. Examples of such a compound are the compound (4-1) to the compound (4-5).
  • a desirable ratio of the optically active compound is approximately 5 parts by weight or less. A more desirable ratio is in the range of approximately 0.01 parts by weight to approximately 2 parts by weight.
  • an antioxidant is composed. Added to the product.
  • a preferred example of the antioxidant is a compound (5) wherein n is an integer of 1 to 9.
  • n 1, 3, 5, 7, or 9. Further preferred n is 7. Since the compound (5) in which n is 7 has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after the device has been used for a long time.
  • a desirable ratio of the antioxidant is approximately 50 ppm or more for achieving its effect, and is approximately 600 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature.
  • a more desirable ratio is in the range of approximately 100 ppm to approximately 300 ppm.
  • the ultraviolet absorber examples include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Also preferred are light stabilizers such as sterically hindered amines.
  • a desirable ratio of these absorbers and stabilizers is approximately 50 ppm or more for achieving the effect thereof, and approximately 10,000 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 10,000 ppm.
  • a dichroic dye such as an azo dye or an anthraquinone dye is added to the composition in order to adapt it to a GH (guest host) mode element.
  • a preferred ratio of the dye is in the range of approximately 0.01 part by weight to approximately 10 parts by weight.
  • an antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is added to the composition.
  • a desirable ratio of the antifoaming agent is approximately 1 ppm or more for obtaining the effect thereof, and approximately 1000 ppm or less for preventing a display defect.
  • a more desirable ratio is in the range of approximately 1 ppm to approximately 500 ppm.
  • a polymerizable compound is used to adapt to a polymer support alignment (PSA) type device.
  • Compound (3) is suitable for this purpose.
  • a polymerizable compound different from the compound (3) may be added to the composition together with the compound (3).
  • a polymerizable compound different from the compound (3) may be added to the composition.
  • Preferable examples of such a polymerizable compound are compounds such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. Further preferred examples are acrylate or methacrylate derivatives.
  • the reactivity of the polymerizable compound and the pretilt angle of the liquid crystal molecules can be adjusted by changing the type of the compound (3) or combining a polymerizable compound different from the compound (3) in an appropriate ratio. .
  • By optimizing the pretilt angle a short response time of the element can be achieved. Since the alignment of the liquid crystal molecules is stabilized, a large contrast ratio and a long lifetime can be achieved.
  • a polymerizable compound such as compound (3) is polymerized by ultraviolet irradiation.
  • the polymerization may be performed in the presence of a suitable initiator such as a photopolymerization initiator.
  • a suitable initiator such as a photopolymerization initiator.
  • Appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those skilled in the art and are described in the literature.
  • Omnirad 651 registered trademark; IGM Resins
  • Omnirad 184 registered trademark; IGM Resins
  • Omnirad 1173 registered trademark; IGM Resins
  • a desirable ratio of the photopolymerization initiator is in the range of approximately 0.1 part by weight to approximately 5 parts by weight based on the total amount of the polymerizable compound.
  • a more desirable ratio is in the range of approximately 1 part by weight to approximately 3 parts by weight.
  • a polymerization inhibitor When storing a polymerizable compound such as compound (3), a polymerization inhibitor may be added to prevent polymerization.
  • the polymerizable compound is usually added to the composition without removing the polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine and the like.
  • the polar compound is an organic compound having polarity.
  • a compound having an ionic bond is not included.
  • Atoms such as oxygen, sulfur, and nitrogen are more electronegative and tend to have partial negative charges.
  • Carbon and hydrogen tend to be neutral or have a partial positive charge.
  • Polarity arises from the fact that partial charges are not evenly distributed among different types of atoms in a compound.
  • the polar compound has at least one of partial structures such as —OH, —COOH, —SH, —NH 2 ,>NH,> N—.
  • the polymerizable compound having a cinnamate group or chalcone group and a hydroxyl group as the first additive is synthesized by the method described in JP 2012-87286 A and JP 2012-107198 A.
  • An alignment monomer having an ⁇ -fluoroacrylate group is synthesized with reference to a method described in JP-A-2005-112850.
  • compositions are prepared from the compound thus obtained by known methods. For example, the component compounds are mixed and dissolved in each other by heating.
