WO2020137574A1 - 液晶表示素子 - Google Patents

液晶表示素子 Download PDF

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WO2020137574A1
WO2020137574A1 PCT/JP2019/048656 JP2019048656W WO2020137574A1 WO 2020137574 A1 WO2020137574 A1 WO 2020137574A1 JP 2019048656 W JP2019048656 W JP 2019048656W WO 2020137574 A1 WO2020137574 A1 WO 2020137574A1
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group
liquid crystal
mass
carbon atoms
coo
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PCT/JP2019/048656
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English (en)
French (fr)
Japanese (ja)
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純一 間宮
雄一 井ノ上
淳子 山本
正臣 木村
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Dic株式会社
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Priority to JP2020552916A priority Critical patent/JP6841388B2/ja
Priority to CN201980063140.4A priority patent/CN112840266A/zh
Publication of WO2020137574A1 publication Critical patent/WO2020137574A1/ja

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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
    • C09K19/38—Polymers
    • 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
    • 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
    • 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
    • G02F1/1343—Electrodes
    • 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
    • G02F1/137—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
    • G02F1/139—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on orientation effects in which the liquid crystal remains transparent

Definitions

  • the present invention relates to a liquid crystal display device.
  • a polyimide (PI) film that functions as an alignment film is formed on an electrode in order to induce vertical alignment of liquid crystal molecules when no voltage is applied and to achieve horizontal alignment of liquid crystal molecules when voltage is applied. It is provided.
  • PI polyimide
  • Patent Document 1 in a liquid crystal layer containing a polymer of a liquid crystal compound (liquid crystal molecule) and a polymerizable compound (polymerizable monomer), the voltage holding ratio (VHR) and the ion density are reduced by reducing the residual monomer amount. It is disclosed to improve (ID).
  • the present invention has been made from this point of view, and an object thereof is to provide a liquid crystal display device excellent in liquid crystal alignment, alignment stability, high voltage holding ratio, and stability of voltage holding ratio.
  • Such an object is achieved by the present invention of the following (1) to (12).
  • the polymerizable monomer B is the liquid crystal display device described in (5) or (6), which is represented by the following general formula (P).
  • R p1 represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 15 carbon atoms or —Sp p2 —P p2 [one or adjacent to each other in the alkyl group.
  • —CH 2 which may not be independently substituted with —CH ⁇ CH—, —C ⁇ C—, —O—, —CO—, —COO— or —OCO—,
  • One or more hydrogen atoms present in the alkyl group may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom.
  • P p1 and P p2 each independently represent one of the following general formulas (P p1 -1) to formula (P p1 -9),
  • R p11 and R p12 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and W p11 is a single bond, Represents —O—, —COO—, —OCO— or —CH 2 —, and t p11 represents 0, 1 or 2, but a plurality of R p11 , R p12 , W p11 and/or t p11 are present in the molecule. If present, they may be the same or different and * represents a bond.
  • Sp p1 and Sp p2 each independently represent a single bond or a spacer group
  • a p1 , A p2 and A p3 are each independently, (A p )1,4-cyclohexylene group [one —CH 2 — present in this group or two or more —CH 2 — which are not adjacent to each other may be substituted with —O—. ] (B p ) 1,4-phenylene group [one —CH ⁇ present in this group or two or more —CH ⁇ which are not adjacent to each other may be substituted with —N ⁇ .
  • R AP1 and R AP2 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 10 carbon atoms [one of the alkyl groups Alternatively, two or more —CH 2 — may be substituted with —O— or —CO—, and one or two or more hydrogen atoms in the alkyl group are independently a halogen atom or a hydroxyl group. May be replaced with.], W AP1 represents a single bond, —O—, —COO—, —OCO— or —CH 2 —, t AP1 represents 0, 1 or 2, * Represents a bond. )
  • the liquid crystal display device according to any one of (1) to (8), wherein the liquid crystal molecule has a negative dielectric anisotropy ( ⁇ ).
  • the liquid crystal display device according to any one of (1) to (9), which is for driving an active matrix.
  • the liquid crystal display device according to any one of (1) to (10) above, which is a PSA type, PSVA type, VA type, IPS type, FFS type or ECB type.
  • the present invention by optimizing the remaining amount of the polymerizable monomer in the liquid crystal layer, it is possible to provide a liquid crystal display element having excellent characteristics (especially voltage holding ratio).
  • FIG. 1 is an exploded perspective view schematically showing an embodiment of a liquid crystal display element. It is the top view which expanded the area
  • the liquid crystal composition used in the present invention is used for forming a liquid crystal layer included in a liquid crystal display device.
  • the liquid crystal composition of the present embodiment contains liquid crystal molecules having a negative dielectric anisotropy ( ⁇ ) and an alignment aid (polymerizable monomer A) having a function of spontaneously aligning the liquid crystal molecules.
  • the alignment aid is a member (electrode (for example, ITO), substrate (for example, glass substrate, acrylic substrate, transparent substrate, flexible substrate, or the like)) that directly contacts the liquid crystal layer containing the liquid crystal composition, resin layer (for example, color filter).
  • An alignment film, an overcoat layer, etc.) and an insulating film for example, an inorganic material film, SiNx, etc.
  • the alignment aid induces alignment of the liquid crystal molecules, a polymerizable group for polymerization, a mesogenic group similar to the liquid crystal molecules, an adsorption group (polar group) capable of interacting with a member that directly contacts the liquid crystal layer. It preferably has an orientation-inducing group. It is preferable that the adsorption group and the orientation-inducing group are bound to the mesogen group, and the polymerizable group is substituted on the mesogen group, the adsorption group and the orientation-inducing group directly or via a spacer group as necessary.
  • the polymerizable group is preferably substituted with the mesogen group in a state of being incorporated in the adsorption group.
  • * at the left end and * at the right end in the chemical formulas represent a bond.
  • orientation-inducing group has a function of inducing the orientation of liquid crystal molecules, and is preferably a group represented by the following general formula (AK).
  • R AK1 represents a linear or branched alkyl group having 1 to 20 carbon atoms. However, one or two or more non-adjacent —CH 2 — groups in the alkyl group are independently —CH ⁇ CH—, —C ⁇ C—, —O—, —CO—, —COO— or It may be substituted with —OCO—, and one or more hydrogen atoms in the alkyl group may be independently substituted with a halogeno group.
  • R AK1 preferably represents a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably a linear alkyl group having 1 to 20 carbon atoms, and more preferably a linear alkyl group. More preferably, it represents an alkyl group having 1 to 8 carbon atoms. Further, one or two or more non-adjacent —CH 2 — groups in the alkyl group are independently —CH ⁇ CH—, —C ⁇ C—, —O—, so that oxygen atoms are not directly adjacent to each other. It may be substituted with —CO—, —COO— or —OCO—.
  • the hydrogen atom in the alkyl group may be substituted with a fluorine atom, a chlorine atom or a fluorine atom.
  • the orientation-inducing group is preferably bonded to the opposite side of the mesogen group from the adsorption group.
  • Polymerizable group The polymerizable group is represented by P AP1 ⁇ and is preferably bonded to the mesogen group via Sp AP1 ⁇ (single bond or spacer group).
  • P AP1 is preferably a group selected from the group represented by the following general formulas (AP-1) to (AP-9).
  • R AP1 and R AP2 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms.
  • one or more —CH 2 — in the alkyl group may be substituted with —O— or —CO— so that oxygen atoms are not directly adjacent to each other, and one or two —CH 2 — in the alkyl group may be substituted.
  • the above hydrogen atoms may be independently substituted with a halogen atom or a hydroxyl group.
  • W AP1 represents a single bond, —O—, —COO—, —OCO— or —CH 2 —.
  • t AP1 represents 0, 1 or 2.
  • P AP1 is preferably a group represented by the following general formula (AP-1) to general formula (AP-7), and is represented by the following general formula (AP-1) or general formula (AP-2).
  • Group represented by formula (AP-1) is more preferable.
  • Sp AP1 is preferably a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, and more preferably a single bond or a linear alkylene group having 1 to 20 carbon atoms. It is more preferable to represent a single bond or a linear alkylene group having 2 to 10 carbon atoms.
  • one or two or more non-adjacent —CH 2 — in the alkylene group are independently —CH ⁇ CH—, —C ⁇ C—, so that oxygen atoms are not directly adjacent to each other. It may be substituted with —O—, —CO—, —COO— or —OCO—.
  • the number of P AP1 ⁇ Sp AP1 ⁇ is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, and 2 or more and 4 or less. More preferably, 2 or 3 is particularly preferable, and 2 is most preferable.
  • the hydrogen atom in P AP1- Sp AP1- may be substituted with a polymerizable group, an adsorption group described later and/or the above-mentioned orientation-inducing group.
  • P AP1- Sp AP1- may be bonded to a polymerizable group, a mesogenic group, an adsorption group described below and/or the orientation-inducing group.
  • P AP1 -Sp AP1- is preferably bonded to a mesogen group, an adsorption group described later or the above-mentioned orientation-inducing group, and more preferably bonded to a mesogen group or an adsorption group described later.
  • P AP1 and/or Sp AP1 ⁇ are present in the molecule, they may be the same or different from each other.
  • the mesogen group means a group having a rigid portion, for example, a group having at least one cyclic group, preferably a group having 2 to 4 cyclic groups, and 3 to 4 cyclic groups. Groups are more preferred.
