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WO2018105291A1 - Composition de cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

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

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Publication number
WO2018105291A1
WO2018105291A1 PCT/JP2017/040198 JP2017040198W WO2018105291A1 WO 2018105291 A1 WO2018105291 A1 WO 2018105291A1 JP 2017040198 W JP2017040198 W JP 2017040198W WO 2018105291 A1 WO2018105291 A1 WO 2018105291A1
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Prior art keywords
liquid crystal
compound
carbons
composition
phenylene
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PCT/JP2017/040198
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English (en)
Japanese (ja)
Inventor
将之 齋藤
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JNC Corp
JNC Petrochemical Corp
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JNC Corp
JNC Petrochemical Corp
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Priority to JP2018554871A priority Critical patent/JPWO2018105291A1/ja
Priority to CN201780075415.7A priority patent/CN110050054A/zh
Priority to TW106140346A priority patent/TW201821598A/zh
Publication of WO2018105291A1 publication Critical patent/WO2018105291A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • 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 liquid crystal composition having a positive dielectric anisotropy, a liquid crystal display device containing the composition, and the like.
  • the present invention relates to a liquid crystal composition containing a reactive compound such as a dimerizable compound or an isomerizable compound, in which the orientation of liquid crystal molecules is controlled by the action of the compound, and a liquid crystal display device.
  • the classification based on the operation mode of the liquid crystal molecules is as follows: PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS. (In-plane switching), VA (vertical alignment), FFS (fringe field switching), FPA (field-induced photo-reactive alignment) mode.
  • the classification based on the element drive system is PM (passive matrix) and AM (active matrix). PM is classified into static and multiplex, and AM is classified into TFT (thin film insulator), MIM (metal insulator metal), 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.
  • the elastic constant of the composition is related to the contrast of the device. In order to increase the contrast in the device, a large elastic constant in the composition is more preferable.
  • the optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large optical anisotropy or a small optical anisotropy, ie an appropriate optical anisotropy is required.
  • the product ( ⁇ n ⁇ d) of the optical anisotropy ( ⁇ n) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio.
  • the appropriate product value depends on the type of operation mode. For a device with a mode such as TN, a suitable value is about 0.45 ⁇ m. In this case, a composition having a large optical anisotropy is preferable for a device having a small cell gap.
  • a large dielectric anisotropy in the composition contributes to a low threshold voltage, a small power consumption and a large contrast ratio in the device. Therefore, a large dielectric anisotropy is preferable.
  • a large specific resistance in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase in the initial stage is preferable.
  • a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase after being used for a long time is preferable.
  • the stability of the composition against ultraviolet rays and heat is related to the lifetime of the liquid crystal display device. When their 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 AM device.
  • Patent Document 1 There has been reported a method using a reactive compound such as a dimerizable compound or an isomerizable compound instead of an alignment film such as polyimide (Patent Document 1).
  • this compound 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 substrate is irradiated with linearly polarized light at a temperature higher than the upper limit temperature of the liquid crystal composition.
  • the reactive compound is dimerized or isomerized by this linearly polarized light, the molecules are arranged in a certain direction.
  • a horizontal alignment mode element such as IPS and FFS and a vertical alignment mode element such as VA can be manufactured.
  • One object of the present invention is to provide a liquid crystal composition containing a reactive compound. Another object is to provide a combination of a reactive compound and a liquid crystal composition in which dissolution and phase separation proceed easily. Another purpose is to have a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, a large dielectric anisotropy, a large dielectric constant in the minor axis direction of the liquid crystal molecules, and a large specific resistance. It is to provide a liquid crystal composition satisfying at least one of properties such as high stability to ultraviolet light, high stability to heat, and a large elastic constant.
  • Another object is to provide a liquid crystal composition having an appropriate balance between at least two of these characteristics. Another object is to provide a liquid crystal display device in which the orientation of liquid crystal molecules is controlled by utilizing such a composition. Another object is to provide an AM device having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime.
  • the present invention contains a reactive compound such as a dimerizable compound or an isomerizable compound as an additive, and at least one compound selected from the group of compounds represented by formula (1) as a first component
  • the present invention relates to a liquid crystal composition having positive dielectric anisotropy and a liquid crystal display element containing the composition.