  • compositions have a minimum temperature of about ⁇ 10 ° C. or lower, a maximum temperature of about 70 ° C. or higher, and an optical anisotropy in the range of about 0.07 to about 0.20.
  • a composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the ratio of the component compounds or by mixing other liquid crystal compounds.
  • compositions having optical anisotropy in the range of about 0.10 to about 0.30 may be prepared by this method.
  • a device containing this composition has a large voltage holding ratio.
  • This composition is suitable for an AM device.
  • This composition is particularly suitable for a transmissive AM device.
  • This composition can be used as a composition having a nematic phase, or can be used as an optically active composition by adding an optically active compound.
  • This composition can be used for an AM device. Further, it can be used for PM elements.
  • This composition can be used for an AM device and a PM device having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, and FPA.
  • Use for an AM device having a VA, OCB, IPS mode or FFS mode is particularly preferable.
  • the alignment of liquid crystal molecules may be parallel to or perpendicular to the glass substrate.
  • These elements may be reflective, transmissive, or transflective. Use in a transmissive element is preferred. It can also be used for an amorphous silicon-TFT device or a polycrystalline silicon-TFT device.
  • NCAP non-curvilinear-aligned-phase
  • PD polymer-dispersed
  • the first is a step of adding the first additive to the liquid crystal composition and heating and dissolving the composition at a temperature higher than the upper limit temperature.
  • the second is a step of injecting this composition into a liquid crystal display element.
  • the third is a step of irradiating polarized ultraviolet rays while heating the liquid crystal composition to a temperature higher than the upper limit temperature.
  • the first additive is dimerized or isomerized by linearly polarized light, and at the same time polymerization proceeds.
  • a preferable integrated light quantity (J / cm 2 ) of linearly polarized ultraviolet light is 0.1 to 20 J / cm 2 when it reaches the element surface.
  • a preferable range of the integrated light amount is 0.1 to 10 J / cm 2 , and a more preferable range is 0.1 to 7 J / cm 2 .
  • the integrated light quantity (J / cm 2 ) can be obtained by illuminance of ultraviolet rays (unit: mW / cm 2 ) ⁇ irradiation time (unit: sec).
  • the temperature condition at the time of irradiation with linearly polarized ultraviolet rays is preferably set similarly to the above heat treatment temperature. Since the time of irradiation with the linearly polarized ultraviolet rays is calculated from the lamp illuminance, it is preferable that the time is as high as possible from the viewpoint of production efficiency.
  • the polymer composed of the first additive is formed and fixed on the substrate as a thin film. Since this polymer is arranged in a certain direction at the molecular level, the thin film functions as a liquid crystal alignment film. By this method, a liquid crystal display element having no alignment film such as polyimide can be manufactured.
  • the present invention will be described in more detail with reference to examples. The invention is not limited by these examples.
  • the present invention includes a mixture of the composition of Example 1 and the composition of Example 2.
  • the invention also includes a mixture of at least two of the example compositions.
  • the synthesized compound was identified by a method such as NMR analysis. The characteristics of the compound, composition and device were measured by the methods described below.
  • NMR analysis DRX-500 manufactured by Bruker BioSpin Corporation was used for measurement.
  • the sample was dissolved in a deuterated solvent such as CDCl 3, and the measurement was performed at room temperature, 500 MHz, and 16 times of integration.
  • Tetramethylsilane was used as an internal standard.
  • CFCl 3 was used as an internal standard and the number of integrations was 24.
  • s is a singlet
  • d is a doublet
  • t is a triplet
  • q is a quartet
  • quint is a quintet
  • sex is a sextet
  • m is a multiplet
  • br is broad.
  • GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for measurement.
  • the carrier gas is helium (2 mL / min).
  • the sample vaporization chamber was set at 280 ° C, and the detector (FID) was set at 300 ° C.
  • capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m; stationary liquid phase is dimethylpolysiloxane; nonpolar) manufactured by Agilent Technologies Inc. was used.
  • the column was held at 200 ° C. for 2 minutes and then heated to 280 ° C. at a rate of 5 ° C./min.
  • a sample was prepared in an acetone solution (0.1% by weight), and 1 ⁇ L thereof was injected into the sample vaporization chamber.
