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WO2019004021A1 - Élément d'affichage à cristaux liquides, composition de cristaux liquides, et composé - Google Patents

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

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Publication number
WO2019004021A1
WO2019004021A1 PCT/JP2018/023449 JP2018023449W WO2019004021A1 WO 2019004021 A1 WO2019004021 A1 WO 2019004021A1 JP 2018023449 W JP2018023449 W JP 2018023449W WO 2019004021 A1 WO2019004021 A1 WO 2019004021A1
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WIPO (PCT)
Prior art keywords
fluorine
hydrogen
liquid crystal
diyl
replaced
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2018/023449
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English (en)
Japanese (ja)
Inventor
平井　吉治
和寛 荻田
史尚 近藤
浩史 遠藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JNC Corp
JNC Petrochemical Corp
Original Assignee
JNC Corp
JNC Petrochemical Corp
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Filing date
Publication date
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Priority to JP2019526832A priority Critical patent/JPWO2019004021A1/ja
Priority to CN201880026399.7A priority patent/CN110546558A/zh
Publication of WO2019004021A1 publication Critical patent/WO2019004021A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/273—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a twelve-membered ring
    • C07C13/275—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a twelve-membered ring the twelve-membered ring being unsaturated
    • C07C13/277—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a twelve-membered ring the twelve-membered ring being unsaturated with a cyclododecatriene ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • 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
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • 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 device, a liquid crystal composition and a compound containing a liquid crystal composition having positive dielectric anisotropy.
  • the present invention relates to a liquid crystal display device using a liquid crystal composition which contains an alignment control layer-forming monomer having a vinylene group in a partial structure and can achieve alignment of liquid crystal molecules by the action of this compound.
  • phase change PC
  • TN twisted nematic
  • STN super twisted nematic
  • EOB electrically controlled birefringence
  • OCB optically compensated bend
  • IPS modes are modes such as (in-plane switching), VA (vertical alignment), FFS (fringe field switching), and FPA (field-induced photo-reactive alignment).
  • PM passive matrix
  • AM active matrix
  • PM is classified into static, multiplex, etc.
  • AM is classified into thin film transistor (TFT), metal insulator metal (MIM), etc.
  • TFT thin film transistor
  • MIM metal insulator metal
  • the classification of TFT is amorphous silicon and polycrystal silicon. The latter are classified into high temperature type and low temperature type according to the manufacturing process.
  • Source based classifications are reflective based on natural light, transmissive based on back light, and semi-transmissive based on both natural light and back light.
  • the liquid crystal display element contains a liquid crystal composition having a nematic phase.
  • This composition has suitable properties. By improving the properties of this composition, an AM element having good properties can be obtained.
  • the association between the two properties is summarized in Table 1 below. The characteristics of the composition will be further described based on commercially available AM devices.
  • the temperature range of the nematic phase is related to the usable temperature range of the device.
  • the preferred upper temperature limit of the nematic phase is about 70 ° C. or higher, and the preferred lower temperature limit of the nematic phase is about -10 ° C. or lower.
  • the viscosity of the composition is related to the response time of the device. Short response times are preferred for displaying motion pictures on the device. Even shorter response times of 1 millisecond are desirable. Thus, low viscosity in the composition is preferred. Smaller viscosities at lower temperatures are more preferred.
  • the optical anisotropy of the composition is related to the contrast ratio of the device.
  • a large or small optical anisotropy ie a suitable optical anisotropy
  • the product ( ⁇ n ⁇ d) of the optical anisotropy ( ⁇ n) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio.
  • the appropriate product value depends on the type of operating mode. This value is in the range of about 0.30 ⁇ m to about 0.40 ⁇ m in the VA mode device and in the range of about 0.20 ⁇ m to about 0.30 ⁇ m in the IPS mode or FFS mode device. In these cases, compositions with large optical anisotropy are preferred for small cell gap devices.
  • the large dielectric anisotropy in the composition contributes to low threshold voltage, low power consumption and high contrast ratio in the device. Therefore, large dielectric anisotropy is preferred.
  • the large resistivity in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a large specific resistance at the initial stage is preferred. After prolonged use, compositions having high specific resistance are 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 element used for a liquid crystal monitor, a liquid crystal television, etc.
  • an AM device having a TN mode a composition having positive dielectric anisotropy is used.
  • a composition having negative dielectric anisotropy is used.
  • an AM device having an IPS mode or an FFS mode a composition having positive or negative dielectric anisotropy is used.
  • a liquid crystal display device of the polymer supported alignment (PSA) type a liquid crystal composition containing a polymer is used. First, a composition to which a small amount of a polymerizable compound is added is injected into the device. Next, the composition is irradiated with ultraviolet light while applying a voltage between the substrates of the device. The polymerizable compound polymerizes to form a polymer network in the composition.
  • the polymer can control the alignment of liquid crystal molecules, thereby reducing the response time of the device and improving the image sticking.
  • Such an effect of the polymer can be expected to devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
  • IPS mode, FFS mode, and ECB mode it is necessary to align liquid crystal molecules in a substantially horizontal direction with respect to the main surface of the substrate when no voltage is applied.
  • alignment films such as polyimide have been used.
  • Patent Documents 1 to 3 In recent years, with the progress of narrowing of the liquid crystal panel, the adhesion width of the alignment film and the sealing agent is narrowed, and the adhesion strength is weakened, and peeling may progress from the interface between the alignment film and the sealing agent. In order to prevent such problems, methods without using an alignment film such as conventional polyimides have been proposed (Patent Documents 1 to 3).
  • the substrate is irradiated with linearly polarized light at a temperature higher than the upper limit temperature of the liquid crystal composition.
  • the low molecular weight compound or polymer is dimerized or isomerized by this linear polarization, the molecules are aligned in a certain direction.
  • IPS and FFS a device of horizontal alignment mode
  • VA a device of vertical alignment mode
  • Patent Document 4 discloses a polymer dispersed liquid crystal optical element including a polymer resin obtained by photopolymerizing a chiral nematic liquid crystal and a (meth) acrylate compound having a stilbene skeleton.
  • the liquid crystal optical element here is for reducing the drive voltage and the hysteresis.
  • Chiral nematic liquid crystal is an essential component, and it is a polymer dispersed liquid crystal optical element which is in a transparent state or selective reflection state when no voltage is applied and in a scattering state when voltage is applied, so that the configuration is different from the present invention.
  • the (meth) acrylate compound having a stilbene skeleton induces the horizontal alignment of the liquid crystal compound by polarized light irradiation.
  • An object of the present invention is to provide a liquid crystal display device which does not require a conventional alignment film made of polyimide or the like and a process for forming the same by using a liquid crystal composition containing a monomer for forming an alignment control layer. Furthermore, in order to realize a liquid crystal display element excellent in transmittance characteristics and contrast ratio, an object is to provide an alignment control layer-forming monomer which exhibits good compatibility with a liquid crystal composition and has no coloring.
  • the present invention uses a liquid crystal display device, a liquid crystal composition, and a compound that use a liquid crystal composition having an alignment control layer forming monomer having a vinylene group in a partial structure and having a positive dielectric anisotropy.
  • the present invention by using a liquid crystal composition containing an alignment control layer-forming monomer, it is possible to manufacture a liquid crystal display element which is difficult to peel even with a narrow frame.
  • a liquid crystal display element excellent in the transmittance characteristics and the contrast ratio can be realized by using the alignment control layer-forming monomer which is excellent in the solubility in the liquid crystal composition and is not colored.