  • the cyclic group may be linked by a linking group.
  • the mesogen group preferably has a skeleton similar to that of liquid crystal molecules (liquid crystal compound) used in the liquid crystal layer.
  • the “cyclic group” refers to an atomic group in which constituent atoms are cyclically bonded, and includes a carbocycle, a heterocycle, a saturated or unsaturated cyclic structure, a monocyclic and bicyclic structure, Includes polycyclic structures, aromatics, non-aromatics and the like.
  • the cyclic group may contain at least one hetero atom, and may be further substituted with at least one substituent (halogeno group, polymerizable group, organic group (alkyl group, alkoxy group, aryl group, etc.).
  • the mesogen group preferably contains two or more monocyclic rings.
  • the mesogen group is preferably represented by, for example, general formula (AL).
  • Z AL1 is a single bond, —CH ⁇ CH—, —CF ⁇ CF—, —C ⁇ C—, —COO—, —OCO—, —OCOO—, —CF 2 O—, —OCF 2 —.
  • -CH CHCOO -
  • one or two or more non-adjacent —CH 2 — in the alkylene group may be substituted with —O—, —COO— or —OCO— so that oxygen atoms are not directly adjacent.
  • a AL1 and A AL2 each independently represent a divalent cyclic group.
  • One or more hydrogen atoms in Z AL1 , A AL1 and A AL2 may be independently substituted with a halogeno group, an adsorbing group, P AP1- Sp AP1 -or a monovalent organic group.
  • m AL1 represents an integer of 1 to 5.
  • Z AL1 is preferably a single bond or an alkylene group having 2 to 20 carbon atoms, more preferably a single bond or an alkylene group having 2 to 10 carbon atoms, and a single bond.
  • Z AL1 has a single bond in which rings are directly connected to each other or an even number of atoms that directly connect the rings to each other.
  • the form is preferred. For example, in the case of —CH 2 —CH 2 COO—, the number of atoms directly connecting the rings is four.
  • a AL1 and A AL2 each independently represent a divalent cyclic group.
  • the divalent cyclic group include 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2, 5-diyl group, tetrahydrothiopyran-2,5-diyl group, thiophene-2,5-diyl group, 1,4-bicyclo(2.2.2)octylene group, decahydronaphthalene-2,6-diyl group , Pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2 ,6-diyl group,
  • these groups may be unsubstituted or substituted with a substituent.
  • the substituent is preferably a fluorine atom or an alkyl group having 1 to 8 carbon atoms.
  • the alkyl group may be substituted with a fluorine atom or a hydroxyl group.
  • one or more hydrogen atoms in the cyclic group may be substituted with a halogeno group, an adsorptive group, P AP1- Sp AP1 -or a monovalent organic group.
  • the monovalent organic group is a group having a chemical structure formed by the organic compound being in the form of a monovalent group, and is formed by removing one hydrogen atom from the organic compound.
  • An atomic group examples of the monovalent organic group include an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, and an alkenyloxy having 2 to 15 carbon atoms. Groups, etc., preferably an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 14 carbon atoms, and an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.
  • an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms or 1 to 2 carbon atoms is more preferable.
  • An alkoxy group is particularly preferable, and an alkyl group having 1 or 2 carbon atoms or an alkoxy group having 1 carbon atom is most preferable.
  • one or two or more non-adjacent —CH 2 — in the above alkyl group, alkenyl group, alkoxy group and alkenyloxy group may be substituted with —O—, —COO— or —OCO—.
  • the monovalent organic group may have a role as the above-mentioned orientation-inducing group.
  • m AL1 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 2 or 3.
  • the general formula (AL) is a structure in which two hydrogen atoms are eliminated from these compounds.
  • one or more hydrogen atoms in the cyclohexane ring, benzene ring or naphthalene ring are each independently a halogeno group, P AP1 -Sp AP1.
  • -It may be substituted with a monovalent organic group (for example, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms), an adsorption group or an orientation inducing group.
  • formulas (me-8) to (me-44) preferred forms are formulas (me-8) to (me-44), and more preferred forms are formulas (me-8) to (me-10) and formulas (me-12) to (Me-18), formulas (me-22) to (me-24), formulas (me-26) to (me-27) and formulas (me-29) to (me-44), and more preferred forms Are expressions (me-12), (me-14), (me-16), (me-22) to (me-24), (me-29), (me-34), (me-36). To (me-37) and (me-42) to (me-44).
  • a particularly preferred form is the following general formula (AL-1) or (AL-2), and a most preferred form is the following general formula (AL-1).
  • X AL101 to X AL118 and X AL201 to X AL214 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogeno group, P APl- Sp APl ⁇ represents an adsorption group described later or the above-mentioned orientation-inducing group.
  • Ring A AL11, Ring A AL12 and ring A AL21 each independently represent a cyclohexane ring or a benzene ring. Any one or more of X AL101 to X AL118 and X AL201 to X AL214 are substituted with an adsorption group described later.
  • any one or more of X AL101 to X AL118 and X AL201 to X AL214 are substituted with the orientation-inducing group. Adsorptive group and the orientation induced group will be described later, P AP1 -Sp AP1 - may be substituted with.
  • the general formula (AL-1) or the general formula (AL-2) has one or two or more P AP1 -Sp APl- in its molecule.
  • X AL101 is preferably the above-mentioned orientation-inducing group.
  • at least one of X AL109 , X AL110 and X AL111 is preferably an adsorption group described below, and both X AL109 and X AL110 are adsorption groups described below or X AL110 is described later. Is more preferable, and X AL110 is further preferable to be an adsorption group described later.
  • At least one of X AL109 , X AL110, and X AL111 is preferably P AP1 -Sp AP1 -, or an adsorption group having a polymerizable site in the structure, among the adsorption groups described below. , both or one of X AL109 and X AL111 is P AP1 -Sp AP1 - is more preferable.
  • one or two of X AL104 to X AL108 and X AL112 to X AL116 are independently an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.
  • X AL105 , X AL106, and X AL107 are each independently an alkyl group having 1 to 3 carbon atoms or a fluorine atom.
  • X AL201 is preferably the above-mentioned orientation-inducing group.
  • at least one of X AL207 , X AL208 and X AL209 is preferably an adsorption group described below, and both X AL207 and X AL208 are adsorption groups described below or X AL208 is described later. Is more preferable, and X AL208 is further preferable to be an adsorption group described later.
  • X AL207 , X AL208 and X AL209 is P AP1 -Sp AP1- of the adsorption groups described below or an adsorption group having a polymerizable site in the structure.
  • X AL2 07 and X AL 209 , or both are more preferably P AP1 —Sp AP1 ⁇ .
  • one or two of X AL202 to X AL206 and X AL210 to X AL214 are independently an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.
  • X AL204, X AL205 or X AL206 are each independently preferably an alkyl group or a fluorine atom of 1 to 3 carbon atoms.
  • Adsorption group is a group having a role of adsorbing with an adsorbent which is a layer that comes into contact with the liquid crystal composition such as a substrate, a film and an electrode.
  • Adsorption is generally classified into chemisorption in which a chemical bond (covalent bond, ionic bond, or metal bond) is formed to adsorb between the adsorbent and the adsorbate, and physical adsorption other than chemisorption.
  • the adsorption may be either chemical adsorption or physical adsorption, but physical adsorption is preferable.
  • the adsorption group is preferably a group capable of physically adsorbing to the adsorption medium, and more preferably a group capable of binding to the adsorption medium by intermolecular force.
  • the form of binding to the adsorbent medium by intermolecular force include a form of interaction such as permanent dipole, permanent quadrupole, dispersive force, charge transfer force or hydrogen bond.
  • a preferred form of the adsorptive group is a form capable of binding to the adsorbent by hydrogen bonding.
  • the adsorbing group may serve as either a donor or an acceptor of protons that mediate hydrogen bonding, or both.
  • the adsorptive group is preferably a group containing a polar element having an atomic group in which a carbon atom and a hetero atom are linked (hereinafter, the “adsorptive group” is also referred to as a “polar group”).
  • the polar element refers to an atomic group in which a carbon atom and a hetero atom are directly linked.
  • the hetero atom is preferably at least one selected from the group consisting of N, O, S, P, B and Si, and at least one selected from the group consisting of N, O and S. Is more preferable, at least one selected from the group consisting of N and O is more preferable, and O is particularly preferable.
  • the valence of the polar element is not particularly limited, such as monovalent, divalent, and trivalent, and the number of polar elements in the adsorbing group is not particularly limited.
  • the orientation aid preferably has 1 to 8 adsorption groups in one molecule, more preferably 1 to 4 adsorption groups, and further preferably 1 to 3 adsorption groups.
  • the adsorption group, excluding a polymerizable group and orientation induced group a hydrogen atom is P AP1 -Sp AP1 in adsorptive group - substituted with structural and P AP1 -Sp AP1 - hydrogen atoms in the -OH The structure substituted with is included in the adsorptive group.
  • the adsorptive group contains one or more polar elements and is roughly classified into a cyclic group type and a chain group type.
  • the cyclic group type is a form including a cyclic group having a cyclic structure containing a polar element in its structure
  • the chain group type is a cyclic group having a cyclic structure containing a polar element in its structure. It is a form that does not include.
  • the chain group type is a form having a polar element in a linear or branched chain group, and may have a cyclic structure which does not include a polar element in a part thereof.
  • the cyclic group-type adsorptive group means a form having a structure containing at least one polar element in a cyclic atomic arrangement.