  • the recorder is a C-R5A Chromatopac manufactured by Shimadzu Corporation, or an equivalent product.
  • the obtained gas chromatogram showed the peak retention time and peak area corresponding to the component compounds.
  • capillary column As a solvent for diluting the sample, chloroform, hexane or the like may be used.
  • the following capillary column may be used.
  • HP-1 from Agilent Technologies Inc. (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m), Rtx-1 from Restek Corporation (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m), BP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m) manufactured by SGE International Pty.
  • a capillary column CBP1-M50-025 length 50 m, inner diameter 0.25 mm, film thickness 0.25 ⁇ m
  • Shimadzu Corporation may be used.
  • the ratio of the liquid crystal compound contained in the composition may be calculated by the following method.
  • a mixture of liquid crystal compounds is detected by a gas chromatograph (FID).
  • the area ratio of peaks in the gas chromatogram corresponds to the ratio (weight ratio) of liquid crystal compounds.
  • the correction coefficient of each liquid crystal compound may be regarded as 1. Therefore, the ratio (% by weight) of the liquid crystal compound can be calculated from the peak area ratio.
  • Measurement sample When measuring the characteristics of the composition and the device, the composition was used as it was as a sample.
  • a sample for measurement was prepared by mixing this compound (15% by weight) with mother liquid crystals (85% by weight). The characteristic value of the compound was calculated from the value obtained by the measurement by extrapolation.
  • (Extrapolated value) ⁇ (Measured value of sample) ⁇ 0.85 ⁇ (Measured value of mother liquid crystal) ⁇ / 0.15.
  • the ratio of the compound and the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% by weight in this order. changed.
  • the maximum temperature, optical anisotropy, viscosity, and dielectric anisotropy values for the compound were determined.
  • the following mother liquid crystals were used.
  • the ratio of the component compounds is shown by weight%.
  • Measurement method The characteristics were measured by the following method. Many of these methods have been modified by the methods described in the JEITA standard (JEITA ED-2521B) established by the Japan Electronics and Information Technology Industries Association (hereinafter referred to as JEITA). Was the way. No thin film transistor (TFT) was attached to the TN device used for the measurement.
  • JEITA Japan Electronics and Information Technology Industries Association
  • nematic phase (NI; ° C.): A sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when a part of the sample changed from a nematic phase to an isotropic liquid.
  • the upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”.
  • T C Minimum temperature of nematic phase
  • a sample having a nematic phase is placed in a glass bottle and placed in a freezer at 0 ° C., ⁇ 10 ° C., ⁇ 20 ° C., ⁇ 30 ° C., and ⁇ 40 ° C. for 10 days. After storage, the liquid crystal phase was observed. For example, when the sample remained in a nematic phase at ⁇ 20 ° C. and changed to a crystalline or smectic phase at ⁇ 30 ° C., the TC was described as ⁇ 20 ° C.
  • the lower limit temperature of the nematic phase may be abbreviated as “lower limit temperature”.
  • Viscosity Bulk viscosity; ⁇ ; measured at 20 ° C .; mPa ⁇ s: An E-type viscometer manufactured by Tokyo Keiki Co., Ltd. was used for the measurement.
  • Viscosity (rotational viscosity; ⁇ 1; measured at 25 ° C .; mPa ⁇ s): The measurement was performed according to the method described in M. ⁇ Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). I followed. A sample was put in a VA device having a distance (cell gap) between two glass substrates of 20 ⁇ m. This element was applied stepwise in increments of 1 volt within a range of 39 to 50 volts. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds).
  • the dielectric constants ( ⁇ and ⁇ ) were measured as follows. 1) Measurement of dielectric constant ( ⁇ ): An ethanol (20 mL) solution of octadecyltriethoxysilane (0.16 mL) was applied to a well-cleaned glass substrate. The glass substrate was rotated with a spinner and then heated at 150 ° C. for 1 hour. A sample was put in a VA element in which the distance between two glass substrates (cell gap) was 4 ⁇ m, and the element was sealed with an adhesive that was cured with ultraviolet rays. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant ( ⁇ ) in the major axis direction of the liquid crystal molecules was measured.
  • Threshold voltage (Vth; measured at 25 ° C .; V): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement.