  • the step of forming the alignment film is unnecessary, and the manufacturing cost of the liquid crystal display element can be reduced.
  • liquid crystal composition and “liquid crystal display element” may be abbreviated as “composition” and “element”, respectively.
  • “Liquid crystal display element” is a generic term for liquid crystal display panels and liquid crystal display modules.
  • the “liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase or a smectic phase and has no liquid crystal phase, but has a composition for the purpose of adjusting properties such as temperature range, viscosity and dielectric anisotropy of the nematic phase. It is a generic term for compounds mixed in a substance.
  • This compound has, for example, a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod like.
  • the "polymerizable compound” is a compound to be added for the purpose of forming a polymer in the composition. Liquid crystalline compounds having an alkenyl are 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, UV absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like are added to this composition as necessary. .
  • the proportion of the liquid crystal compound is represented by a weight percentage (% by weight) based on the weight of the liquid crystal composition without the additive even when the additive is added.
  • the proportion of the additive is expressed as a weight percentage (part by weight) based on the weight of the liquid crystal composition without the additive. That is, the proportions of the liquid crystal compound and the additive are calculated based on the total weight of the liquid crystal compound. Parts per million by weight (ppm) may be used.
  • the proportion of the polymerization initiator 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”.
  • the “lower limit temperature of the nematic phase” may be abbreviated as the “lower limit temperature”.
  • “High resistivity” means that the composition has high resistivity in the initial stage and has high resistivity after prolonged use.
  • the "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 at the initial stage, and after a long period of use, it has a large voltage not only at room temperature but near the upper temperature. It means having a retention rate. Aging test may be used to study the characteristics of the composition or device.
  • the expression "increase the dielectric anisotropy” means that in the case of a composition having a positive dielectric anisotropy, the value increases positively, and a composition having a negative dielectric anisotropy. In the case of goods, it means that the value increases negatively.
  • the compound represented by 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. In the expression “at least one 'A' may be replaced by 'B'”, when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is two Even in the case of three or more, their positions can be selected without limitation. This rule also applies to the expression "at least one 'A' 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-.
  • the symbol of terminal group R 1 was used for a plurality of compounds.
  • two groups represented by any two R 1 may be identical or different.
  • R 1 of compound (1-1) is ethyl and R 1 of compound (1-2) is ethyl.
  • R 1 of the compound (1-1) is ethyl and R 1 of the compound (1-2) is propyl.
  • This rule also applies to symbols such as other end groups.
  • the index 'a' is 2
  • two rings A are present.
  • two rings represented by two rings A may be identical or different.
  • This rule also applies to any two rings A when the index 'a' is greater than two.
  • 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 6-membered ring and fused ring.
  • diagonal lines crossing one side of the hexagon indicate that any hydrogen on the ring may be replaced by a group such as -Sp 1 -P 1 .
  • a subscript such as 'e' indicates the number of groups replaced. There is no such substitution when the subscript 'e' is 0 (zero). When the subscript 'e' is 2 or more, a plurality of -Sp 1 -P 1 exists on the ring F 3 . Plural groups represented by -Sp 1 -P 1 may be identical or different.
  • 2-fluoro-1,4-phenylene means the following two divalent groups.
  • fluorine may be leftward (L) or rightward (R).
  • L leftward
  • R rightward
  • This rule also applies to asymmetric bivalent groups generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl.
  • divalent linking groups such as carbonyloxy (-COO- or -OCO-).
  • the alkyl of the liquid crystal compound is linear or branched and does not contain cyclic alkyl. Linear alkyls are preferred over branched alkyls. The same is true for end groups such as alkoxy and alkenyl.
  • the configuration of 1,4-cyclohexylene is preferably trans rather than cis in order to increase the maximum temperature.
  • the present invention includes the following items.
  • a liquid crystal layer is sandwiched between a pair of substrates which are disposed opposite to each other and pasted through a sealing agent, An alignment control layer for controlling the alignment of liquid crystal molecules is provided between the pair of substrates and the liquid crystal layer,
  • the orientation control layer contains at least one compound selected from the group of compounds represented by formulas (A) to (D) as a first additive, and a liquid crystal compound.
  • the liquid crystal display element which consists of a polymer produced
  • P 10 , P 20 , P 30 and P 40 are independently selected from groups represented by formulas (Q-1) to (Q-5) Is the basis;
  • M 10 , M 20 and M 30 independently represent hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine
  • C 1 -C 5 alkyl substituted with Sp 10 , Sp 20 and Sp 40 independently represent a single bond or alkylene having 1 to 12 carbon atoms, and at least one hydrogen of this alkylene is replaced by fluorine, chlorine or the formula (Q-6)
  • at least one -CH 2 - may be replaced by -O-, -CO-, -COO-, or -OCO-
  • Ring A 40 is 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-2,5-diyl, pyrimidine-2,5-diyl, pyridine 2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta [a] phenanthrene-3,17-diyl, or 2,3, 4,7,8,9,10,11,12,13,14,15,16,
  • k 10 and n 10 are independently an integer of 0 to 3, and the sum of k 10 and n 10 is an integer of 1 to 6;
  • n 20 is 1 or 2;
  • n 30 is 1 or 2;
  • Item 2 The liquid crystal composition according to item 1, wherein the alignment control layer-forming monomer in the liquid crystal composition is Formula (A-1), Formula (A-2), Formula (B), Formula (C-1) and Formula (D-1) Liquid crystal display device.
  • P 10 , P 20 , P 30 , P 40 , P 50 and P 60 are independently a group selected from the group represented by formula (Q-1);
  • M 10 , M 20 and M 30 are independently hydrogen, fluorine, methyl or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced by fluorine;
  • Sp 10 , Sp 20 and Sp 40 independently represent a single bond or alkylene having 1 to 12 carbon atoms, and at least one hydrogen of this alkylene may be replaced by fluorine or the formula (Q-6)
  • At least one -CH 2 - may be replaced by -O-, -CO-, -COO-, or
  • the alignment control layer forming monomer in the liquid crystal composition is represented by formula (A-1), formula (A-2) or formula (B), and P 10 , P 20 , P 30 , P 40 , P 50 and P 60 are Independently a group selected from the group represented by formula (Q-1);
  • M 10 , M 20 and M 30 are independently hydrogen, fluorine, methyl or trifluoromethyl;
  • Sp 10 and Sp 20 are independently a single bond or alkylene having 1 to 12 carbons, and at least one hydrogen of this alkylene may be replaced by fluorine or the formula (Q-6), and at least one of -CH 2 -may be replaced by -O-, -CO-, -COO-, or -OCO-;
  • M 10 , M 20 and M 30 independently represent hydrogen, fluorine, methyl or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced by fluorine;
  • Sp 41 is independently a single bond or alkylene having 1 to
  • Item 4 The liquid crystal display according to any one of items 1 to 3, wherein the proportion of the monomer for forming an alignment control layer in the liquid crystal composition is in the range of 0.1 parts by weight to 10 parts by weight based on the total amount of liquid crystal compounds. element.
  • Item 5 The liquid crystal display element according to any one of items 1 to 4, containing at least one compound selected from the group of compounds represented by formula (1) as a first component.
  • R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons;
  • 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
  • X 1 and X 2 are each independently hydrogen or fluorine;
  • Item 6 The liquid crystal display according to any one of items 1 to 5, containing at least one compound selected from the group of compounds represented by formulas (1-1) to (1-39) as a first component element.