  • the cyclic group is as described above. Therefore, the cyclic group-type adsorptive group only needs to include a cyclic group containing a polar element, and the entire adsorptive group may be branched or linear.
  • a chain-type adsorptive group is a structure that does not include a cyclic atomic array containing polar elements in the molecule and contains at least one polar element in a linear atomic array (which may be branched). Means a form having.
  • the chain group refers to an atomic group in which the constituent atoms do not include a cyclic atomic array in the structural formula and the constituent atoms are linearly (may be branched), and are acyclic.
  • the chain group refers to a linear or branched aliphatic group, and may include either a saturated bond or an unsaturated bond. Therefore, the chain group includes, for example, an alkyl group, an alkenyl group, an alkoxy group, an ester group, an ether group or a ketone group.
  • the hydrogen atom in these groups is substituted with at least one substituent (reactive functional group (vinyl group, acryl group, methacryl group, etc.), chain organic group (alkyl group, cyano group, etc.)) Good.
  • substituent reactive functional group (vinyl group, acryl group, methacryl group, etc.)
  • chain organic group alkyl group, cyano group, etc.
  • the chain group may be linear or branched.
  • the cyclic group-type adsorbing group may be a heteroaromatic group having 3 to 20 carbon atoms (including a condensed ring) or a heteroalicyclic group having 3 to 20 carbon atoms (including a condensed ring).
  • a heteroaromatic group having 3 to 12 carbon atoms (including a condensed ring) or a heteroalicyclic group having 3 to 12 carbon atoms (including a condensed ring) is more preferable, and a 5-membered hetero group. It is more preferably an aromatic group, a 5-membered heteroalicyclic group, a 6-membered heteroaromatic group, or a 6-membered heteroalicyclic group.
  • the hydrogen atom in these ring structures may be substituted with a halogeno group, a linear or branched alkyl group having 1 to 5 carbon atoms or an alkyloxy group.
  • the chain-type adsorptive group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms in which a hydrogen atom in the structure or —CH 2 — is substituted with a polar element. It should be noted that one or two or more non-adjacent —CH 2 — groups in the alkyl group are replaced with —CH ⁇ CH—, —C ⁇ C—, —O—, —CO—, —COO— or —OCO—. May be done.
  • the chain-type adsorptive group preferably includes one or more polar elements at the end thereof.
  • a hydrogen atom in the adsorptive group may be replaced with a polymerizable group.
  • the polar element include a polar element containing an oxygen atom (hereinafter, oxygen-containing polar element), a polar element containing a nitrogen atom (hereinafter, nitrogen-containing polar element), and a polar element containing a phosphorus atom (hereinafter, phosphorus-containing polar). Element), a polar element containing a boron atom (hereinafter, boron-containing polar element), a polar element containing a silicon atom (hereinafter, silicon-containing polar element), or a polar element containing a sulfur atom (hereinafter, sulfur-containing polar element). .
  • the polar element is preferably a nitrogen-containing polar element or an oxygen-containing polar element, and more preferably an oxygen-containing polar element.
  • At least one group selected from the group consisting of a hydroxyl group, an alkylol group, an alkoxy group, a formyl group, a carboxyl group, an ether group, a carbonyl group, a carbonate group and an ester group or the group is a carbon atom. It is preferably a group linked to an atom.
  • the nitrogen-containing polar element at least one group selected from the group consisting of a cyano group, a primary amino group, a secondary amino group, a tertiary amino group, a pyridyl group, a carbamoyl group and a ureido group, or the group having carbon It is preferably a group linked to an atom.
  • a cyclic group having an oxygen-containing polar element hereinafter, oxygen-containing cyclic group
  • a cyclic group having a nitrogen-containing polar element hereinafter, nitrogen-containing cyclic group
  • an oxygen-containing polar group One or more selected from the group consisting of a chain group having an element (hereinafter, oxygen-containing chain group) and a chain group having a nitrogen-containing polar element (hereinafter, nitrogen-containing chain group) It is preferable to include the group itself or the group.
  • the oxygen-containing cyclic group preferably contains any of the following groups having an oxygen atom as an ether group in the ring structure.
  • the oxygen-containing cyclic group preferably contains any of the following groups having an oxygen atom as a carbonyl group, a carbonate group and an ester group in the ring structure.
  • the nitrogen-containing cyclic group preferably contains any of the following groups.
  • the oxygen-containing chain group preferably contains any of the following groups.
  • R at1 represents an alkyl group having 1 to 5 carbon atoms.
  • Z at1 represents a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms, or a linear or branched alkenylene group having 2 to 18 carbon atoms.
  • —CH 2 — in the alkylene group or alkenylene group may be substituted with —O—, —COO—, —C( ⁇ O)—, or —OCO— so that oxygen atoms are not directly adjacent to each other.
  • X at1 represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms.
  • —CH 2 — in the alkyl group may be substituted with —O—, —COO—, —C( ⁇ O)—, or —OCO— so that oxygen atoms are not directly adjacent to each other.
  • the nitrogen-containing chain group preferably contains any of the following groups.
  • R at , R bt , R ct and R dt each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • the adsorbing group is preferably a group represented by the following general formula (AT).
  • Sp AT1 represents a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms.
  • the hydrogen atom in the alkylene group may be substituted with —OH, —CN, —W AT1 —Z AT1 or P AP1 —Sp AP1 —, and —CH 2 — in the alkylene group is directly bonded to the oxygen atom. It may be substituted with a cyclic group, —O—, —COO—, —C( ⁇ O)—, —OCO—, —CH ⁇ CH— or —OCO—COO— so as not to bond.
  • W AT1 represents a single bond or the following general formula (WAT1) or (WAT2).
  • Z AT1 represents a monovalent group containing a polar element.
  • the hydrogen atom in Z AT1 may be replaced by —OH, —CN or P AP1 —Sp AP1 —.
  • Sp WAT1 and Sp WAT2 each independently represent a single bond, a linear or branched alkylene group having 1 to 25 carbon atoms, and a hydrogen atom in the alkylene group is —OH, — CN or P AP1 —Sp AP1 — may be substituted, and —CH 2 — in the alkylene group is a cyclic group, —O—, —COO—, —C( ⁇ O) so that an oxygen atom is not directly bonded.
  • Sp AT1 , Sp WAT1 and Sp WAT2 each independently represent a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, and a single bond or a linear carbon atom number. It is more preferable to represent an alkylene group having 1 to 20 and even more preferable to represent a single bond or a linear alkylene group having 2 to 10 carbon atoms. Further, in Sp AT1 , Sp WAT1 and Sp WAT2 , one or more —CH 2 — in the alkylene group may independently be —CH ⁇ CH—, — so that an oxygen atom is not directly bonded.
  • Sp AT1 and Sp WAT1 are each independently, -W AT1 -Z AT1 or P AP1 -Sp AP1 - it may be substituted with.
  • Z AT1 represents a monovalent group containing a polar element, and is preferably a group represented by the following general formula (ZAT1-1) or (ZAT1-2).
  • Sp ZAT11 and Sp ZAT12 each independently represent a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms.
  • the hydrogen atom in the alkylene group may be substituted with —OH, —CN, —Z ZAT11 —R ZAT11 or P AP1 —Sp AP1 —, and —CH 2 — in the alkylene group is directly bonded to the oxygen atom. It may be substituted with a cyclic group, —O—, —COO—, —C( ⁇ O)—, —OCO— or —CH ⁇ CH— so as not to be adjacent to each other.
  • Z ZAT11 represents a group containing a polar element.
  • the structure represented by the ring containing Z ZAT12 in the general formula (ZAT1-2) represents a 5- to 7-membered ring.
  • the hydrogen atom in Z ZAT11 and Z ZAT12 may be substituted with —OH, —CN or P AP1 —Sp AP1 —.
  • the group represented by the general formula (ZAT1-1) is preferably a group represented by the following general formulas (ZAT1-1-1) to (ZAT1-1-30).
  • the hydrogen atom bonded to the carbon atom may be substituted with —OH, —CN or P AP1 —Sp AP1 —.
  • Sp ZAT11 represents a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms.
  • the hydrogen atom in the alkylene group may be substituted with —OH, —CN, —Z ZAT11 —R ZAT11 or P AP1 —Sp AP1 —, and —CH 2 — in the alkylene group is directly bonded to the oxygen atom.
  • R ZAT11 represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms.
  • a hydrogen atom in the alkyl group may be replaced by —OH, —CN or P AP1 —Sp AP1 —, and —CH 2 — in the alkyl group is a cyclic group so that an oxygen atom is not directly bonded.
  • the group represented by the general formula (ZAT1-2) is preferably a group represented by the following general formulas (ZAT1-2-1) to (ZAT1-2-9).
  • the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, —OH, —CN or P AP1 —Sp AP1 —.
  • Sp ZAT11 represents a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms.
  • Examples of the group represented by the general formula (ZAT1-1) include the following groups.
  • R tc represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or P AP1 —Sp AP1 —.
  • a hydrogen atom in the alkyl group may be replaced by —OH, —CN or P AP1 —Sp AP1 —
  • —CH 2 — in the alkyl group is a cyclic group so that oxygen atoms are not directly adjacent to each other.
  • Hydrogen atoms in the molecule, P AP1 -Sp AP1 - may be substituted with. * Represents a bond.