  • R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons;
  • ring A is 1,4-cyclohexylene, 1,4 -Phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane -2,5-diyl, or tetrahydropyran-2,5-diyl;
  • Z 1 is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy;
  • X 1 and X 2 are independently hydrogen or It is fluorine;
  • Y 1 is fluorine, chlorine, carbon number of 1 was replaced with at least one hydrogen fluorine or chlorine 12 alkyl, at least one hydrogen Alkoxy having 1 to 12 carbon atoms replaced by nitrogen or chlorine, or al
  • One advantage of the present invention is to provide a liquid crystal composition containing a reactive compound. Another advantage is to provide a combination of a reactive compound and a liquid crystal composition in which dissolution and phase separation proceed easily. Another advantage is that the upper limit temperature of the nematic phase, the lower limit temperature of the nematic phase, small viscosity, suitable optical anisotropy, large dielectric anisotropy, large dielectric constant in the minor axis direction of liquid crystal molecules, large specific resistance It is to provide a liquid crystal composition satisfying at least one of properties such as high stability to ultraviolet light, high stability to heat, and a large elastic constant. Another advantage is to provide a liquid crystal composition having an appropriate balance between at least two of these properties.
  • Another advantage is to provide a liquid crystal display device in which the orientation of liquid crystal molecules is controlled by utilizing such a composition.
  • Another advantage is to provide an AM device having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime.
  • liquid crystal composition and “liquid crystal display element” may be abbreviated as “composition” and “element”, respectively.
  • “Liquid crystal display element” is a general term for liquid crystal display panels and liquid crystal display modules.
  • “Liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and a composition that does not have a liquid crystal phase but has 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 liquid crystal composition as necessary.
  • the ratio of the liquid crystal compound is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition not containing the additive even when the additive is added.
  • the ratio of the additive is expressed as a percentage by weight (% by weight) based on the weight of the liquid crystal composition not containing the additive. 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 upper limit temperature of the nematic phase may be abbreviated as “the upper limit temperature”.
  • “Lower limit temperature of nematic phase” may be abbreviated as “lower limit temperature”.
  • High specific resistance means that the composition has a large specific resistance not only at room temperature in the initial stage but also at a temperature close to the upper limit temperature of the nematic phase. It means having a large specific resistance even at a close temperature.
  • High voltage holding ratio means that the device has a large voltage holding ratio not only at room temperature in the initial stage but also at a temperature close to the upper limit temperature of the nematic phase. It means having a large voltage holding ratio even at a temperature close to.
  • compositions or devices characteristics may be examined before and after a aging test (including an accelerated deterioration test).
  • the expression “increasing dielectric anisotropy” means that when the composition has a positive dielectric anisotropy, the value increases positively, and the composition having a negative dielectric anisotropy When it is a thing, it means that the value increases negatively.
  • the compound represented by the formula (1) may be abbreviated as “compound (1)”. At least one compound selected from the group of compounds represented by formula (1) may be abbreviated as “compound (1)”. “Compound (1)” means one compound represented by formula (1), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas.
  • the expression “at least one‘ A ’” means that the number of ‘A’ is arbitrary.
  • the expression “at least one 'A' may be replaced by 'B'” means that when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is 2 Even when there are more than two, their positions can be selected without restriction. This rule also applies to the expression “at least one 'A' is replaced by 'B'".
  • Expressions such as “at least one —CH 2 — may be replaced by —O—” are used herein.
  • —CH 2 —CH 2 —CH 2 — may be converted to —O—CH 2 —O— by replacing non-adjacent —CH 2 — with —O—.
  • adjacent —CH 2 — is not replaced by —O—.
  • —O—O—CH 2 — (peroxide) is formed by this replacement. That is, this expression includes both “one —CH 2 — may be replaced with —O—” and “at least two non-adjacent —CH 2 — may be replaced with —O—”. means. This rule applies not only to replacement with —O— but also to replacement with a divalent group such as —CH ⁇ CH— or —COO—.
  • 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
  • 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 Z 2 , ring B, and the like.
  • 2-Fluoro-1,4-phenylene means the following two divalent groups.
  • fluorine may be leftward (L) or rightward (R).
  • This rule also applies to bilaterally asymmetric groups produced 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.
  • Item 1 Containing at least one of a dimerizable compound and an isomerizable compound as an additive, and at least one compound selected from the group of compounds represented by formula (1) as a first component, A liquid crystal composition having a rate anisotropy.