  • R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons.
  • Item 7. The liquid crystal display element according to item 5 or 6, wherein the proportion of the first component in the liquid crystal composition is in the range of 10% by weight to 85% by weight.
  • Item 8. The liquid crystal display element according to any one of items 1 to 7, containing at least one compound selected from the group of compounds represented by formula (2) as a second component.
  • R 2 and R 3 independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen is fluorine or chlorine
  • Ring B and Ring C are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5 substituted alkenyl having 2 to 12 carbon atoms; - be-difluoro-1,4-phenylene;
  • Z 2 is a single bond, ethylene or carbonyloxy,;
  • b is 1, 2 or 3.
  • Item 9. Liquid crystal display according to any one of items 1 to 8, comprising at least one compound selected from the group of compounds represented by formula (2-1) to formula (2-13) as a second component: element.
  • R 2 and R 3 independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or It is alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.
  • Item 10 The liquid crystal display element according to item 8 or 9, wherein the proportion of the second component in the liquid crystal composition is in the range of 10% by weight to 85% by weight.
  • Item 11. The liquid crystal display element according to any one of items 1 to 10, containing at least one compound selected from the group of compounds represented by formula (3) as a third component.
  • R 4 and R 5 independently represent 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, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, 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 - be difluorochroman-2,6-diyl;
  • Item 12. The liquid crystal display according to any one of items 1 to 11, containing at least one compound selected from the group of compounds represented by formula (3-1) to formula (3-22) as a third component: element.
  • R 4 and R 5 independently represent 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 carbons.
  • Item 13 The liquid crystal display element according to item 11 or 12, wherein the proportion of the third component is in the range of 3% by weight to 25% by weight.
  • Item 14 The liquid crystal display according to any one of items 1 to 13, wherein the liquid crystal composition further contains at least one compound selected from the group of polymerizable compounds represented by Formula (4) as a second additive element.
  • ring F 3 and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine -2-yl or pyridin-2-yl in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen May be replaced by C 1-12 alkyl substituted with fluorine or chlorine;
  • ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1 , 2-Diy
  • P 1 , P 2 and P 3 are independently selected from the group of polymerizable groups represented by Formula (P-1) to Formula (P-5) Item 15.
  • M 1 , M 2 and M 3 independently represent hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine And C 1 -C 5 alkyl substituted by
  • Item 16. Any one of items 1 to 15, which comprises at least one compound selected from the group of polymerizable compounds represented by formula (4-1) to formula (4-27) as a second additive in a liquid crystal composition
  • the liquid crystal display element as described in 1 or 2.
  • P 4 , P 5 and P 6 independently represent each of the polymerizable groups represented by formulas (P-1) to (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.
  • Item 17 The liquid crystal display device according to any one of items 14 to 16, wherein the proportion of the second additive in the liquid crystal composition is in the range of 0.03 to 10 parts by weight based on the total amount of liquid crystal compounds .
  • the upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy (measured at 25 ° C.) at a wavelength of 589 nm is 0.07 or more, and the dielectric anisotropy (measured at 25 ° C.) at a frequency of 1 kHz is 2 Item 18.
  • the liquid crystal display element according to any one of items 1 to 17, which is the above.
  • Item 19 The liquid crystal composition according to any one of items 1 to 18 and an electrode between a pair of substrates, and irradiating linearly polarized light at or above the upper limit temperature of the nematic phase, The liquid crystal display element which the orientation control layer formation monomer in the said liquid crystal composition reacted.
  • Item 20 The liquid crystal display according to any one of items 1 to 19, wherein an operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and a driving method of the liquid crystal display element is an active matrix method. element.
  • Item 22 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 1 to 17 and in which a polymerizable compound in the liquid crystal composition is polymerized.
  • Item 23 Item 18. Use of the liquid crystal composition in the liquid crystal display element according to any one of items 1 to 17 in a liquid crystal display element.
  • Item 24 Use of the liquid crystal composition in the liquid crystal display device according to any one of items 1 to 17 in a polymer supported alignment type liquid crystal display device.
  • Item 25 The compound represented by Formula (A-2).
  • P 50 and P 60 independently represent a group selected from the group represented by formula (Q-1);
  • M 10 , M 20 and M 30 are independently hydrogen, fluorine, methyl or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced by fluorine;
  • Sp 50 and Sp 60 are independently alkylene having 1 to 12 carbon atoms, and at least one hydrogen of this alkylene may be replaced by fluorine or the formula (Q-6), and at least one —CH 2 - May be replaced by -O-, -CO-, -COO-, or -OCO-;
  • M 10 , M 20 and M 30 independently represent hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or 1 carbon having at least one hydrogen replaced with fluorine or chlorine From 5 to 5 alkyl;
  • Sp 41 is independently a single bond or alkylene having 1 to 12 carbon atoms, and at least one
  • Item 26 Item 26. Use of the compound according to item 25 as a monomer for forming an orientation control layer.
  • Item 27 Item 18. A liquid crystal composition in a liquid crystal display element according to any one of items 1 to 17.
  • the present invention also includes the following items.
  • the above composition further containing at least one of additives such as an optically active compound, an antioxidant, an ultraviolet light absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound object.
  • additives such as an optically active compound, an antioxidant, an ultraviolet light absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound object.
  • AM element containing the above composition containing the above composition.
  • a polymer supported orientation (PSA) type AM element containing the above composition further containing a polymerizable compound.
  • (E) A device containing the composition described above and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA.
  • (F) A transmission type 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 control layer forming monomer contained in the liquid crystal composition used for the liquid crystal display element of this invention is demonstrated.
  • the orientation control layer-forming monomer means a compound that absorbs polarized light and causes a reaction such as dimerization or isomerization, and in the present invention, the formula (A), the formula (A-1), the formula (A-2)
  • the compounds represented by Formula (B), Formula (C), Formula (C-1), Formula (D) and Formula (D-1) are used.
  • P 10 , P 20 , P 30 , P 40 , P 50 and P 60 independently represent a group selected from the groups represented by formulas (Q-1) to (Q-5),
  • M 10 , M 20 and M 30 independently represent hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine And C 1 -C 5 alkyl substituted by Preferably, it is a formula (Q-1), and M 10 , M 20 and M 30 are independently hydrogen, fluorine, methyl or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced by fluorine is there.
  • M 10 , M 20 and M 30 are independently hydrogen, fluorine, methyl or trifluoromethyl.
  • Sp 10 , Sp 20 and Sp 40 independently represent a single bond or alkylene having 1 to 12 carbon atoms, and at least one hydrogen of this alkylene is replaced by fluorine, chlorine or the formula (Q-6) Also, at least one -CH 2- may be replaced by -O-, -CO-, -COO-, or -OCO-.
  • it is a single bond or an alkylene having 1 to 12 carbon atoms, and at least one hydrogen of this alkylene may be replaced by fluorine, and at least one —CH 2 — is —O—, —CO— , -COO-, or -OCO- may be substituted.
  • More preferred Sp 40 is a single bond.
  • Sp 30 is independently a single bond or alkylene having 1 to 12 carbon atoms, and at least one hydrogen of this alkylene may be replaced by fluorine, chlorine or the formula (Q-6), and at least one — CH 2- may be replaced by -O-, -CO-, -COO-, or -OCO-.