  • the orientation aid is preferably in a form in which the polar element contained in the adsorptive group or the polar element contained in the polymerizable group is localized.
  • the adsorptive group is an important structure for vertically aligning liquid crystal molecules, and when the adsorptive group and the polymerizable group are adjacent to each other, a better alignment property can be obtained and a good liquid crystal composition can be obtained. Shows solubility.
  • the orientation aid is preferably in a form having a polymerizable group and an adsorptive group on the same ring of the mesogen group.
  • Such a form includes a form in which one or more polymerizable groups and one or more adsorption groups are respectively bonded on the same ring, and at least one or one or more adsorption groups of the one or more polymerizable groups.
  • a hydrogen atom in the spacer group bonded to the polymerizable group may be replaced with an adsorptive group, and further, a hydrogen atom in the adsorptive group may be replaced with a polymerizable group through the spacer group.
  • the orientation aid is preferably a compound represented by the following general formula (SAL).
  • the hydrogen atom bonded to the carbon atom is a linear or branched alkyl group having 1 to 25 carbon atoms, —OH, —CN, —Sp AT1 —W AT1 —Z AT1 or P AP1 —Sp AP1. It may be replaced with-. However, the hydrogen atom in the alkyl group may be substituted with —OH, —CN, —Sp AT1 —W AT1 —Z AT1 or P AP1 —Sp AP1 —, and —CH 2 — in the alkyl group is oxygen.
  • R AK1 has the same meaning as R AK1 in formula (AK).
  • a AL1 and A AL2 each independently have the same meaning as A AL1 and A AL2 in formula (AL).
  • Z AL1 has the same meaning as Z AL1 in formula (AL).
  • m AL1 has the same meaning as m AL1 in formula (AL).
  • Sp AT1 has the same meaning as Sp AT1 in formula (AT).
  • W AT1 has the same meaning as W AT1 in formula (AT).
  • Z AT1 has the same meaning as Z AT1 in formula (AT).
  • the compound represented by the general formula (SAL) is preferably a compound represented by the following formulas (SAL-1.1) to (SAL-2.10).
  • the amount of the alignment aid contained in the liquid crystal composition is preferably about 0.01 to 10% by mass.
  • the more preferable lower limit values thereof are 0.05% by mass and 0.1% by mass from the viewpoint of aligning the liquid crystal molecules more preferably.
  • the more preferable upper limit value thereof is 7% by mass, 5% by mass, 4% by mass, 3% by mass, and 1% by mass from the viewpoint of improving response characteristics.
  • the liquid crystal composition used in the present invention preferably contains a polymerizable compound (polymerizable monomer B) having no adsorptive group (polar group). Such a polymerizable compound has a function of imparting a predetermined pretilt angle to liquid crystal molecules.
  • This polymerizable compound is preferably represented by the following general formula (P).
  • the liquid crystal composition may contain two or more kinds of this polymerizable compound.
  • R p1 represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 15 carbon atoms, or —Sp p2 —P p2 .
  • one or two or more non-adjacent —CH 2 — present in the alkyl group are each independently —CH ⁇ CH—, —C ⁇ C—, —O—, —CO—, —COO. It may be substituted with -or -OCO-.
  • one or more hydrogen atoms present in the alkyl group may be independently substituted with a cyano group, a fluorine atom or a chlorine atom.
  • P p1 and P p2 each independently represent one of the following general formulas (P p1 -1) to (P p1 -9).
  • R p11 and R p12 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and W p11 is a single bond, Represents —O—, —COO—, —OCO— or —CH 2 —, and t p11 represents 0, 1 or 2, but a plurality of R p11 , R p12 , W p11 and/or t p11 are present in the molecule. If present, they may be the same or different.
  • Sp p1 and Sp p2 each independently represent a single bond or a spacer group.
  • a p1 , A p2 and A p3 are each independently, (A p )1,4-cyclohexylene group (one —CH 2 — present in this group or two or more —CH 2 — not adjacent to each other may be substituted with —O—.
  • m p1 represents 0, 1, 2 or 3.
  • a p3 is the m p1 is 0, when A p1 is the group (c p), it may be a single bond. Note that the alignment aid is excluded from the polymerizable compound.
  • R p1 is preferably —Sp p2 —P p2 . It is preferable that P p1 and P p2 are each independently one of the general formulas (P p1 -1) to formula (P p1 -3), and more preferably (P p1 -1). R p11 and R p12 are preferably each independently a hydrogen atom or a methyl group. tp11 is preferably 0 or 1. W p11 is preferably a single bond, —CH 2 — or —C 2 H 4 —. m p1 is preferably 0, 1 or 2, and is preferably 0 or 1.
  • Z p1 and Z p2 present in the molecule are single bonds.
  • only one of Z p1 and Z p2 existing in the molecule is —CH ⁇ CH—COO—, —COO—CH ⁇ CH—, —(CH 2 ) 2 —COO—, —(CH 2 ) 2
  • Sp p1 and Sp p2 each independently represent a single bond or a spacer group, and the spacer group is preferably an alkylene group having 1 to 30 carbon atoms.
  • the hydrogen atom in the alkylene group may be replaced with a halogen atom.
  • Sp p1 and Sp p2 are preferably each independently a linear alkylene group having 1 to 10 carbon atoms or a single bond.
  • a p1 , A p2 and A p3 are each independently preferably a 1,4-phenylene group or a 1,4-cyclohexylene group, and more preferably a 1,4-phenylene group.
  • the 1,4-phenylene group is preferably substituted with one fluorine atom, one methyl group or one methoxy group in order to improve the compatibility with liquid crystal molecules (liquid crystal compounds).
  • the amount of the polymerizable compound contained in the liquid crystal composition is preferably 0.05 to 10% by mass, more preferably 0.1 to 8% by mass, and 0.1 to 5% by mass. It is more preferably 0.1 to 3% by mass, further preferably 0.2 to 2% by mass, further preferably 0.2 to 1.3% by mass, and 0. It is particularly preferably 0.2 to 1% by mass, and most preferably 0.2 to 0.5% by mass.
  • the preferable lower limit values thereof are 0.01% by mass, 0.03% by mass, 0.05% by mass, 0.08% by mass, 0.1% by mass and 0.15% by mass. %, 0.2% by mass, 0.25% by mass, 0.3% by mass.
  • the preferable upper limit values are 10% by mass, 8% by mass, 5% by mass, 3% by mass, 1.5% by mass, 1.2% by mass, and 1% by mass. %, 0.8% by mass, and 0.5% by mass.
  • the amount of the polymerizable compound When the amount of the polymerizable compound is small, the effect of adding the polymerizable compound to the liquid crystal composition is unlikely to appear, and for example, depending on the type of the liquid crystal molecule or the alignment aid, the alignment regulating force of the liquid crystal molecule is weak or weak with time. There may be problems such as being lost.
  • the amount of the polymerizable compound is too large, for example, depending on the illuminance of ultraviolet rays, the amount of the polymerizable compound remaining after curing increases, the curing takes time, and the reliability of the liquid crystal composition decreases. There may be problems. Therefore, it is preferable to set the amount of the polymerizable compound in consideration of these balances.
  • Preferred examples of the polymerizable compound represented by the general formula (P) include the polymerizable compounds represented by the following formulas (P-1-1) to (P-1-46).
  • P p11 , P p12 , Sp p11 and Sp p12 have the same meanings as P p1 , P p2 , Sp p1 and Sp p2 in the general formula (P).
  • polymerizable compound represented by the general formula (P) also include the polymerizable compounds represented by the following formulas (P-2-1) to (P-2-12).
  • P p21 , P p22 , Sp p21, and Sp p22 have the same meanings as P p1 , P p2 , Sp p1, and Sp p2 in the general formula (P).
  • preferable examples of the polymerizable compound represented by the general formula (P) also include the polymerizable compounds represented by the following formulas (P-3-1) to (P-3-15).
  • P p31 , P p32 , Sp p31, and Sp p32 have the same meanings as P p1 , P p2 , Sp p1, and Sp p2 in the general formula (P).
  • polymerizable compound represented by the general formula (P) also include the polymerizable compounds represented by the following formulas (P-4-1) to (P-4-15).
  • P p41 , P p42 , Sp p41, and Sp p42 have the same meanings as P p1 , P p2 , Sp p1, and Sp p2 in the general formula (P).
  • the liquid crystal composition of the present invention has, as liquid crystal molecules, general formulas (N-01), (N-02), (N-03), (N-04) and (N-05). It is preferable to contain one kind or two or more kinds selected from the compounds represented by These compounds correspond to compounds having dielectrically negative anisotropy. These compounds have a negative sign of ⁇ and have an absolute value larger than 2.
  • ⁇ of the compound is a value extrapolated from the measured value of the dielectric anisotropy of the composition obtained by adding the compound to a composition that is dielectrically almost neutral at 25° C.
  • R 21 and R 22 each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or 2 to 8 represents an alkenyloxy group, and one or two or more non-adjacent —CH 2 — groups in each group independently represent —CH ⁇ CH—, —C ⁇ C—, —O—, — It may be substituted with CO—, —COO— or —OCO—, and each Z 1 independently represents a single bond, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —COO—. , —OCO—, —OCF 2 —, —CF 2 O—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—, and m independently represents 1 or 2.
  • R 21 is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms. .. However, when Z 1 represents a bond other than a single bond, R 21 is preferably an alkyl group having 1 to 3 carbon atoms.