  • R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons;
  • ring A is 1,4-cyclohexylene, 1,4 -Phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane -2,5-diyl, or tetrahydropyran-2,5-diyl;
  • Z 1 is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy;
  • X 1 and X 2 are independently hydrogen or It is fluorine;
  • Y 1 is fluorine, chlorine, carbon number of 1 was replaced with at least one hydrogen fluorine or chlorine 12 alkyl, at least one hydrogen Alkoxy having 1 to 12 carbon atoms replaced by nitrogen or chlorine, or al
  • At least one compound selected from the group of cinnamic acid, cinnamic acid ester, polyvinyl cinnamate, chalcone, 4-hydroxychalcone, 4′-hydroxychalcone, coumarin, azobenzene, and derivatives thereof Item 2.
  • Item 3 The liquid crystal composition according to item 1 or 2, which contains at least one compound selected from the group of cinnamic acid, polyvinyl cinnamate, 4-hydroxychalcone, and 4′-hydroxychalcone as an additive.
  • Item 4. The liquid crystal composition according to any one of items 1 to 3, comprising at least one compound selected from the group of compounds represented by formulas (1-1) to (1-35) as a first component: object.
  • R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons.
  • Item 5 The liquid crystal according to any one of Items 1 to 4, wherein a ratio of the additive is in the range of 0.1 wt% to 10 wt%, and a ratio of the first component is in the range of 10 wt% to 85 wt%. Composition.
  • Item 6. The liquid crystal composition according to any one of items 1 to 5, comprising at least one compound selected from the group of compounds represented by formula (2) as the second component.
  • R 2 and R 3 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen is fluorine or chlorine.
  • Substituted alkenyl having 2 to 12 carbon atoms; ring B and ring C are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5 -Difluoro-1,4-phenylene;
  • Z 2 is a single bond, ethylene, or carbonyloxy;
  • b is 1, 2, or 3.
  • Item 7. The liquid crystal composition according to any one of items 1 to 6, comprising at least one compound selected from the group of compounds represented by formulas (2-1) to (2-13) as a second component: object.
  • R 2 and R 3 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or C2-C12 alkenyl in which at least one hydrogen is replaced by fluorine or chlorine.
  • Item 8 The liquid crystal composition according to item 6 or 7, wherein the ratio of the second component is in the range of 10% by weight to 85% by weight.
  • Item 9 The liquid crystal composition according to any one of items 1 to 8, comprising at least one compound selected from the group of compounds represented by formula (3) as a third component.
  • R 4 and R 5 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons.
  • Ring D and Ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is fluorine or chlorine 1,4-phenylene, naphthalene-2,6-diyl substituted with, naphthalene-2,6-diyl, chroman-2,6-diyl with at least one hydrogen replaced with fluorine or chlorine, or at least one Chroman-2,6-diyl in which hydrogen is replaced by fluorine or chlorine;
  • ring E 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;
  • Item 10 The liquid crystal composition according to any one of items 1 to 9, comprising at least one compound selected from the group of compounds represented by formulas (3-1) to (3-22) as a third component: object.
  • R 4 and R 5 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or It is alkenyloxy having 2 to 12 carbon atoms.
  • Item 11 The liquid crystal composition according to item 9 or 10, wherein the ratio of the third component is in the range of 3% by weight to 25% by weight.
  • the upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C.) is 0.07 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C.) is 2.
  • the liquid crystal composition according to any one of items 1 to 11, which is the above.
  • Item 13 A liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 12.
  • Item 14 The liquid crystal display element according to item 13, wherein the operation mode of the liquid crystal display element is a TN mode, an ECB mode, an OCB mode, an IPS mode, an FFS mode, or an FPA mode, and the driving method of the liquid crystal display element is an active matrix method .
  • Item 15 The liquid crystal display element according to item 13, 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 16 Use of the liquid crystal composition according to any one of items 1 to 12 in a liquid crystal display device.
  • the present invention includes the following items.
  • (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 subject of the present invention is a liquid crystal composition containing a reactive compound (Patent Document 1) such as a dimerizable compound or an isomerizable compound.
  • the composition contains at least one dimerizable compound or at least one isomerizable compound.
  • the composition may contain both dimerizable and isomerizable compounds.
  • An example of a dimerizable compound is a compound having a cinnamoyl group.
  • Examples of isomerizable compounds are compounds having an azo group.
  • a reactive compound means a compound that absorbs polarized light and causes a reaction such as dimerization or isomerization.
  • dimerization is sometimes expressed as a crosslinking reaction.