  • M 10 , M 20 and M 30 independently represent hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or 1 carbon having at least one hydrogen replaced with fluorine or chlorine To 5 alkyl.
  • Sp 41 is independently a single bond or alkylene having 1 to 12 carbon atoms, and at least one hydrogen of this alkylene may be replaced by fluorine or chlorine, and at least one —CH 2 — is —O -, -CO-, -COO-, or -OCO- may be substituted.
  • Sp 50 and Sp 60 are independently alkylene having 1 to 12 carbon atoms, and at least one hydrogen of this alkylene may be replaced by fluorine, chlorine or the formula (Q-6), and at least one — CH 2- may be replaced by -O-, -CO-, -COO-, or -OCO-.
  • it is an alkylene having 2 to 12 carbon atoms, and at least one hydrogen of this alkylene may be replaced by fluorine, chlorine or the formula (Q-6), and at least one —CH 2 — is —O— , -CO-, -COO-, or -OCO- may be substituted.
  • Ring A 10 and ring A 20 are independently phenyl, 4-biphenyl, 1-naphthyl, 2-naphthyl, pyrimidin-2-yl, pyrimidin-5-yl, pyridin-2-yl, pyridin-5-yl, Fluoren-2-yl, fluoren-3-yl, phenanthren-2-yl, or anthracene-2-yl, in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbon atoms, It may be substituted by alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons, or alkenyloxy having 2 to 11 carbons, and in these groups, at least one hydrogen is replaced by fluorine or chlorine It is also good.
  • Ring A 11 , ring A 21 , ring A 12 , ring A 22 and ring A 30 are 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-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perthene Hydrocyclopenta [a] phenanthrene-3,17-diyl or 2,3,4,
  • Ring A 40 is 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-2,5-diyl, pyrimidine-2,5-diyl, pyridine 2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta [a] phenanthrene-3,17-diyl, or 2,3, 4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopent
  • Ring A 11 and ring A 21 are independently 1,4-phenylene and naphthalene-2,6-diyl, in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, or at least One hydrogen may be replaced by C 1-12 alkyl substituted with fluorine.
  • R 10 and R 20 independently represent hydrogen, fluorine, cyano, alkyl having 1 to 10 carbons, or alkyl having 1 to 10 carbons in which at least one hydrogen is replaced by fluorine .
  • Preferred is a single bond, ethylene, methyleneoxy, -COO-, -OCO-, or -OCOO-, and more preferred is a single bond, -COO- or -OCO-.
  • Z 12 is -CO- or -OCO-.
  • Z 20 and Z 21 are independently a single bond, alkylene having 1 to 6 carbons or alkenylene having 2 to 6 carbons, but at least one is alkenylene having 2 to 6 carbons.
  • R 30 , R 40 , R 41 and R 50 are independently hydrogen, fluorine, chlorine, alkyl having 1 to 10 carbons, or alkyl having 1 to 10 carbons in which at least one hydrogen is replaced by fluorine .
  • k 10 and n 10 are independently an integer of 0 to 3, and the sum of k 10 and n 10 is an integer of 1 to 6, and preferably, the sum of k 10 and n 10 is an integer of 1 to 4 is there.
  • n 20 is 1 or 2;
  • n 30 is 1 or 2;
  • the irradiation of ultraviolet light causes the photoisomerization from a trans form to a cis form and formation of a cyclobutane ring due to dimerization when the monomer for forming an orientation control layer having a vinylene group is irradiated.
  • This property can be used to prepare a thin film capable of aligning liquid crystal molecules.
  • the ultraviolet light to be irradiated is suitably linear polarized light.
  • an alignment control layer-forming monomer 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 alignment control layer-forming monomer. This composition is injected into an element not having an alignment film.
  • the device is irradiated with linearly polarized light while warming the device to the upper temperature limit of the nematic phase to promote photoisomerization and dimerization of the orientation control layer-forming monomer.
  • the photoisomerized compounds and the dimerized compounds are arranged in a certain direction.
  • photopolymerization also occurs to form a thin film on the substrate.
  • the formed thin film has a function as a liquid crystal alignment film.
  • compositions used in the present invention will be described in the following order. First, the composition of the composition will be described. Second, the main properties of the component compounds and the main effects of the compounds on the composition and the device are explained. Third, the combination of components in the composition, the preferred ratio of the components and the basis thereof will be described. Fourth, the preferred embodiments of the component compounds are described. Fifth, preferred component compounds are shown. Sixth, additives that may be added to the composition will be described. Seventh, the synthesis methods of the component compounds will be described. Eighth, the application of the composition will be described. Ninth, a method of manufacturing a device will be described.
  • composition of the composition contains a plurality of liquid crystal compounds.
  • the composition may contain an additive.
  • the additive is an optically active compound, an antioxidant, an ultraviolet light absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, a polar compound and the like.
  • This composition is classified into the composition A and the composition B from the viewpoint of the liquid crystal compound.
  • Composition A may further contain other liquid crystal compounds in addition to the liquid crystal compound selected from compound (1) and 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 substantially consists only of the liquid crystal compound selected from the compound (1) and the compound (2).
  • the term "substantially” means that the composition may contain additives but does not contain other liquid crystal compounds.
  • Composition B has a smaller number of components than composition A.
  • Composition B is preferable to composition A in terms of cost reduction.
  • Composition A is preferable to composition B from the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds.
  • the main properties of the component compounds and the main effects of the compounds on the composition and the device are explained.
  • the main properties of the component compounds are summarized in Table 2 based on the effects of the present invention.
  • L means large or high, M medium, and S small or low.
  • L, M and S are classifications based on qualitative comparisons between component compounds, and the symbol 0 (zero) means that the dielectric anisotropy is extremely small.
  • the orientation control layer forming monomer is a first additive.
  • the alignment control layer-forming monomers are aligned at a molecular level in a uniform direction when dimerization or isomerization is performed by polarization. Therefore, the thin film prepared from the alignment control layer forming monomer aligns liquid crystal molecules in the same manner as an alignment film such as polyimide.
  • the compound (1) which is the first component raises the dielectric anisotropy.
  • the second component, compound (2) lowers the viscosity or raises the upper limit temperature.
  • the third component, compound (3) raises the dielectric constant in the minor axis direction.
  • the second additive, compound (4) gives a polymer by polymerization, which shortens the response time of the device and improves the image sticking.
  • the preferred proportion of the first additive, the alignment control layer-forming monomer is about 0.1 parts by weight or more based on the total amount of the liquid crystal compound to align the liquid crystal molecules, and to prevent display defects of the device. It is 10 parts by weight or less. A further preferred ratio is in the range of about 0.3 parts by weight to about 6 parts by weight. An especially desirable ratio is in the range of about 0.5 parts by weight to about 4 parts by weight.
  • the preferred proportion of the first component is about 10% by weight or more to raise the dielectric anisotropy, and about 85% by weight or less to lower the lower limit temperature or to lower the viscosity.
  • a further preferred ratio is in the range of about 15% by weight to about 80% by weight.
  • An especially desirable ratio is in the range of about 20% by weight to about 75% by weight.
  • the preferred proportion of the second component is about 10% by weight or more to raise the upper limit temperature or to lower the viscosity, and about 85% by weight or less to raise the dielectric anisotropy.
  • a further preferred ratio is in the range of about 15% by weight to about 80% by weight.