  • R 22 is preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and is an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. More preferably, it is more preferably an alkoxy group having 1 to 4 carbon atoms.
  • R 21 and R 22 can also be alkenyl groups.
  • R 21 and R 22 are each independently selected from the groups represented by the following formulas (R1) to (R5) (the black dots in each formula represent carbon atoms in the ring structure). It is preferable that the formula (R1) or the formula (R2) is more preferable. However, the content of the compound in which R 21 and R 22 are alkenyl groups is preferably as small as possible, and it is often preferable not to contain them.
  • Z 1 is preferably a single bond.
  • Z 1 is preferably —CH 2 CH 2 — or —CH 2 O—.
  • the fluorine atom of the compounds represented by the general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) is replaced with a chlorine atom of the same halogen group. It may have been done. However, the content of the compound substituted with a chlorine atom is preferably as small as possible, and is preferably not contained.
  • the hydrogen atom present on the ring of the compounds represented by the general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) may be a fluorine atom or a It may be substituted with a chlorine atom. However, the content of the compound substituted with a chlorine atom is preferably as small as possible, and is preferably not contained.
  • R 22 is preferably an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms.
  • Examples of the compound represented by the general formula (N-01) include the general formula (N-01-1), the general formula (N-01-2), the general formula (N-01-3) and the general formula (N-01 It is preferable to contain one kind or two or more kinds selected from the compounds represented by -4).
  • R 21 has the same meaning as described above, and R 23 independently represents an alkoxy group having 1 to 4 carbon atoms.
  • the liquid crystal composition preferably contains a polymerizable monomer and a compound represented by the general formula (N-01-1) or the general formula (N-01-4).
  • the general formula (N-01-3) is used. It is preferred to be free of the compound represented.
  • the compound represented by the general formula (N-02) is selected from compounds represented by the general formula (N-02-1), the general formula (N-02-2) and the general formula (N-02-3). It is preferable to contain one kind or two or more kinds.
  • R 21 has the same meaning as described above, and R 23 independently represents an alkoxy group having 1 to 4 carbon atoms.
  • the liquid crystal composition preferably contains a polymerizable monomer and a compound represented by the general formula (N-02-1).
  • the liquid crystal composition preferably contains a polymerizable monomer and a compound represented by the general formula (N-02-3).
  • the liquid crystal composition includes a polymerizable monomer, a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4) and a compound represented by the general formula (N-02-1). It is particularly preferred to simultaneously contain the compounds mentioned.
  • the liquid crystal composition includes a polymerizable monomer, a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4) and a compound represented by the general formula (N-02-3). It is particularly preferred to simultaneously contain the compounds mentioned.
  • the compound represented by the general formula (N-03) it is preferable to contain one kind or two or more kinds of the compound represented by the general formula (N-03-1).
  • R 21 has the same meaning as described above, and R 23 represents an alkoxy group having 1 to 4 carbon atoms.
  • the liquid crystal composition is preferably a combination of a polymerizable monomer and a compound represented by the general formula (N-03-1).
  • the liquid crystal composition includes a polymerizable monomer, a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4) and a compound represented by the general formula (N-03-1). It is particularly preferred to simultaneously contain the compounds mentioned.
  • the compound represented by the general formula (N-04) it is preferable to contain one kind or two or more kinds of the compound represented by the general formula (N-04-1).
  • R 21 has the same meaning as described above, and R 23 represents an alkoxy group having 1 to 4 carbon atoms.
  • the liquid crystal composition includes a polymerizable monomer, a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4) and a compound represented by the general formula (N-04-1). It is particularly preferred to simultaneously contain the compounds mentioned.
  • the compound represented by the general formula (N-05) is preferably selected from compounds represented by the formula (N-05-1) to the formula (N-05-3).
  • the lower limit of the preferred content of the compound represented by formula (N-01) is 0% by mass, 1% by mass, 5% by mass, and 10% by mass with respect to the total amount of the liquid crystal composition. %, 20% by mass, 30% by mass, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass Yes, 75% by mass, 80% by mass.
  • the upper limit of the preferred content is 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, 45% by mass, 35% by mass, 25% by mass, 20% by mass, 15% by mass and 10% by mass.
  • the lower limit of the preferred content of the compound represented by formula (N-02) is 0% by mass, 1% by mass, 5% by mass, and 10% by mass with respect to the total amount of the liquid crystal composition. %, 20% by mass, 30% by mass, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass Yes, 75% by mass, 80% by mass.
  • the upper limit of the preferred content is 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, 45% by mass, 35% by mass, 25% by mass, 20% by mass, 15% by mass and 10% by mass.
  • the lower limit of the preferred content of the compound represented by the general formula (N-03) is 0% by mass, 1% by mass, 5% by mass, and 10% by mass with respect to the total amount of the liquid crystal composition. %, 20% by mass, 30% by mass, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass Yes, 75% by mass, 80% by mass.
  • the upper limit of the preferred content is 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, 45% by mass, 35% by mass, 25% by mass, 20% by mass, 15% by mass and 10% by mass.
  • the lower limit of the preferred content of the compound represented by formula (N-04) is 0% by mass, 1% by mass, 5% by mass, and 10% by mass with respect to the total amount of the liquid crystal composition. %, 20% by mass, 30% by mass, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass Yes, 75% by mass, 80% by mass.
  • the upper limit of the preferred content is 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, 45% by mass, 35% by mass, 25% by mass, 20% by mass, 15% by mass and 10% by mass.
  • the lower limit of the preferred content of the compound represented by formula (N-05) is 0% by mass, 2% by mass, 5% by mass, and 8% by mass with respect to the total amount of the liquid crystal composition. %, 10% by mass, 13% by mass, 15% by mass, 17% by mass, and 20% by mass.
  • the upper limit of the preferred content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, It is 13 mass %.
  • the liquid crystal composition contains the polymerizable monomer in an amount of 0.1 to 15% by mass, the compound represented by the general formula (N-01-1) in an amount of 1 to 20% by mass, and the general formula (N-01-4). It is particularly preferable to contain 1 to 30% by mass of the compound represented by the formula (1) and 1 to 20% by mass of the compound represented by the general formula (N-04-1).
  • the liquid crystal composition may further contain one kind or two or more kinds of the compounds represented by the general formula (N-06).
  • the compound represented by the general formula (N-06) is effective for adjusting various physical properties, but should be used for obtaining a large refractive index anisotropy ( ⁇ n), a high T NI and a large ⁇ .
  • the lower limit of the preferred content of the compound represented by formula (N-06) is 0% by mass, 2% by mass, 5% by mass, and 8% by mass with respect to the total amount of the liquid crystal composition. %, 10% by mass, 13% by mass, 15% by mass, 17% by mass, and 20% by mass.
  • the upper limit of the preferred content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, 13% by mass, 10% by mass and 5% by mass.
  • the liquid crystal composition preferably contains one kind or two or more kinds selected from the compounds represented by the general formula (NU-01) to the general formula (NU-06).
  • R NU11 , R NU12 , R NU21 , R NU22 , R NU31 , R NU32 , R NU41 , R NU42 , R NU51 , R NU52 , R NU61 and R NU62 each independently have 1 carbon atom.
  • One or more —CH 2 — may be independently substituted by —CH ⁇ CH—, —C ⁇ C—, —O—, —CO—, —COO— or —OCO—.
  • R NU11 , R NU12 , R NU21 , R NU22 , R NU31 , R NU32 , R NU41 , R NU42 , R NU51 , R NU52 , R NU61 and R NU62 each independently have the number of carbon atoms. It is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, and an alkyl group having 1 to 5 carbon atoms or an alkenyl having 2 to 3 carbon atoms. More preferably, it is a group.
  • At least one of R NU11 , R NU21 , R NU31 , R NU41 , R NU51 and R NU61 is preferably an alkenyl group having 2 to 3 carbon atoms.
  • the preferable content of such a compound having an alkenyl group is 10% by mass or more, 20% by mass or more, 25% by mass or more, and 30% by mass or more based on the total amount of the liquid crystal composition. , 40 mass% or more, 45 mass% or more, and 50 mass% or more.
  • the content of the compound having an alkenyl group is preferably 40% by mass or less, 35% by mass or less, and 30% by mass or less.
  • R NU11 is alkyl group having a carbon number of 2 ⁇ 4
  • R NU12 is preferably an alkenyl group having 2 to 3 carbon atoms.
  • R NU11 is alkyl group having a carbon number of 2 ⁇ 4
  • R NU12 is preferably an alkenyl group having 2 to 3 carbon atoms.
  • R NU51 is an alkenyl group having 2 to 3 carbon atoms
  • R NU52 is preferably an alkyl group having 2 to 3 carbon atoms.
  • R NU11 is alkyl group having a carbon number of 2 ⁇ 4
  • R NU12 is preferably an alkenyl group having 2 to 3 carbon atoms.
  • R NU51 and R NU41 are each independently an alkenyl group having 2 to 3 carbon atoms
  • R NU52 and R NU42 are each independently an alkyl group having 2 to 3 carbon atoms. ..
  • the liquid crystal composition preferably contains the compound represented by the general formula (NU-01) or the general formula (NU-02).
  • the liquid crystal composition preferably contains the compounds represented by the general formula (NU-01) and the general formula (NU-03).
  • the liquid crystal composition preferably contains the compounds represented by the general formula (NU-04) and the general formula (NU-05).