  • reactive compounds are cinnamic acid (S-1), cinnamic acid ester (S-2), polyvinyl cinnamate (S-3), chalcone (S-4), 4-hydroxychalcone (S- 5) 4′-hydroxychalcone (S-6), coumarin (S-7), or azobenzene (S-8).
  • R is alkyl or aryl.
  • a derivative means an organic compound in which a part of the molecular structure (for example, hydrogen) is replaced with another atom or another atomic group.
  • the original organic compound and its derivative have a common partial structure.
  • Examples of other atoms are fluorine, chlorine, and bromine.
  • Examples of other atomic groups are aliphatic groups such as alkyl and alkenyl.
  • Other examples are hydroxy (—OH), alkoxy (—OR), amino (—NH 2 ), alkylamino (—NH—R, —NR 2 ), alkoxycarbonyl (—COOR), and acyloxy (—OCOR) Are polar groups.
  • Another example is a polymerizable group such as acryloyloxy (—OCO—CH ⁇ CH 2 ) and methacryloyloxy (—OCO—C (CH 3 ) ⁇ CH 2 ).
  • Cinnamic acid has the structure C 6 H 5 —CH ⁇ CH—COOH.
  • —CO—CH ⁇ CH—C 6 H 5 is referred to as a cinnamoyl group. Since the double bond of the cinnamoyl group is sandwiched between a benzene ring and a carbonyl, it is a functional group that is easily dimerized by light. Cinnamic acid dimerizes in the solid phase with ultraviolet rays to form a cyclobutane ring. Utilizing this property, a thin film capable of aligning liquid crystal molecules from cinnamic acid can be prepared. In order to prepare this thin film, linearly polarized light is suitable for the ultraviolet rays to be irradiated.
  • cinnamic acid is added to the liquid crystal composition in the range of 0.1 wt% to 10 wt%, and the composition is heated to dissolve the cinnamic acid.
  • This composition is injected into a device having no alignment film.
  • the temperature of the element is returned to room temperature, and cinnamic acid is deposited on the substrate.
  • the cinnamic acid is dimerized by irradiating the thin film of cinnamic acid with linearly polarized light while heating the device. Since the molecules of the dimer are arranged in a certain direction, the thin film functions as a liquid crystal alignment film.
  • Aromatic azo compounds are isomerized by linearly polarized light. At this time, the thin film of the azo compound is arranged in a certain direction at the molecular level, and thus has a function as a liquid crystal alignment film.
  • composition of the present invention will be described in the following order. First, the composition of the composition will be described. Second, the main characteristics of the component compounds and the main effects of the compounds on the composition will be explained. Third, the combination of components in the composition, the preferred ratio of the components, and the basis thereof will be described. Fourth, a preferred form of the component compound will be described. Fifth, preferred component compounds are shown. Sixth, additives that may be added to the composition will be described. Seventh, a method for synthesizing the component compounds will be described. Eighth, the use of the composition will be described. Ninth, a method for manufacturing an element will be described.
  • composition of the composition will be explained.
  • the composition of the present invention is classified into Composition A and Composition B.
  • the composition A may further contain other liquid crystal compounds, additives and the like in addition to the liquid crystal compounds selected from the compound (1), the compound (2), and the compound (3).
  • the “other liquid crystal compound” is a liquid crystal compound different from the compound (1), the compound (2), and the compound (3).
  • Such compounds are mixed into the composition for the purpose of further adjusting the properties.
  • Additives include optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like.
  • Composition B consists essentially of a liquid crystalline compound selected from compound (1), compound (2), and compound (3). “Substantially” means that the composition may contain an additive but no other liquid crystal compound. Composition B has fewer components than composition A. From the viewpoint of reducing the cost, the composition B is preferable to the composition A. The composition A is preferable to the composition B from the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds.
  • the main characteristics of the component compounds and the main effects of the compounds on the 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 a qualitative comparison among the component compounds, and 0 (zero) means extremely small.
  • the reactive compound is an additive. This compound is arranged in a certain direction at the molecular level when dimerization or isomerization is performed by polarized light. Therefore, a thin film prepared from a reactive compound aligns liquid crystal molecules in the same manner as an alignment film such as polyimide.
  • Compound (1) increases the dielectric anisotropy.
  • Compound (2) decreases the viscosity or increases the maximum temperature.
  • Compound (3) increases the dielectric constant in the minor axis direction.
  • first component + additive first component + second component + additive, first component + third component + additive, or first component + second component + third component + Additive.