  • An especially desirable ratio is in the range of about 20% by weight to about 75% by weight.
  • the preferred proportion of the third component is about 3% by weight or more to increase the dielectric constant in the minor axis direction, and about 25% by weight or less to reduce the lower limit temperature.
  • a further preferred ratio is in the range of about 5% by weight to about 20% by weight.
  • An especially desirable ratio is in the range of about 5% by weight to about 15% by weight.
  • the second additive is added to the composition for the purpose of being adapted to a polymer-supported oriented device.
  • the preferred proportion of this additive is about 0.03 parts by weight or more based on the total amount of liquid crystal compounds in order to align liquid crystal molecules, and about 10 parts by weight or less in order to prevent display defects of the device.
  • a further preferred ratio is in the range of about 0.1 parts by weight to about 2 parts by weight.
  • An especially desirable ratio is in the range of about 0.2 parts by weight to about 1.0 parts 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 in order to increase the stability to ultraviolet light or heat.
  • R 2 and R 3 independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 carbons in which at least one hydrogen is replaced by fluorine or chlorine To 12 alkenyls.
  • Desirable R 2 or R 3 is alkenyl having 2 to 12 carbons to lower the viscosity, and alkyl having 1 to 12 carbons to increase 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 to increase the stability to ultraviolet light or heat, and alkoxy having 1 to 12 carbons to increase the dielectric constant in the short axis direction.
  • Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More preferred alkyl is methyl, ethyl, propyl, butyl or pentyl to lower the viscosity.
  • Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. More preferred alkoxy is methoxy or ethoxy to lower 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 preferred alkenyl is vinyl, 1-propenyl, 3-butenyl or 3-pentenyl to reduce viscosity.
  • Trans is preferable in the alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity and the like.
  • Cis is preferred for alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl.
  • linear alkenyls are preferable to branched ones.
  • Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy or 4-pentenyloxy. More preferred alkenyloxy is allyloxy or 3-butenyloxy to lower the viscosity.
  • Preferred examples of the 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 to increase the dielectric anisotropy.
  • Preferred examples of the 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.
  • Preferred ring A is 1,4-phenylene or 2-fluoro-1,4-phenylene to increase the optical anisotropy. Tetrahydropyran-2,5-diyl is Or And preferably It is.
  • Ring B and ring C are each 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 to reduce viscosity, or 1,4-phenylene to increase 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 in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen It is chroman-2,6-diyl substituted with fluorine or chlorine.
  • the preferred ring D or ring F is 1,4-cyclohexylene to lower the viscosity, tetrahydropyran-2,5-diyl to increase the dielectric constant in the short axis direction, and to increase the optical anisotropy And 1,4-phenylene.
  • Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,4, 5-trifluoronaphthalene-2,6-diyl or 7,8-difluorochroman-2,6-diyl.
  • Preferred ring E is 2,3-difluoro-1,4-phenylene to increase 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 to lower the viscosity, and difluoromethyleneoxy to raise the dielectric anisotropy.
  • Z 2 is a single bond, ethylene or carbonyloxy. Preferred Z 2 is a single bond to lower 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 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 dielectric anisotropy.
  • Y 1 represents fluorine, chlorine, an alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, an alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or It is C2-C12 alkenyloxy in which one hydrogen is replaced by fluorine or chlorine. Desirable Y 1 is fluorine to lower the lower limit temperature.
  • alkyl in which at least one hydrogen is replaced by fluorine or chlorine is trifluoromethyl.
  • alkoxy in which at least one hydrogen is replaced by fluorine or chlorine is trifluoromethoxy.
  • alkenyloxy in which at least one hydrogen is replaced by fluorine or chlorine is trifluorovinyloxy.
  • a is 1, 2, 3 or 4; Desirable a is 2 to lower the lower limit temperature, and 3 to increase the dielectric anisotropy.
  • b is 1, 2 or 3; Preferred b is 1 to lower the viscosity and 2 or 3 to raise the upper temperature limit.
  • 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 to lower the viscosity and 2 or 3 to raise the upper temperature limit. Desirable d is 0 to lower the viscosity and 1 to lower the lower limit 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 groups represented by formula (P-1) to formula (P-5). Further preferable P 1 , P 2 or P 3 is a group represented by formula (P-1), formula (P-2) or 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 formula (P-1).
  • the wavy lines in formulas (P-1) to (P-5) indicate the binding site.
  • M 1 , M 2 and M 3 independently represent hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine
  • C 1 -C 5 alkyl substituted by Preferred M 1 , M 2 or M 3 is hydrogen or methyl to increase the reactivity.
  • Further preferred M 1 is hydrogen or methyl
  • further preferred M 2 or M 3 is hydrogen.
  • Ring F 3 and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl, or Pyridin-2-yl, in which ring 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 It may be substituted by alkyl having 1 to 12 carbon atoms.
  • Preferred ring F 3 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, in these rings, At least one hydrogen is fluor
  • Preferred Z 6 or Z 7 is a single bond, -CH 2 -CH 2- , -CH 2 O-, -OCH 2- , -COO-, or -OCO-. Further preferred Z 6 or Z 7 is a single bond.
  • H is 0, 1 or 2; Preferred h is 0 or 1.
  • e, f and g are 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 preferred orientation control layer-forming monomer preferably has at least two or more polymerizable groups.
  • the alignment control layer obtained after polymerization is considered to be a flexible film, so the alignment control layer is easily deformed in the temperature environment for driving the liquid crystal display element, and the alignment control force is also easily reduced.
  • Become When at least two or more polymerizable groups are present, it is believed that the crosslinking density of the orientation control layer obtained after polymerization is increased and a strong film is formed, so that deformation of the orientation control layer is considered to be difficult to occur even in high temperature environments.
  • the site which causes dimerization or isomerization by polarization is a vinylene group. Even in the case of having a chalcone structure or a cinnamate structure containing a vinylene group, the same effect is preferable.
  • a spacer may be introduced between the polymerizable group and the central 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.
  • Two or more types of orientation control layer-forming monomers may be used in combination. The preferred orientation control layer-forming monomers are specifically exemplified.
  • Compound (A-1-4) to Compound (A- 1-7), Compound (A-A-5), Compound (A-A-7), Compound (A-2-1) to Compound (A-2) -2), n in the compound (A-2-7) to the compound (A-2-12) is independently 2 to 12.
  • n is 2 to 10.
  • the preferred compound (1) is the compound (1-1) to the compound (1-39) described in item 6.
  • at least one of the first components is a compound (1-4), a compound (1-12), a compound (1-14), a compound (1-15), a compound (1-17), a compound (1 1-18), compound (1-23), compound (1-24), compound (1-27), compound (1-29), or compound (1-30).
  • At least two of the first components are a compound (1-12) and a compound (1-15), a compound (1-14) and a compound (1-27), a compound (1-18) and a compound (1-24),
  • the combination of Compound (1-18) and Compound (1-29), Compound (1-24) and Compound (1-29), or Compound (1-29) and Compound (1-30) is preferred.
  • the preferred compound (2) is the compound (2-1) to the compound (2-13) described in item 9.
  • at least one of the second components is a compound (2-1), a compound (2-3), a compound (2-5), a compound (2-6), or a compound (2-7) Is preferred.
  • At least two of the second components are the compound (2-1) and the compound (2-5), the compound (2-1) and the compound (2-6), the compound (2-1) and the compound (2-7), the compound The combination of (2-3) and the compound (2-5), the compound (2-3) and the compound (2-6), the compound (2-3) and the compound (2-7) is preferred.