  • the light source was a halogen lamp.
  • a sample is placed in a normally black mode VA element in which the distance between two glass substrates (cell gap) is 4 ⁇ m and the rubbing direction is anti-parallel, and an adhesive that cures the element with ultraviolet rays is used. And sealed.
  • the voltage (60 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 20V by 0.02V.
  • the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured.
  • a voltage-transmittance curve was created in which the transmittance was 100% when the light amount reached the maximum and the transmittance was 0% when the light amount was the minimum.
  • the threshold voltage was expressed as a voltage when the transmittance reached 10%.
  • VHR-1 Voltage holding ratio
  • the TN device used for the measurement had a polyimide alignment film, and the distance between two glass substrates (cell gap) was 5 ⁇ m. . This element was sealed with an adhesive that was cured with ultraviolet rays after the sample was placed.
  • the TN device was charged by applying a pulse voltage (60 microseconds at 5 V).
  • the decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined.
  • Area B was the area when it was not attenuated.
  • the voltage holding ratio was expressed as a percentage of area A with respect to area B.
  • VHR-2 Voltage holding ratio (VHR-2; measured at 80 ° C .;%): The voltage holding ratio was measured in the same procedure as above except that it was measured at 80 ° C. instead of 25 ° C. The obtained value was expressed as VHR-2.
  • VHR-3 Voltage holding ratio
  • the TN device used for the measurement had a polyimide alignment film, and the cell gap was 5 ⁇ m.
  • a sample was injected into this element and irradiated with light for 20 minutes.
  • the light source was an ultra high pressure mercury lamp USH-500D (manufactured by USHIO), and the distance between the element and the light source was 20 cm.
  • a decaying voltage was measured for 16.7 milliseconds.
  • a composition having a large VHR-3 has a large stability to ultraviolet light.
  • VHR-3 is preferably 90% or more, and more preferably 95% or more.
  • VHR-4 Voltage holding ratio
  • the TN device injected with the sample was heated in a constant temperature bath at 80 ° C. for 500 hours, and then the voltage holding ratio was measured to determine the stability against heat. Evaluated. In the measurement of VHR-4, a voltage decaying for 16.7 milliseconds was measured. A composition having a large VHR-4 has a large stability to heat.
  • the response time was expressed as the time required for the change from 90% transmittance to 10% transmittance (fall time; millisecond).
  • the compounds in Examples were represented by symbols based on the definitions in Table 3 below.
  • Table 3 the configuration regarding 1,4-cyclohexylene is trans.
  • the number in parentheses after the symbol corresponds to the compound number.
  • the symbol ( ⁇ ) means other liquid crystal compounds.
  • the ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition.
  • Example 1 of device The composition containing the first additive was injected into an element having no raw material alignment film. After irradiation with linearly polarized ultraviolet rays, the orientation of liquid crystal molecules in this device was confirmed.
  • the raw materials are a composition such as the composition (M1) to the composition (M22), the compound (A-1-1-1), the compound (B-1-2-1), the compound (B-1-3- It selected suitably from the 1st additives like 1).
  • the composition is as follows.
  • the first additive is compound (A-1-1-1), compound (A-1-7-1), compound (B-1-2-1) and compound (B-1-3-1). is there.
  • the element While heating the IPS element at 90 ° C., the element was irradiated with ultraviolet rays (313 nm, 5.0 J / cm 2 ) linearly polarized from the normal direction to obtain an element on which an orientation control layer was formed.
  • the irradiated ultraviolet rays are linearly polarized by passing through a polarizer.
  • the element on which the alignment control layer was formed was set on a polarizing microscope, and the alignment state of the liquid crystal was observed.
  • the polarizer and analyzer of the polarizing microscope were arranged so that their transmission axes were orthogonal to each other.
  • the orientation direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarizing microscope are parallel, that is, the angle formed by the orientation direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarization microscope is 0 degree.
  • the device was placed on a horizontal rotation stage of a polarizing microscope. Light was irradiated from the lower side of the element, that is, from the polarizer side, and the presence or absence of light passing through the analyzer was observed. Since no light transmitted through the analyzer was observed, the orientation was determined to be “good”. In addition, when the light which permeate
  • the element was rotated on the horizontal rotation stage of the polarizing microscope, and the angle formed by the transmission axis of the polarizer of the polarizing microscope and the alignment direction of the liquid crystal molecules was changed from 0 degree.