  • the liquid crystal composition preferably contains the compound represented by the general formula (NU-05) or the general formula (NU-06).
  • the liquid crystal composition preferably contains compounds represented by the general formula (NU-01) and the general formula (NU-05).
  • the liquid crystal composition preferably contains a compound represented by the general formula (NU-01) or the general formula (NU-06).
  • the liquid crystal composition preferably contains compounds represented by the general formula (NU-01), the general formula (NU-05) and the general formula (NU-06).
  • the content of the compound represented by the general formula (NU-01) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and further preferably 25 to 45% by mass. preferable.
  • the content of the compound represented by the general formula (NU-02) is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and further preferably 5 to 20% by mass. preferable.
  • the content of the compound represented by the general formula (NU-03) is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, and further preferably 0 to 10% by mass. preferable.
  • the content of the compound represented by the general formula (NU-04) is preferably 3 to 30% by mass, more preferably 3 to 20% by mass, and further preferably 3 to 10% by mass. preferable.
  • the content of the compound represented by the general formula (NU-05) is preferably 0 to 30% by mass, more preferably 1 to 20% by mass, and further preferably 3 to 20% by mass. preferable.
  • the content of the compound represented by the general formula (NU-06) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and further preferably 3 to 10% by mass. preferable.
  • the liquid crystal composition of the present invention has, as liquid crystal molecules, a compound having a terphenyl structure or a tetraphenyl structure and a dielectric anisotropy ⁇ of greater than +2, that is, one compound having a positive dielectric anisotropy Two or more types can be contained.
  • ⁇ of the compound is a value extrapolated from the measured value of the dielectric anisotropy of the composition obtained by adding the compound to a composition that is dielectrically almost neutral at 25° C.
  • the compounds are used in combination according to desired properties such as solubility at low temperature, transition temperature, electrical reliability, and refractive index anisotropy.
  • a liquid crystal composition containing a polymerizable monomer is used. The reactivity of the polymerizable monomer in the product can be accelerated.
  • a compound having a terphenyl structure or a tetraphenyl structure and a dielectric anisotropy ⁇ of more than +2 has a preferable lower limit of the content of 0.1% by mass with respect to the total amount of the liquid crystal composition. 0.5% by mass, 1% by mass, 1.5% by mass, 2% by mass, 2.5% by mass, 3% by mass, 4% by mass, 5% by mass And 10% by mass.
  • the upper limit of the preferred content is 20% by mass, 15% by mass, 10% by mass, 9% by mass, 8% by mass, and 7% by mass with respect to the total amount of the liquid crystal composition. , 6% by mass, 5% by mass, 4% by mass and 3% by mass.
  • compounds represented by the formula (M-8.51) to the formula (M-8.54) A compound represented by formula (M-7.1) to a compound represented by formula (M-7.4), a compound represented by formula (M-7.11) to formula (M-7.14)
  • the compound preferably contains a compound represented by the formula (M-7.21) to the formula (M-7.24).
  • the liquid crystal composition of the present invention in order to increase the T NI, the formula (L-7.1) ⁇ formula (L-7.4), the formula (L-7.11) ⁇ formula (L-7. 13), formula (L-7.21) to formula (L-7.23), formula (L-7.31) to formula (L-7.34), formula (L-7.41) to formula (L-7.41) L-7.44) and a compound of formula (L-7.51) to formula (L-7.53), which has four rings and is substantially zero in dielectric (generally in the range of -2 to +2). Good.
  • the liquid crystal composition in the present invention may contain a normal nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, an antioxidant, an ultraviolet absorber, a light stabilizer or an infrared absorber in addition to the above compounds.
  • the antioxidant include hindered phenols represented by the general formula (H-1) to the general formula (H-4).
  • R H1's each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 2 carbon atoms. represents an alkenyl group or an alkenyloxy group having a carbon number of 2 to 10 ⁇ 10, one -CH 2 present in the radical - or non-adjacent two or more -CH 2 - are each independently , -O- or -S- may be substituted, and one or more hydrogen atoms present in the group may be independently substituted with a fluorine atom or a chlorine atom.
  • each R H1 independently represents an alkyl group having 2 to 7 carbon atoms, an alkoxy group having 2 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or 2 to 7 carbon atoms. It is preferably an alkenyloxy group having 7 carbon atoms, and more preferably an alkyl group having 3 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms.
  • M H4 is an alkylene group having 1 to 15 carbon atoms (one or two or more —CH 2 — in the alkylene group is -O -, - CO -, - COO -, - OCO- may be substituted in), -.
  • MH4 has 2 to 12 carbon atoms.
  • those having 3 to 10 carbon atoms are more preferred, those having 4 to 10 carbon atoms are more preferred, those having 5 to 10 carbon atoms are particularly preferred, and those having 6 to 10 carbon atoms are preferred. Is most preferred.
  • one or two or more non-adjacent —CH ⁇ s in the 1,4-phenylene group may be substituted with —N ⁇ . .. Further, each hydrogen atom in the 1,4-phenylene group may be independently substituted with a fluorine atom or a chlorine atom.
  • one or two or more non-adjacent —CH 2 — groups in the 1,4-cyclohexylene group is represented by —O— or —S—. It may be substituted. Further, each hydrogen atom in the 1,4-cyclohexylene group may be independently substituted with a fluorine atom or a chlorine atom.
  • examples of the antioxidant include compounds represented by formulas (H-11) to (H-15).
  • the nematic phase-isotropic liquid phase transition temperature (T NI ) of the liquid crystal composition is preferably 60 to 120° C., more preferably 70 to 100° C., and further preferably 70 to 85° C. preferable. In addition, in this specification, TNI is expressed as high at 60° C. or higher.
  • T NI is preferably 70 to 80° C.
  • T NI is preferably 80 to 90° C.
  • outdoor display applications such as PID (Public Information Display).
  • T NI is preferably 90 to 110° C.
  • the liquid crystal composition preferably has a refractive index anisotropy ( ⁇ n) at 20° C. of 0.08 to 0.14, more preferably 0.09 to 0.13, and 0.09 to 0.14. More preferably, it is 12. More specifically, when it corresponds to a thin cell gap, the refractive index anisotropy ( ⁇ n) is preferably 0.10 to 0.13, and when it corresponds to a thick cell gap, the refractive index anisotropy ( ⁇ n) is ⁇ n) is preferably 0.08 to 0.10. In the present specification, 0.09 or more is expressed as a large ⁇ n.
  • the liquid crystal composition has a rotational viscosity ( ⁇ 1 ) at 20° C.
  • preferably 50 to 160 mPa ⁇ s preferably 50 to 160 mPa ⁇ s, more preferably 55 to 160 mPa ⁇ s, and further preferably 60 to 160 mPa ⁇ s
  • the liquid crystal composition preferably has a dielectric anisotropy ( ⁇ ) at 20° C. of ⁇ 2.0 to ⁇ 8.0, more preferably ⁇ 2.0 to ⁇ 6.0, and ⁇ 2. It is more preferably from 0.0 to -5.0, particularly preferably from -2.5 to -4.0, and most preferably from -2.5 to -3.5.
  • the preferable upper limit of the total content of the compounds having an alkenyl group is 10% by mass, 8% by mass, 6% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass and 0% by mass.
  • the total preferable range of the content of the compound having an alkenyl group is 0 to 10% by mass, 0 to 8% by mass, 0 to 5% by mass, 0 to 4% by mass, 0 ⁇ 3% by mass, and 0 ⁇ 2% by mass.
  • the compound represented by the general formula (NU-01) is excluded.
  • the liquid crystal composition contains a polymerizable monomer which is an essential component, and further includes the general formula (N-01), the general formula (N-02), the general formula (N-03), the general formula (N-04), Compounds containing one kind or two or more kinds selected from the compounds represented by the formula (N-05) and the general formula (N-06), and further represented by the general formulas (NU-01) to (NU-06) It is preferable to contain one kind or two or more kinds selected from the following.
  • the upper limit of the total of these contents is 100 mass %, 99 mass %, 98 mass %, 97 mass %, 96 mass %, 95 mass %, 94 mass %, 93 mass %, 92 mass %, 91 mass %.
  • the liquid crystal display device of the present invention is particularly useful as a liquid crystal display device for driving an active matrix, and is of VA type, FFS type, IPS type, PSA type, PSVA type, PS-IPS type or PS-FFS type, NPS type. , PI-less type, ECB type liquid crystal display elements, etc., but it is particularly preferably used for PSA type, PSVA type, VA type, IPS type, FFS type or ECB type liquid crystal display elements.
  • FIG. 1 is an exploded perspective view schematically showing an embodiment of a liquid crystal display device
  • FIG. 2 is an enlarged plan view of a region surrounded by I line in FIG. Note that, in FIGS. 1 and 2, for convenience, dimensions and ratios thereof are exaggerated and may be different from actual ones. Further, the materials, dimensions, and the like shown below are examples, and the present invention is not limited thereto, and can be appropriately changed within the scope of the invention.
  • the liquid crystal display element 1 shown in FIG. 1 includes an active matrix substrate AM and a color filter substrate CF arranged to face each other, and a liquid crystal layer 4 sandwiched between the active matrix substrate AM and the color filter substrate CF.
  • the active matrix substrate AM includes a first substrate 2, a pixel electrode layer 5 provided on the surface of the first substrate 2 on the liquid crystal layer 4 side, and a surface of the first substrate 2 on the opposite side of the liquid crystal layer 4. It has the 1st polarizing plate 7 provided.