  • the preferred compound (3) is the compound (3-1) to the compound (3-22) described in Item 12.
  • at least one of the third components is a compound (3-1), a compound (3-3), a compound (3-4), a compound (3-6), a compound (3-8), or a compound (3-10) is preferred.
  • At least two of the third components are the compound (3-1) and the compound (3-6), the compound (3-3) and the compound (3-6), the compound (3-3) and the compound (3-10), The combination of Compound (3-4) and Compound (3-6), Compound (3-4) and Compound (3-8), or Compound (3-6) and Compound (3-10) is preferred.
  • additives that may be added to the composition will be described.
  • Such additives include optically active compounds, antioxidants, ultraviolet light 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 compounds are compound (Op-1) to compound (Op-5).
  • the preferred proportion of the optically active compound is about 5 parts by weight or less based on the total amount of liquid crystal compounds.
  • a further preferred ratio is in the range of about 0.01 parts by weight to about 2 parts by weight.
  • Is added to the Preferred examples of the antioxidant are compounds (G) in which n is an integer of 1 to 9, and the like.
  • n 1, 3, 5, 7 or 9. More preferably, n is 7. Since the compound (G) in which n is 7 has low volatility, it is effective to maintain 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.
  • the preferred proportion of the antioxidant is about 50 ppm or more to obtain its effect, and is about 600 ppm or less so as not to lower the upper temperature limit or to raise the lower temperature limit.
  • a further preferred ratio is in the range of about 100 ppm to about 300 ppm.
  • UV absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like.
  • light stabilizers such as sterically hindered amines.
  • the preferred proportion of these absorbents and stabilizers is about 50 ppm or more to obtain the effect, and about 10000 ppm or less so as not to lower the upper temperature limit or to raise the lower temperature limit.
  • a further preferred ratio is in the range of about 100 ppm to about 10000 ppm.
  • a dichroic dye such as an azo dye or an anthraquinone dye is added to the composition.
  • the preferred proportion of dye is in the range of about 0.01 parts by weight to about 10 parts by weight, based on the total amount of liquid crystal compounds.
  • an antifoam agent such as dimethyl silicone oil, methylphenyl silicone oil or the like is added to the composition.
  • the preferable proportion of the antifoaming agent is about 1 ppm or more in order to obtain the effect, and is about 1000 ppm or less in order to prevent display defects.
  • a further preferred ratio is in the range of about 1 ppm to about 500 ppm.
  • Polymerizable compounds are used to make them compatible with polymer-supported oriented (PSA) type devices.
  • Compound (4) is suitable for this purpose. Along with the compound (4), a polymerizable compound different from the compound (4) may be added to the composition. Instead of the compound (4), a polymerizable compound different from the compound (4) may be added to the composition.
  • Preferred examples of such polymerizable compounds are compounds such as acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes) and vinyl ketones. Further preferred examples are derivatives of acrylate or methacrylate.
  • the reactivity of the polymerizable compound and the pretilt angle of the liquid crystal molecule can be adjusted by changing the type of the compound (4) or by combining the polymerizable compound different from the compound (4) in an appropriate ratio. .
  • By optimizing the pretilt angle short response times of the device can be achieved. Since the alignment of liquid crystal molecules is stabilized, a large contrast ratio and a long lifetime can be achieved.
  • a polymerizable compound such as a compound (4) or an orientation control layer forming monomer is polymerized by ultraviolet irradiation. It may be polymerized in the presence of a suitable initiator such as a photoinitiator. Appropriate conditions for polymerization, appropriate types of initiators, and appropriate amounts are known to the person skilled in the art and are described in the literature.
  • the photopolymerization initiator Omnirad 651 registered trademark; IGM Resins
  • Omnirad 184 registered trademark; IGM Resins
  • Omnirad 1173 registered trademark; IGM Resins
  • the preferred proportion of the photoinitiator is in the range of about 0.1 parts by weight to about 5 parts by weight based on the total amount of polymerizable compounds. A further preferred ratio is in the range of about 1 part by weight to about 3 parts by weight.
  • a polymerization inhibitor When storing a polymerizable compound such as a compound (4) or a monomer for forming an orientation control layer, a polymerization inhibitor may be added to prevent polymerization.
  • the polymerizable compound is usually added to the composition without removing the polymerization inhibitor.
  • polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butyl catechol, 4-methoxyphenol, phenothiazine and the like.
  • Polar compounds are organic compounds with polarity.
  • compounds having an ionic bond are not included. Atoms such as oxygen, sulfur and nitrogen are more electronegative and tend to have a partial negative charge. Carbon and hydrogen tend to be neutral or have a partial positive charge.
  • Polarity results from the inhomogeneous distribution of partial charges among different types of atoms in the compound.
  • the polar compound has at least one of partial structures such as -OH, -COOH, -SH, -NH 2 ,>NH,> N-.
  • Alignment control layer forming monomers having a vinylene group are disclosed in WO 2013/077343, WO 2002/048281, WO 2015/004947, US Publication 2013-0277609, JP-A-63-8361. It synthesize
  • An alignment control layer-forming monomer having an ⁇ -fluoroacrylate group is synthesized by the method described in JP-A-2005-112850.
  • compositions are prepared from the compounds thus obtained by known methods. For example, the component compounds are mixed and dissolved together by heating.
  • compositions have a lower temperature limit of about -10.degree. C. or lower, an upper temperature limit of about 70.degree. 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 proportions of the component compounds, or by mixing other liquid crystal compounds. Additionally, compositions having optical anisotropy in the range of about 0.10 to about 0.30 may be prepared by this method. Devices containing this composition have a large voltage holding ratio.
  • This composition is suitable for an AM device.
  • This composition is particularly suitable for transmissive AM devices.
  • This composition can be used as a composition having a nematic phase, or as an optically active composition by adding an optically active compound.
  • This composition can be used for an AM device. Furthermore, the use to PM element is also possible.
  • This composition can be used for AM devices and PM devices having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA.
  • the use for AM devices having VA, OCB, IPS mode or FFS mode is particularly preferred.
  • the alignment of liquid crystal molecules may be parallel to or perpendicular to the glass substrate.
  • These elements may be reflective, transmissive or semi-transmissive. Its use for transmission type devices is preferred.
  • the use for amorphous silicon-TFT elements or polycrystalline silicon-TFT elements is also possible.
  • the composition can be used for an element of NCAP (nematic curvilinear aligned phase) type prepared by microencapsulation or a element of PD (polymer dispersed) type in which a three-dimensional network polymer is formed in the composition.
  • the first is a step of adding an alignment control layer-forming monomer to the liquid crystal composition and heating the composition to a temperature higher than the upper limit temperature to dissolve it.
  • the second is a step of injecting the composition into a liquid crystal display element. In this step, when the liquid crystal composition is heated and injected at a temperature higher than the upper limit temperature, shear stress can be reduced when the liquid crystal composition flows in the cell, and the generation of alignment defects can be easily prevented.
  • the third is a step of irradiating linearly polarized ultraviolet light while heating the liquid crystal composition to a temperature higher than the upper limit temperature.
  • the alignment control layer-forming monomer is dimerized or isomerized by linearly polarized ultraviolet light, and at the same time polymerization also proceeds.