  • a further preferred combination is first component + second component + additive.
  • a desirable ratio of the additive is approximately 0.1% by weight or more for aligning liquid crystal molecules, and approximately 10% by weight or less for preventing display defects of the device.
  • a further preferred ratio is in the range of approximately 0.3% by weight to approximately 6% by weight.
  • a particularly preferred ratio is in the range of approximately 0.5% by weight to approximately 4% by weight.
  • a desirable ratio of the first component is approximately 10% by weight or more for increasing the dielectric anisotropy, and approximately 85% by weight or less for decreasing the minimum temperature or decreasing the viscosity.
  • a more desirable ratio is in the range of approximately 15% by weight to approximately 80% by weight.
  • a particularly preferred ratio is in the range of approximately 20% by weight to approximately 75% by weight.
  • a desirable ratio of the second component is approximately 10% by weight or more for increasing the maximum temperature or decreasing the viscosity, and approximately 85% by weight or less for increasing the dielectric anisotropy.
  • a more desirable ratio is in the range of approximately 15% by weight to approximately 80% by weight.
  • a particularly preferred ratio is in the range of approximately 20% by weight to approximately 75% by weight.
  • a desirable ratio of the third component is approximately 3% by weight or more for increasing the dielectric constant in the minor axis direction, and approximately 25% by weight or less for decreasing the minimum temperature.
  • a more desirable ratio is in the range of approximately 5% by weight to approximately 20% by weight.
  • a particularly desirable ratio is in the range of approximately 5% by weight to approximately 15% by weight.
  • R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons. Desirable R 1 is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat.
  • R 2 and R 3 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon 2 having at least one hydrogen replaced with fluorine or chlorine. To 12 alkenyl.
  • Desirable R 2 or R 3 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 4 and R 5 are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons.
  • Desirable R 4 or R 5 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 constant in the minor axis direction.
  • 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.
  • linear alkenyl is preferable to branching.
  • Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. More desirable alkenyloxy is allyloxy or 3-butenyloxy for decreasing the viscosity.
  • alkyl in which at least one hydrogen is replaced by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl. Or 8-fluorooctyl. Further preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl or 5-fluoropentyl for increasing the dielectric anisotropy.
  • alkenyl in which at least one hydrogen is replaced by fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro -4-pentenyl, or 6,6-difluoro-5-hexenyl. Further preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl for decreasing the viscosity.
  • Ring A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene Pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl.
  • Desirable ring A is 1,4-phenylene or 2-fluoro-1,4-phenylene for increasing the optical anisotropy. Tetrahydropyran-2,5-diyl is Or And preferably It is.
  • Ring B and ring C are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene.
  • Preferred ring B or ring C is 1,4-cyclohexylene for decreasing the viscosity, or 1,4-phenylene for increasing the optical anisotropy.
  • Ring D and Ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is replaced by fluorine or chlorine 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl, chroman-2,6-diyl, in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen Chroman-2,6-diyl replaced with fluorine or chlorine.
  • Preferred ring D or ring F is 1,4-cyclohexylene for decreasing the viscosity, and tetrahydropyran-2,5-diyl for increasing the dielectric constant in the minor axis direction, for increasing the optical anisotropy.
  • Ring E 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 E is 2,3-difluoro-1,4-phenylene for increasing the dielectric constant in the minor axis direction.
  • Z 1 is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy. Desirable Z 1 is a single bond for decreasing the viscosity, and difluoromethyleneoxy for increasing the dielectric anisotropy.
  • Z 2 is a single bond, ethylene, or carbonyloxy. Desirable Z 2 is a single bond for decreasing the viscosity.
  • Z 3 and Z 4 are independently a single bond, ethylene, carbonyloxy, or methyleneoxy. Preferred Z 3 or Z 4 is a single bond for decreasing the viscosity, and methyleneoxy for increasing the dielectric constant in the minor axis direction.
  • X 1 and X 2 are independently hydrogen or fluorine. Desirable X 1 or X 2 is fluorine for increasing the dielectric anisotropy.
  • Y 1 is fluorine, chlorine, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine, alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine, or at least C2-C12 alkenyloxy in which one hydrogen is replaced by fluorine or chlorine. Desirable Y 1 is fluorine for decreasing the minimum temperature.
  • a preferred example of an alkyl in which at least one hydrogen is replaced by fluorine or chlorine is trifluoromethyl.