  • the color filter substrate CF is formed on the second substrate 3, the common electrode layer 6 provided on the liquid crystal layer 4 side of the second substrate 3, and the surface of the second substrate 3 opposite to the liquid crystal layer 4. It has a second polarizing plate 8 provided and a color filter 9 provided between the second substrate 3 and the common electrode layer 6.
  • the liquid crystal layer 4 is a vertical alignment type using negative dielectric anisotropy, and in the liquid crystal layer 4, liquid crystal molecules are applied to the substrates AM and CF in a state where no voltage is applied between the electrode layers 5 and 6. Align almost vertically.
  • the liquid crystal display element 1 includes the first polarizing plate 7, the first substrate 2, the pixel electrode layer 5, the liquid crystal layer 4, the common electrode layer 6, the color filter 9,
  • the second substrate 3 and the second polarizing plate 8 are laminated in this order.
  • the first substrate 2 and the second substrate 3 are each formed of a material having flexibility such as a glass material or a plastic material. Both the first substrate 2 and the second substrate 3 may have a light-transmitting property, or only one of them may have a light-transmitting property. In the latter case, the other substrate may be composed of an opaque material such as a metallic material or a silicon material.
  • the pixel electrode layer 5 includes a plurality of gate bus lines 11 for supplying a scanning signal, a plurality of data bus lines 12 for supplying a display signal, and a plurality of pixel electrodes 13.
  • FIG. 2 shows a pair of gate bus lines 11 and 11 and a pair of data bus lines 12 and 12.
  • the plurality of gate bus lines 11 and the plurality of data bus lines 12 are arranged in a matrix so as to intersect with each other, and the region surrounded by these forms a unit pixel of the liquid crystal display element 1.
  • One pixel electrode 13 is formed in each unit pixel.
  • Each pixel may be composed of a plurality of sub-pixels.
  • the pixel electrode 13 includes, for example, two trunk portions that are orthogonal to each other and have a cross shape, and a plurality of branch portions that branch from each trunk portion and that are inclined at an angle of approximately 45° with respect to each trunk portion (so-called). Fishbone structure).
  • the pixel electrode 13 can also be regarded as an electrode having a structure having a slit formed between the branch portions. According to the pixel electrode 13 having such a structure, the liquid crystal molecules are tilted and aligned in the four directions in which the branches are tilted with respect to the trunk. Therefore, four divided domains are formed in one pixel, and the viewing angle of the liquid crystal display element 1 can be widened.
  • each branch portion is preferably about 1 to 5 ⁇ m, more preferably about 2 to 4 ⁇ m.
  • the distance S between the adjacent branch portions is preferably about 1 to 5 ⁇ m, more preferably about 2 to 4 ⁇ m.
  • the gate bus line 11 and the data bus line 12 are preferably formed of, for example, Al, Cu, Au, Ag, Cr, Ta, Ti, Mo, W, Ni, or an alloy containing these, and Mo, Al, or More preferably, it is formed of an alloy containing these.
  • the pixel electrode 13 is composed of, for example, a transparent electrode in order to improve the light transmittance.
  • the transparent electrode is formed by sputtering a compound such as ZnO, InGaZnO, SiGe, GaAs, IZO (Indium Zinc Oxide), ITO (Indium Tin Oxide), SnO, TiO, AZTO (AlZnSnO).
  • the average thickness of the transparent electrode is preferably about 10 to 200 nm.
  • a transparent electrode can be formed as a polycrystalline ITO film by baking an amorphous ITO film.
  • the common electrode layer 6 has, for example, a plurality of striped common electrodes (transparent electrodes) that are provided side by side.
  • This common electrode can also be formed similarly to the pixel electrode 13.
  • the color filter 9 can be formed by, for example, a pigment dispersion method, a printing method, an electrodeposition method, a dyeing method, or the like.
  • a curable coloring composition for a color filter is supplied onto the second substrate 3 so as to have a predetermined pattern, and then heated or irradiated with light to be cured.
  • the color filter 9 can be obtained by performing this operation for three colors of red, green, and blue.
  • the color filter 9 may be arranged on the first substrate 2 side.
  • the liquid crystal display element 1 may be provided with a black matrix (not shown) from the viewpoint of preventing light leakage.
  • This black matrix is preferably formed in a portion corresponding to the thin film transistor.
  • the black matrix may be arranged on the second substrate 3 side together with the color filter 9, or may be arranged on the first substrate 2 side together with the color filter 9, and the black matrix may be arranged on the first substrate 2 side.
  • the color filters 9 may be individually arranged on the second substrate 3 side. Further, the black matrix may be formed by a portion in which the respective colors of the color filter 9 are overlapped and the transmittance is reduced.
  • the active matrix substrate AM and the color filter substrate CF are attached to each other in their peripheral regions by a sealing material (sealing material) composed of an epoxy thermosetting composition, an acrylic UV curable composition, or the like.
  • a sealing material composed of an epoxy thermosetting composition, an acrylic UV curable composition, or the like.
  • a spacer may be arranged between the active matrix substrate AM and the color filter substrate CF to hold a distance between them. Examples of the spacer include granular spacers such as glass particles, plastic particles, and alumina particles, and resin spacer columns formed by a photolithography method.
  • the average distance between the active matrix substrate AM and the color filter substrate CF (that is, the average thickness of the liquid crystal layer 4) is preferably about 1 to 100 ⁇ m.
  • the first polarizing plate 7 and the second polarizing plate 8 can be designed to have a good viewing angle and good contrast by adjusting the positional relationship of their transmission axes. Specifically, it is preferable that the first polarizing plate 7 and the second polarizing plate 8 are arranged so that their transmission axes are orthogonal to each other so that they operate in the normally black mode. In particular, it is preferable that one of the first polarizing plate 7 and the second polarizing plate 8 is arranged such that the transmission axis thereof is substantially 45° with the alignment direction of the liquid crystal molecules when a voltage is applied. ..
  • the liquid crystal display element 1 may include a retardation film for widening the viewing angle.
  • an alignment film such as a polyimide alignment film is provided on the liquid crystal layer 4 side of at least one of the active matrix substrate AM and the color filter substrate CF so as to be in contact with the liquid crystal layer 4. it can.
  • at least one of the active matrix substrate AM and the color filter substrate CF may not have the alignment film.
  • the method for manufacturing a liquid crystal display element of the present embodiment includes a preparatory step [1] for preparing a substrate and a liquid crystal composition, an assembly step [2] for assembling each part, and at least one of an alignment aid and a polymerizable compound. And a polymerization step [3] for polymerizing.
  • a preparatory step [1] for preparing a substrate and a liquid crystal composition includes a preparatory step [1] for preparing a substrate and a liquid crystal composition, an assembly step [2] for assembling each part, and at least one of an alignment aid and a polymerizable compound. And a polymerization step [3] for polymerizing.
  • the sealing material is drawn in a closed loop bank shape by using a dispenser along at least one edge of the active matrix substrate AM and the color filter substrate CF.
  • a predetermined amount of the liquid crystal composition is dropped inside the sealing material, and then the active matrix substrate AM and the color filter substrate CF are arranged to face each other so as to contact the liquid crystal composition under reduced pressure.
  • ODF One Drop Fill
  • the liquid crystal composition as described above has little influence on, for example, a sudden change in pressure or impact in the dropping device that occurs at the time of dropping, and can continue dropping stably for a long time. Therefore, the yield of the liquid crystal display element 1 can be maintained high.
  • the sealing material is cured by irradiation with ultraviolet rays (active energy rays) and heating. Depending on the type of the sealing material, the sealing material may be cured by only one of ultraviolet irradiation and heating.
  • the alignment aid and the polymerizable compound is polymerized by irradiating the liquid crystal composition with active energy rays such as ultraviolet rays and electron beams.
  • active energy rays such as ultraviolet rays and electron beams.
  • a polymer layer (a polymer of at least one of an alignment aid and a polymerizable compound) that controls the liquid crystal alignment is formed at the interface of the liquid crystal layer 4, and the liquid crystal display element 1 is obtained.
  • an appropriate polymerization rate is desirable. Therefore, during the polymerization, it is preferable to irradiate the active energy rays singly, in combination, or sequentially.
  • a polarized light source or a non-polarized light source may be used.
  • the polymerization When the polymerization is performed in a state where the two substrates are opposed to each other so as to contact the liquid crystal composition as in the present embodiment, at least the substrate located on the irradiation surface side is suitable for the active energy rays. It must have good transparency. Further, the polymerization may be carried out in multiple steps as follows. Specifically, first, conditions such as an electric field, a magnetic field, or temperature are adjusted to change the alignment state of liquid crystal molecules. In this state, the liquid crystal composition is irradiated with active energy rays to polymerize at least one of the alignment aid and the polymerizable compound. Next, the liquid crystal composition is irradiated with an activation energy ray without applying an electric field or a magnetic field to polymerize the remaining unpolymerized material (residual monomer).
  • conditions such as an electric field, a magnetic field, or temperature are adjusted to change the alignment state of liquid crystal molecules.
  • the liquid crystal composition is irradiated with active energy rays to polymer
  • the frequency of the applied alternating current is preferably about 10 Hz to 10 kHz, and more preferably about 60 Hz to 10 kHz.
  • the alternating voltage to be applied is selected depending on the desired pretilt angle of the liquid crystal display element 1. That is, the pretilt angle of the liquid crystal display element 1 can be controlled by adjusting the applied AC voltage.