  • the preferable integrated light quantity (J / cm 2 ) of linearly polarized ultraviolet light is 0.1 to 20 J / cm 2 at the time of reaching 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 determined by the illuminance of ultraviolet light (unit: mW / cm 2 ) ⁇ irradiation time (unit: sec).
  • the temperature conditions at the time of linearly polarized ultraviolet irradiation be set in the same manner as the above heat treatment temperature. Since the time of linearly polarized ultraviolet irradiation is calculated from the lamp illuminance, it is preferable to perform with the highest possible illuminance from the viewpoint of production efficiency.
  • the polymer composed of this alignment control layer-forming monomer is aligned in a fixed direction at the molecular level and immobilized on the substrate, so the thin film has a function as a liquid crystal alignment film. By this method, a liquid crystal display device having no alignment film such as polyimide can be manufactured.
  • the present invention comprises a mixture of the composition of Example 1 and the composition of Example 2.
  • the present invention also includes a mixture of at least two of the compositions of the Examples.
  • the compound synthesized was identified by a method such as NMR analysis. The properties of the compounds, compositions and devices were measured by the methods described below.
  • NMR analysis For measurement, DRX-500 manufactured by Bruker Biospin Ltd. was used. In the measurement of 1 H-NMR, the sample was dissolved in a deuterated solvent such as CDCl 3, and the measurement was performed at room temperature under conditions of 500 MHz and 16 integrations. Tetramethylsilane was used as an internal standard. In the 19 F-NMR measurement, CFCl 3 was used as an internal standard, and the integration was performed 24 times. In the description of nuclear magnetic resonance spectrum, s is singlet, d is doublet, t is triplet, q is quartet, quin is quintet, sex is sextet, m is multiplet, br is broad.
  • a GC-14B gas chromatograph made 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 columns DB-1 length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m; fixed liquid phase is dimethylpolysiloxane; nonpolar
  • the column was kept at 200 ° C. for 2 minutes and then heated to 280 ° C. at a rate of 5 ° C./minute.
  • the 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 Model C-R5A Chromatopac manufactured by Shimadzu Corporation, or its equivalent.
  • the obtained gas chromatogram showed the retention time of the peak corresponding to the component compound and the area of the peak.
  • capillary column As a solvent for diluting the sample, chloroform, hexane or the like may be used.
  • the following capillary column may be used to separate the component compounds.
  • HP-1 (30 m in length, 0.32 mm in diameter, 0.25 ⁇ m in thickness) manufactured by Agilent Technologies Inc.
  • Rtx-1 (30 m in length, 0.32 mm in inside diameter, 0.25 ⁇ m in film thickness) manufactured by Restek Corporation
  • BP-1 (30 m in length, 0.32 mm in inner diameter, 0.25 ⁇ m in film thickness) manufactured by SGE International Pty. Ltd.
  • a capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 ⁇ m) manufactured by Shimadzu Corporation may be used for the purpose of preventing overlapping of compound peaks.
  • the proportion of the liquid crystal compound contained in the composition may be calculated by the following method.
  • the mixture of liquid crystal compounds is detected by gas chromatography (FID).
  • the area ratio of peaks in the gas chromatogram corresponds to the ratio (weight ratio) of the liquid crystalline compound.
  • 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 area ratio of the peaks.
  • 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 the base liquid crystal (85% by weight). The characteristic values of the compound were calculated by extrapolation from the values obtained by the measurement.
  • (Extrapolated value) ⁇ (measured value of sample) ⁇ 0.85 ⁇ (measured value of mother liquid crystal) ⁇ / 0.15.
  • the proportion of the compound and the base liquid crystal is 10 wt%: 90 wt%, 5 wt%: 95 wt%, 1 wt%: 99 wt% changed.
  • the values of the upper limit temperature, the optical anisotropy, the viscosity, and the dielectric anisotropy of the compound were determined by this extrapolation method.
  • Measurement method The measurement of the characteristics was performed by the following method. Many of these are modified methods or methods described in the JEITA standard (JEITA ED-2521B), which is deliberately established by the Japan Electronics and Information Technology Industries Association (hereinafter referred to as JEITA). It was a method. A thin film transistor (TFT) was not attached to the TN device used for the measurement.
  • TFT thin film transistor
  • Upper limit temperature of nematic phase (NI; ° C.): The sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarization microscope and heated at a rate of 1 ° C./min. The temperature was measured when part of the sample changed from the nematic phase to the isotropic liquid.
  • the upper limit temperature of the nematic phase may be abbreviated as "upper limit temperature”.
  • T C Lower limit temperature of nematic phase
  • a sample having a nematic phase is placed in a glass bottle and kept for 10 days in a freezer at 0 ° C., -10 ° C., -20 ° C., -30 ° C. and -40 ° C. After storage, the liquid crystal phase was observed. For example, the sample remained in the -20 ° C. in a nematic phase, when changed to -30 ° C. At crystals or a smectic phase 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
  • E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used.
  • Viscosity (rotational viscosity; ⁇ 1; measured at 25 ° C .; mPa ⁇ s): Measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995) I obeyed. The sample was placed in a TN device having a twist angle of 0 ° and a distance between two glass substrates (cell gap) of 5 ⁇ m. The device was applied stepwise in steps of 0.5 V in the range of 16 V to 19.5 V. After 0.2 seconds of no application, application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds).
  • the peak current and peak time of transient current generated by this application were measured.
  • the rotational viscosity value was obtained from these measured values and the formula (8) described on page 40 in the article of M. Imai et al.
  • the value of the dielectric anisotropy necessary for this calculation was measured in the item (6) using the device whose rotational viscosity was measured.
  • Threshold voltage (Vth; measured at 25 ° C .; V): An LCD-5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement.
  • the light source was a halogen lamp.
  • the sample was placed in a normally white mode TN device in which the distance between two glass substrates (cell gap) is 0.45 / ⁇ n ( ⁇ m) and the twist angle is 80 degrees.
  • the voltage (32 Hz, rectangular wave) applied to this element was gradually increased by 0.02 V from 0 V to 10 V.
  • the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured.
  • a voltage-transmittance curve was created in which the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum.
  • the threshold voltage was represented by the voltage at 90% transmittance.
  • VHR-1 Voltage holding ratio
  • the TN device used for measurement had a polyimide alignment film, and the distance between two glass substrates (cell gap) was 5 ⁇ m. .
  • the element was sealed with an adhesive that cures with ultraviolet light after the sample was placed.
  • a pulse voltage 60 microseconds at 5 V was applied to the TN device to charge it.
  • the decaying voltage was measured with a high-speed voltmeter for 16.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined.
  • the area B was the area when it did not decay.
  • the voltage holding ratio was expressed as a percentage of the area A to the area B.
  • VHR-2 Voltage holding ratio (VHR-2; measured at 80 ° C .;%): The voltage holding ratio was measured by the same procedure as described above except that measurement was performed 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 the device and irradiated with light for 20 minutes.
  • the light source was an ultra-high pressure mercury lamp USH-500D (manufactured by Ushio Inc.), and the distance between the element and the light source was 20 cm.
  • the decaying voltage was measured for 16.7 milliseconds.
  • Compositions having large VHR-3 have high stability to ultraviolet light. 90% or more is preferable and 95% or more of VHR-3 is more preferable.
  • VHR-4 Voltage holding ratio
  • the TN device injected with the sample is heated in a thermostatic chamber at 80 ° C. for 500 hours, and then the voltage holding ratio is measured and stability to heat Was evaluated. In the measurement of VHR-4, the decaying voltage was measured for 16.7 milliseconds. Compositions having large VHR-4 have high thermal stability.