  • the intensity of the light transmitted through the analyzer increases as the angle formed by the transmission axis of the polarizer of the polarizing microscope and the alignment direction of the liquid crystal molecules increases, and is almost maximized when the angle is 45 degrees. confirmed.
  • the liquid crystal molecules were aligned in a substantially horizontal direction with respect to the main surface of the substrate of the device, and determined to be “horizontal alignment”. In Example 1, no light leakage was observed, so the orientation was good.
  • the liquid crystal molecules were horizontally aligned.
  • Example 2 To the composition (M2), the compound (B-1-2-1) as the first additive was added at a ratio of 0.5 part by weight. Using this mixture, a device was produced in the same manner as in Example 1. When the presence or absence of light leakage was observed by the same method as in Example 1, no light leakage was observed, so the orientation was good. The liquid crystal molecules were horizontally aligned.
  • Example 3 The compound (B-1-3-1) as the first additive was added to the composition (M11) at a ratio of 0.5 part by weight. This mixture was injected into an IPS device having no alignment film at 95 ° C. (above the upper limit temperature of the nematic phase). The device was irradiated with linearly polarized light (313 nm, 2.0 J / cm 2 ) from the normal direction at 100 ° C. (above the upper limit temperature). When the presence or absence of light leakage was observed by the same method as in Example 1, no light leakage was observed, so the orientation was good. The liquid crystal molecules were horizontally aligned.
  • Example 4 To the composition (M1), the first additive, the compound (A-1-1-1) and the compound (A-1-7-1), were each added in a proportion of 0.5 part by weight. Using this mixture, a device was produced in the same manner as in Example 1. When the presence or absence of light leakage was observed by the same method as in Example 1, no light leakage was observed, so the orientation was good. The liquid crystal molecules were horizontally aligned.
  • Comparative Example 1 Only the composition (M1) was injected into an IPS device having no alignment film. When the presence or absence of light leakage was observed by the same method as in Example 1, light leakage was observed, and the orientation was poor.
  • the high maximum temperature of the nematic phase the low minimum temperature of the nematic phase, small viscosity, suitable optical anisotropy, negatively large dielectric anisotropy, large specific resistance, high stability against ultraviolet rays, high stability against heat It can be expected that a liquid crystal display element having a liquid crystal composition satisfying at least one of the above characteristics can be obtained.
  • the liquid crystal composition of the present invention can be used for a liquid crystal monitor, a liquid crystal television and the like.

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Abstract

L'invention fournit une composition de cristaux liquides dans laquelle l'alignement de molécules de cristaux liquides d'un élément d'affichage à cristaux liquides exempt de film d'alignement, est commandé par un monomère d'alignement de structure spécifique incolore, et, en outre, dans laquelle le monomère d'alignement incolore présente une compatibilité satisfaisante. L'invention concerne également un élément d'affichage à cristaux liquides exempt de film d'alignement, dans lequel l'orientation de molécules de cristaux liquides peut être commandée lorsqu'une polarisation et une exposition sont effectuées simultanément à un chauffage à une température dépassant une température de limite supérieure de la composition de cristaux liquides, vis-à-vis de cette composition de cristaux liquides à anisotropie diélectrique négative comprenant en tant que premier additif un monomère d'alignement ayant un groupe cinnamate ou un groupe chalcone, et un groupe hydroxyle.
PCT/JP2018/004042 2017-02-16 2018-02-06 Élément d'affichage à cristaux liquides, et composition de cristaux liquides WO2018150954A1 (fr)

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JP2020041128A (ja) * 2018-09-06 2020-03-19 Jnc株式会社 水平配向型液晶表示素子、液晶組成物、重合性化合物および表示装置、水平配向型液晶表示素子の製造方法、並びに、重合性化合物の配向制御層形成モノマーとしての使用
JP2021051281A (ja) * 2019-09-20 2021-04-01 Jnc株式会社 水平配向型液晶表示素子、液晶組成物、表示装置、および、水平配向型液晶表示素子の製造方法

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