  • the pretilt angle imparted to the liquid crystal molecules is preferably about 85 to 89.5°, more preferably about 87.5 to 89°.
  • the temperature at which the ultraviolet rays are irradiated is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition is maintained.
  • the specific temperature is preferably close to room temperature, that is, typically about 15 to 35°C.
  • a metal halide lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a fluorescent tube, or the like can be used as the lamp that generates ultraviolet rays.
  • the ultraviolet ray to be irradiated is preferably an ultraviolet ray having a wavelength not in the absorption wavelength range of the liquid crystal composition, and it is more preferable to use by cutting a predetermined wavelength as necessary.
  • the intensity of the ultraviolet rays to be applied is preferably about 0.1 mW/cm 2 to 100 W/cm 2 , and more preferably about 2 mW/cm 2 to 50 W/cm 2 .
  • the energy amount of the ultraviolet rays to be irradiated can be adjusted as appropriate, but is preferably about 10 mJ/cm 2 to 500 J/cm 2 , and more preferably about 100 mJ/cm 2 to 200 J/cm 2 .
  • the time for irradiating the ultraviolet rays is appropriately selected depending on the intensity, but is preferably about 10 to 3600 seconds, more preferably about 10 to 600 seconds.
  • a vacuum injection method may be used instead of the drop injection (ODF) method.
  • ODF drop injection
  • the sealing material is screen-printed along the edge of at least one of the active matrix substrate AM and the color filter substrate CF while leaving the injection port.
  • the two substrates AM and CF are bonded together, and the sealing material is thermoset by heating.
  • the liquid crystal composition is injected under vacuum through the injection port into the space defined by the sealing material between the two substrates AM and CF, and then the injection port is sealed.
  • the process proceeds to [3] polymerization step.
  • the liquid crystal display element 1 thus obtained is preferably a PSA type, PSVA type, VA type, IPS type, FFS type or ECB type liquid crystal display element, and more preferably a PSA type liquid crystal display element. More preferable.
  • the present invention is characterized in that the residual amount of the polymerizable monomer (alignment aid and/or polymerizable compound) in the liquid crystal layer 4, that is, the amount of the unreacted polymerizable monomer is adjusted to 200 ppm or less.
  • the amount of the polymerizable monomer remaining in the liquid crystal layer 4 exceeds 200 ppm and increases, the voltage holding ratio (VHR) of the liquid crystal display element 1 sharply decreases.
  • VHR voltage holding ratio
  • the remaining amount of the polymerizable monomer may be 200 ppm or less, preferably 150 ppm or less, and more preferably 100 ppm or less. By adjusting the remaining amount of the polymerizable monomer within such a range, the decrease in the voltage holding ratio of the liquid crystal display element 1 can be further reduced.
  • the total residual amount of them may be within the above range. preferable.
  • the residual amount of each of the alignment aid and the polymerizable compound is preferably 100 ppm or less, more preferably 75 ppm or less, and 50 ppm or less. Is more preferable.
  • the residual amount thereof is preferably 100 ppm or less, more preferably 85 ppm or less.
  • the remaining amount of the polymerizable monomer is preferably as low as possible.
  • the remaining amount of the polymerizable monomer in the liquid crystal layer 4 has a lower limit value, and the specific remaining amount is preferably 10 ppm or more, more preferably 20 ppm or more, and 30 ppm or more. Is more preferable.
  • the residual amount be within the above range.
  • the total residual amount of them is preferably 20 ppm or more, and more preferably 40 ppm or more. It is preferably 60 ppm or more and more preferably 60 ppm or more.
  • the radical is generated.
  • the radicals are less likely to damage the liquid crystal molecules. Therefore, it is possible to reduce the decrease in the voltage holding ratio of the liquid crystal display element 1 over time.
  • the remaining polymerizable monomer is deactivated by itself trapping radicals, if the amount is slightly above, direct damage to the liquid crystal molecules of the polymerizable monomer may be a serious problem. Absent.
  • the polymerizable group is preferably a polymerizable group having an unsaturated bond, more preferably a (meth)acryloyl group, as described above.
  • the intensity, wavelength, energy amount and irradiation time of the active energy ray (ultraviolet ray) with which the liquid crystal composition is irradiated, the type and addition amount of the polymerizable monomer, etc. should be set. Can be adjusted by.
  • the liquid crystal display element of the present invention has been described above based on the embodiment, the present invention is not limited to this, and each configuration may be replaced with any configuration having the same function. May be added.
  • Tni Nematic phase-isotropic liquid phase transition temperature (°C)
  • ⁇ n Refractive index anisotropy at 293K
  • Dielectric constant anisotropy at 293K ⁇ 1 Rotational viscosity at 293K (mPa ⁇ s)
  • K11 Elastic constant of spread at 293K (pN)
  • K33 Elastic constant of bending at 293K (pN)
  • N in the abbreviation is a natural number.
  • composition and physical properties of the liquid crystal mixtures LC-1 and LC-2 are shown in Table 1 below.
  • the alignment aid polymerizable monomer A
  • the following alignment aids SA1 to (SA6) were used.
  • polymerizable compounds PSA1 to (PSA4) were used as the polymerizable compound (polymerizable monomer B).
  • Example 1 Preparation of liquid crystal composition (Example 1) A liquid crystal composition was prepared by mixing the liquid crystal mixture LC-1 with the alignment aid (SA2) in an amount of 0.7 mass% and heating and melting the mixture. Therefore, the polymerizable compound was not mixed in the liquid crystal composition of Example 1. (Examples 2 to 21, Comparative Examples 1 to 5) A liquid crystal composition was prepared in the same manner as in Example 1 except that the types and addition amounts of the liquid crystal mixture, the alignment aid and the polymerizable compound were changed as shown in Table 2.
  • SA2 alignment aid
  • a first substrate (a common electrode substrate) having a transparent electrode layer and no alignment film, and an alignment film having a pixel electrode layer having a transparent pixel electrode driven by an active element are provided.
  • a second substrate (pixel electrode substrate) was prepared.
  • the liquid crystal composition was sandwiched between the second substrates, and the sealing material was cured at 110° C. for 2 hours under normal pressure to form a liquid crystal cell with a cell gap of 3.2 ⁇ m. Obtained.
  • ultraviolet rays were radiated through a filter that cuts ultraviolet rays having a wavelength of 325 nm or less using a high pressure mercury lamp.
  • the illuminance (intensity) measured under the condition of the central wavelength of 365 nm was adjusted so as to be 100 mW/cm 2 , and the integrated light amount of 10 J/cm 2 of ultraviolet rays was irradiated.
  • This ultraviolet irradiation condition was set as irradiation condition 1.
  • the pretilt angle is given to the liquid crystal molecules in the liquid crystal cell by the irradiation of the ultraviolet rays under the irradiation condition 1.
  • the liquid crystal cell was adjusted using a fluorescent UV lamp manufactured by Toshiba Lighting & Technology Co., Ltd. so that the illuminance (intensity) measured under the condition of the central wavelength of 313 nm was 3 mW/cm 2 , and the integrated light amount was 10 J/cm 2.
  • Ultraviolet rays were irradiated at any of (low), 20 J/cm 2 (medium), and 50 J/cm 2 (high). Thereby, a liquid crystal display element was obtained.
  • This ultraviolet irradiation condition was set as irradiation condition 2.
  • the amount of unreacted polymerizable monomer (alignment aid and polymerizable compound) remaining in the liquid crystal cell was reduced by irradiation with ultraviolet rays under irradiation condition 2.
  • Two liquid crystal cells were produced using each liquid crystal composition.
  • the amount of the remaining polymerizable monomer was determined from the ratio of the peak area of the liquid crystal molecule as an index and the peak area of the unreacted polymerizable monomer.
  • the residual amount of the polymerizable monomer was determined from the obtained value and the amount (initial amount) of the polymerizable monomer added when the liquid crystal composition was prepared.
  • VHR voltage holding ratio
  • VHR Change in Voltage Holding Ratio
  • the pretilt angle of liquid crystal molecules was measured using a pretilt angle measuring system (“OPTIPRO” manufactured by Shintech Co., Ltd.). This pretilt angle was used as the initial value.
  • the liquid crystal cell was irradiated with light continuously from the backlight for 10 hours while applying a rectangular voltage of 30 V at a frequency of 100 Hz. After that, the pretilt angle was measured again and used as the pretilt angle (post-test value).
  • the voltage of 30 V is several times larger than the normal driving voltage, and the acceleration test is performed.
  • the value obtained by subtracting the pretilt angle (post-test value) from the measured pretilt angle (initial value) was evaluated as the pretilt angle change amount ( absolute value of pretilt angle change) [°] according to the following criteria.
  • Evaluation criteria S: Change within 0.1° (almost no display failure occurs) A: Change of more than 0.1° and within 0.3 (display defects are unlikely to occur) B: Change of more than 0.3° and less than 0.5° (a considerable display defect occurs) C: Change over 0.5° (unacceptable level due to display failure) The above results are shown in Table 2 below.
  • each example has better vertical alignment, VHR and tilt stability than each comparative example, and is suitable for achieving vertical alignment of liquid crystal molecules in a liquid crystal cell having no alignment film. I knew it was.
  • the residual amount of each polymerizable monomer was 10 ppm or more (particularly 30 ppm or more), it was possible to suppress the change with time (decrease with time) of VHR.

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