  • the rise time ( ⁇ r: millisecond) is the time taken for the transmittance to change from 90% to 10%.
  • the fall time ( ⁇ f: milliseconds) is the time taken to change from 10% transmission to 90% transmission.
  • the response time is represented by the sum of the rise time and the fall time obtained in this manner.
  • the compounds in the examples are represented by symbols based on the definition of Table 3 below.
  • Table 3 the configuration for 1,4-cyclohexylene is trans.
  • the numbers in parentheses after the symbols correspond to the compound numbers.
  • the symbol (-) means other liquid crystal compounds.
  • the proportion (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition.
  • the raw materials are the composition (M1) to the composition (M20), and the alignment control layer-forming monomer is the compound (A-1-1), the compound (A-2-1-1) and the compound (A) -2-2-1), compound (A-2-3), compound (A-2-4), compound (B-1), compound (C-1-1), compound (D-1-5) And Compound (D-1-7) and Compound (D-1-8).
  • the composition is as follows.
  • the first additive is the following compound.
  • the IPS element (above the upper limit temperature) into an IPS device having no alignment film. While the IPS element is heated at 90 ° C. (above the upper limit temperature), the element is irradiated with ultraviolet light (313 nm, 5.0 J / cm 2 ) linearly polarized from the normal direction to the element to form an element with an orientation control layer formed. Obtained. The ultraviolet light to be irradiated becomes linearly polarized light by passing the polarizer. Next, the element on which the orientation control layer was formed was set in a polarization microscope to observe the orientation state of the liquid crystal. The polarizer and the analyzer of the polarization microscope were arranged such that their transmission axes were orthogonal to each other.
  • the alignment direction of the liquid crystal molecules is parallel to the transmission axis of the polarizer of the polarization microscope, that is, the angle between the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarization microscope is 0 degrees.
  • the element was placed on the 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 transmitted through the analyzer was observed. The orientation was determined to be "good” because no light was transmitted through the analyzer.
  • the element was rotated on the horizontal rotation stage of the polarization microscope, and the angle formed by the transmission axis of the polarizer of the polarization microscope and the alignment direction of the liquid crystal molecules was changed from 0 degree.
  • the intensity of light transmitted through the analyzer increases as the angle formed by the transmission axis of the polarizer of the polarizing microscope and the orientation direction of the liquid crystal molecules increases, and is approximately maximized when the angle is 45 degrees. confirmed.
  • the liquid crystal molecules were aligned in a direction substantially horizontal to the main surface of the substrate of the device, and it was judged to be “horizontal alignment”.
  • Examples 2 to 24 Alignment control layer-forming monomers were added from the composition (M1) to the composition (M20) in the combination of Table 4.
  • a device is manufactured in the same manner as in Example 1 except that the temperature at which the liquid crystal is injected and the temperature at which polarized light is exposed are set to the temperatures described in Table 4 using this mixture, and the method similar to Example 1 Observed the presence of light leakage.
  • Comparative Example 1 It injected into the IPS element which does not have an alignment film by the method similar to Example 1 except not adding an alignment control layer formation monomer to a composition (M1), and the heating polarization exposure process was performed. The presence or absence of light leakage was observed in the same manner as in Example 1.
  • the results of Examples 1 to 24 and Comparative Example 1 are summarized in Table 4.
  • Comparative example 2 An IPS element having no alignment layer in the same manner as in Example 1 except that the following composition (R-1) for forming an alignment control layer having a cinnamate structure but not having a polymerizable group is added to the composition (M1). And heated and polarized exposure processing. The alignment state of the liquid crystal was observed in the same manner as in Example 1. In the element, a region where light does not pass through the analyzer was confirmed, while a region where light passed through the analyzer was also confirmed. The orientation was judged to be comprehensively poor.
  • the thin film formed from the alignment control layer forming monomer having two or more polymerizable groups plays an important role in the uniform alignment of liquid crystal molecules. Further, it can be seen that the compatibility with the liquid crystal composition is also good. Similar effects can be obtained from other orientation control layer forming monomers (for example, compound (A-2-1-1), compound (A-2-2-1), compound (A-2-3), compound (A- 2-4), compound (D-1-7), compound (D-1-8), compound (AA-4), compound (AA-13), compound (AA-14), Even in the case of the compound (AA-15)), it can be expected.
  • orientation control layer forming monomers for example, compound (A-2-1-1), compound (A-2-2-1), compound (A-2-3), compound (A- 2-4), compound (D-1-7), compound (D-1-8), compound (AA-4), compound (AA-13), compound (AA-14), Even in the case of the compound (AA-15)
  • liquid crystal display element having characteristics such as a wide temperature range in which the element can be used, a short response time, a high voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime. Is obtained. Furthermore, high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, appropriate optical anisotropy, positive large dielectric anisotropy, large specific resistance, high stability to ultraviolet light, high stability to heat The liquid crystal display device having a liquid crystal composition satisfying at least one of the properties as described above is 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 qui, à l'aide d'un monomère de formation de couche de régulation d'alignement incolore, régule l'alignement de molécules de cristaux liquides d'un élément d'affichage à cristaux liquides dépourvu de film d'alignement, et dans laquelle le monomère de formation de couche de régulation d'alignement incolore présente une compatibilité satisfaisante. Plus précisément, l'invention concerne une composition de cristaux liquides et un élément d'affichage à cristaux liquides qui met en œuvre cette composition de cristaux liquides. Laquelle composition de cristaux liquides comprend un monomère de formation de couche de régulation d'alignement possédant un groupe vinylène dans une sous-structure, et possède une anisotropie diélectrique positive.
PCT/JP2018/023449 2017-06-28 2018-06-20 Élément d'affichage à cristaux liquides, composition de cristaux liquides, et composé Ceased WO2019004021A1 (fr)

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JP2020204726A (ja) * 2019-06-18 2020-12-24 Dic株式会社 液晶表示素子
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TWI741697B (zh) * 2019-08-01 2021-10-01 大陸商江蘇和成顯示科技有限公司 一種液晶組合物及液晶顯示器件

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WO2013161576A1 (fr) * 2012-04-24 2013-10-31 Jnc株式会社 Composé comportant quatre groupes polymérisables, composition de cristaux liquides et élément d'affichage à cristaux liquides
WO2015004947A1 (fr) * 2013-07-10 2015-01-15 Jnc株式会社 Composé polymérisable, composition polymérisable et élément d'affichage à cristaux liquides
WO2018008581A1 (fr) * 2016-07-04 2018-01-11 シャープ株式会社 Dispositif d'affichage à cristaux liquides et procédé de fabrication de dispositif d'affichage à cristaux liquides

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JP2020204726A (ja) * 2019-06-18 2020-12-24 Dic株式会社 液晶表示素子
TWI741697B (zh) * 2019-08-01 2021-10-01 大陸商江蘇和成顯示科技有限公司 一種液晶組合物及液晶顯示器件
CN112679662A (zh) * 2019-10-18 2021-04-20 捷恩智株式会社 聚合性组合物、液晶调光元件、调光窗、智能窗及液晶复合体的用途
CN112679662B (zh) * 2019-10-18 2023-09-26 捷恩智株式会社 聚合性组合物、液晶调光元件、调光窗、智能窗及液晶复合体的用途

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