  • a preferred example of alkoxy in which at least one hydrogen is replaced by fluorine or chlorine is trifluoromethoxy.
  • a preferred example of alkenyloxy in which at least one hydrogen has been replaced by fluorine or chlorine is trifluorovinyloxy.
  • A is 1, 2, 3, or 4. Desirable a is 2 for decreasing the minimum temperature, and 3 for increasing the dielectric anisotropy.
  • b is 1, 2 or 3; Preferred b is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.
  • c is 1, 2, or 3, d is 0 or 1, and the sum of c and d is 3 or less.
  • Preferred c is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.
  • Preferred d is 0 for decreasing the viscosity, and 1 for decreasing the minimum temperature.
  • Preferred reactive compounds are cinnamic acid (S-1), cinnamic acid ester (S-2), polyvinyl cinnamate (S-3), chalcone (S-4), 4-hydroxychalcone (S-5). 4′-hydroxychalcone (S-6), coumarin (S-7), or azobenzene (S-8).
  • the reactive compounds may be derivatives of these compounds as already described. Derivatives such as 4-hydroxyazobenzene and 4- (phenylazo) phenol are also preferred.
  • Further preferred compounds are cinnamic acid (S-1), polyvinyl cinnamate (S-3), 4-hydroxychalcone (S-5), or 4′-hydroxychalcone (S-6).
  • Desirable compound (1) is the compound (1-1) to the compound (1-35) according to item 4.
  • at least one of the first components is compound (1-4), compound (1-12), compound (1-14), compound (1-15), compound (1-17), compound ( 1-18), Compound (1-23), Compound (1-24), Compound (1-27), Compound (1-29), or Compound (1-30) is preferred.
  • At least two of the first components are compound (1-12) and compound (1-15), compound (1-14) and compound (1-27), compound (1-18) and compound (1-24), A compound (1-18) and a compound (1-29), a compound (1-24) and a compound (1-29), or a combination of a compound (1-29) and a compound (1-30) is preferable.
  • Desirable compound (2) is the compound (2-1) to the compound (2-13) according to item 7.
  • at least one of the second components is the compound (2-1), the compound (2-3), the compound (2-5), the compound (2-6), or the compound (2-7). It is preferable.
  • At least two of the third components are compound (2-1) and compound (2-5), compound (2-1) and compound (2-6), compound (2-1) and compound (2-7), compound A combination of (2-3) and compound (2-5), compound (2-3) and compound (2-6), compound (2-3) and compound (2-7) is preferred.
  • Desirable compound (3) is the compound (3-1) to the compound (3-22) according to item 10.
  • at least one of the third components is compound (3-1), compound (3-3), compound (3-4), compound (3-6), compound (3-8), or compound (3-10) is preferred.
  • At least two of the third components are compound (3-1) and compound (3-6), compound (3-3) and compound (3-6), compound (3-3) and compound (3-10), The compound (3-4) and the compound (3-6), the compound (3-4) and the compound (3-8), or a combination of the compound (3-6) and the compound (3-10) is preferable.
  • 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 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% by weight or less. A more desirable ratio is in the range of approximately 0.01% by weight to approximately 2% by weight.
  • an antioxidant is composed. Added to the product.
  • a preferable example of the antioxidant is a compound (5) in which t is an integer of 1 to 9.
  • t is 1, 3, 5, 7, or 9. Further preferred t is 7. Since the compound (5) in which t 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 using the device for a long time.
  • a desirable ratio of the antioxidant is approximately 50 ppm or more for achieving its effect, and is approximately 600 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature.
  • a more desirable ratio is in the range of approximately 100 ppm to approximately 300 ppm.
  • the ultraviolet absorber examples include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Also preferred are light stabilizers such as sterically hindered amines.
  • a desirable ratio of these absorbers and stabilizers is approximately 50 ppm or more for achieving the effect thereof, and approximately 10,000 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 10,000 ppm.
  • a dichroic dye such as an azo dye or an anthraquinone dye is added to the composition in order to adapt it to a GH (guest host) mode element.
  • a preferred ratio of the dye is in the range of approximately 0.01% by weight to approximately 10% by weight.
  • an antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is added to the composition.
  • a desirable ratio of the antifoaming agent is approximately 1 ppm or more for obtaining the effect thereof, and approximately 1000 ppm or less for preventing a display defect.
  • a more desirable ratio is in the range of approximately 1 ppm to approximately 500 ppm.
  • a polymerizable compound is added to the composition in order to adapt it to a polymer support alignment (PSA) type device.
  • the polymerizable compound are compounds having a polymerizable group 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.
  • a desirable ratio of the polymerizable compound is approximately 0.05% by weight or more for achieving the effect thereof, and approximately 10% by weight or less for preventing a display defect. A more desirable ratio is in the range of approximately 0.1% by weight to approximately 2% by weight.
  • the polymerizable compound is polymerized by irradiation with ultraviolet rays.
  • the polymerization may be performed in the presence of an initiator such as a photopolymerization initiator.
  • an initiator such as a photopolymerization initiator.
  • Appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those skilled in the art and are described in the literature.
  • Irgacure 651 registered trademark; BASF
  • Irgacure 184 registered trademark; BASF
  • Darocur 1173 registered trademark; BASF
  • a desirable ratio of the photopolymerization initiator is in the range of approximately 0.1% by weight to approximately 5% by weight based on the weight of the polymerizable compound.
  • a more desirable ratio is in the range of approximately 1% by weight to approximately 3% by weight.
  • a polymerization inhibitor When storing the polymerizable compound, a polymerization inhibitor may be added to prevent polymerization.
  • the polymerizable compound is usually added to the composition without removing the polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone derivatives such as hydroquinone and 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 composition of the present invention mainly has 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 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.
  • a composition having an optical anisotropy in the range of about 0.08 to about 0.25 by controlling the proportion of the component compounds or by mixing other liquid crystal compounds, and further from about 0.10 Compositions having optical anisotropy in the range of about 0.30 may be prepared.
  • 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 TN, 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 a reactive compound 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 and lowering the temperature to room temperature. By reducing the temperature, the reactive compound is deposited on the substrate to form a thin film.
  • the third is a step of irradiating polarized light while heating the liquid crystal composition to a temperature higher than the upper limit temperature.
  • Reactive compounds are dimerized or isomerized by linearly polarized light. Since this compound 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 properties of the compounds and compositions 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 properties of the composition, 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
  • NI nematic phase
  • T C Minimum temperature of nematic phase
  • Viscosity Bulk viscosity; ⁇ ; measured at 20 ° C .; mPa ⁇ s: An E-type viscometer manufactured by Tokyo Keiki Co., Ltd. was used for the measurement.
  • Viscosity (Rotational Viscosity; ⁇ 1; Measured at 25 ° C .; mPa ⁇ s): The measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). I followed. A sample was put in a TN device having a twist angle of 0 ° and a distance (cell gap) between two glass substrates of 5 ⁇ m. A voltage was applied to this device in steps of 0.5 V in the range of 16 V to 19.5 V. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds).
  • the peak current (peak current) and peak time (peak time) of the transient current (transient current) generated by this application were measured.
  • the value of rotational viscosity was obtained from these measured values and the calculation formula (8) described on page 40 in the paper by M. Imai et al.
  • the value of dielectric anisotropy necessary for this calculation was determined by the method described below using the element whose rotational viscosity 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 was put in a normally white mode TN device in which the distance between two glass substrates (cell gap) was 0.45 / ⁇ n ( ⁇ m) and the twist angle was 80 degrees.
  • the voltage (32 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 10V by 0.02V.
  • the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured.
  • a voltage-transmittance curve was created in which the transmittance was 100% when the light amount reached the maximum and the transmittance was 0% when the light amount was the minimum.
  • the threshold voltage was expressed as a voltage when the transmittance reached 90%.
  • VHR-1 Voltage holding ratio
  • the TN device used for the measurement had a polyimide alignment film, and the distance between two glass substrates (cell gap) was 5 ⁇ m. . This element was sealed with an adhesive that was cured 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 rise time ( ⁇ r: rise time; millisecond) is the time required for the transmittance to change from 90% to 10%.
  • the fall time ( ⁇ f: fall time; millisecond) is the time required to change the transmittance from 10% to 90%.
  • the response time was expressed as the sum of the rise time and the fall time thus obtained.
  • Helical pitch (P; measured at room temperature; ⁇ m): The helical pitch was measured by the wedge method. See “Liquid Crystal Handbook", page 196 (2000 published, Maruzen). The sample was poured into a wedge-shaped cell and allowed to stand at room temperature for 2 hours, and then the disclination line interval (d2-d1) was observed with a polarizing microscope (Nikon Corporation, trade name: MM40 / 60 series). The helical pitch (P) was calculated from the following equation in which the angle of the wedge cell was expressed as ⁇ . P 2 ⁇ (d2 ⁇ d1) ⁇ tan ⁇ .
  • Dielectric constant in the minor axis direction ( ⁇ ; measured at 25 ° C.): A sample was put 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 the device, and after 2 seconds, the dielectric constant ( ⁇ ) in the minor axis direction of the liquid crystal molecules was measured.
  • 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 A composition to which a reactive compound was added was injected into an element having no raw material alignment film. After irradiation with linearly polarized light, the orientation of liquid crystal molecules in this device was examined. First, the raw materials will be explained.
  • the raw material is a composition such as the composition (M1) to the composition (M14), such as the compound (S-1), the compound (S-3), the compound (S-5), or the compound (S-6). It selected suitably from the reactive compounds.
  • the composition is as follows.
  • the additives are compound (S-1; cinnamic acid), compound (S-3; polyvinylcinnamic acid), compound (S-5; 4-hydroxychalcone), and compound (S-6; 4′-hydroxy). Chalcone).
  • Example 1 of alignment of liquid crystal molecules The compound (S-1) was added to the composition (M1) at a ratio of 3% by weight. This mixture was injected into an IPS device having no alignment film at 90 ° C. (above the upper limit temperature). After the injection, the compound (S-1) was phase-separated by lowering to 25 ° C. At 100 ° C. (above the upper limit temperature), the device was irradiated with ultraviolet rays (330 nm, 3 J / cm 2 ) linearly polarized from the normal direction. The polarizing element was set on a polarizing microscope in which the polarizer and the analyzer were arranged orthogonally so that the element was parallel to the polarization axis of the linearly polarized light. The device was irradiated with light from below, and the presence or absence of light leakage was observed. When light did not pass through the element, it was judged that the orientation was “good”. When light passing through the element was observed, it was indicated as “defective”.
  • Examples 2 to 7 The compound (S-1) or the compound (S-3) was added from the composition (M2) to the composition (M7). Using this mixture, a device was produced in the same manner as in Example 1. The presence or absence of light leakage was observed in the same manner as in Example 1.
  • Example 8 To the composition (M8), the compound (S-5) was added in a proportion of 3% by weight. This mixture was injected into an IPS device having no alignment film at 90 ° C. (above the upper limit temperature). After the injection, the compound (S-5) was phase-separated by lowering to 25 ° C. The device was irradiated with linearly polarized light (365 nm, 3 J / cm 2 ) from the normal direction at 100 ° C. (above the upper limit temperature). The presence or absence of light leakage was observed in the same manner as in Example 1.
  • linearly polarized light 365 nm, 3 J / cm 2
  • Examples 9 to 14 The compound (S-5) or the compound (S-6) was added from the composition (M9) to the composition (M14). Using this mixture, a device was produced in the same manner as in Example 1. The presence or absence of light leakage was observed in the same manner as in Example 1.
  • Comparative Example 1 The composition (M1) was injected into an IPS device having no alignment film. The presence or absence of light leakage was observed in the same manner as in Example 1. The results of Examples 1 to 14 and Comparative Example 1 are summarized in Table 4.
  • 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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  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
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  • Liquid Crystal Substances (AREA)

Abstract

La présente invention concerne: une composition de cristaux liquides qui contient un composé réactif, par exemple un acide cinnamique, et dans laquelle l'alignement des molécules de cristaux liquides est commandé par l'action du composé; et un élément d'affichage à cristaux liquides. La composition de cristaux liquides comprend un composé réactif en tant qu'additif et un composé spécifique ayant une grande valeur positive d'anisotropie diélectrique en tant que premier composant, et contient éventuellement un composé spécifique ayant une température limite supérieure élevée ou une faible viscosité en tant que deuxième composant ou un composé spécifique ayant une grande valeur négative d'anisotropie diélectrique en tant que troisième composant.
PCT/JP2017/040198 2016-12-08 2017-11-08 Composition de cristaux liquides et élément d'affichage à cristaux liquides Ceased WO2018105291A1 (fr)

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CN112543798A (zh) * 2018-10-02 2021-03-23 Dic株式会社 使用取向助剂的液晶组合物及液晶显示元件、以及其制造方法
JP7014282B2 (ja) 2018-10-02 2022-02-01 Dic株式会社 配向助剤を使用した液晶組成物及び液晶表示素子、およびその製造方法

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