WO2013035811A1 - Composition de cristaux liquides ferroélectriques et dispositif d'affichage à cristaux liquides - Google Patents

Composition de cristaux liquides ferroélectriques et dispositif d'affichage à cristaux liquides Download PDF

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WO2013035811A1
WO2013035811A1 PCT/JP2012/072805 JP2012072805W WO2013035811A1 WO 2013035811 A1 WO2013035811 A1 WO 2013035811A1 JP 2012072805 W JP2012072805 W JP 2012072805W WO 2013035811 A1 WO2013035811 A1 WO 2013035811A1
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liquid crystal
alignment
chiral compound
group
crystal composition
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Japanese (ja)
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直子 沖本
岡部　将人
石川　誠
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大日本印刷株式会社
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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
    • C09K19/02—Liquid crystal materials characterised by optical, electrical or physical properties of the components, in general
    • C09K19/0225—Ferroelectric
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3025—Cy-Ph-Ph-Ph

Definitions

  • the present invention relates to a liquid crystal display element using a ferroelectric liquid crystal composition having impact resistance.
  • Liquid crystal display elements are widely used from large displays to portable information terminals because of their thinness and low power consumption, and their development is actively underway. So far, liquid crystal display elements have been developed and put to practical use, such as TN mode, STN multiplex drive, and active matrix drive using thin layer transistors (TFTs) for TN, but these use nematic liquid crystals. In addition, the response speed of the liquid crystal material is as slow as several ms to several tens of ms, and it cannot be said that it is sufficiently compatible with moving image display.
  • TFTs thin layer transistors
  • Ferroelectric liquid crystal is expected to provide a high-performance liquid crystal display element because it has a superior response speed such as a wide viewing angle because it has a response speed as short as ⁇ s and is suitable for high-speed devices. .
  • the ferroelectric liquid crystal has a higher molecular order than the nematic liquid crystal, so that it is difficult to return to its original state when the regularity of molecular orientation is disturbed by impact, that is, it is very weak to external impact.
  • a method of arranging a partition wall (also referred to as a rib) between a pair of substrates has been proposed (see, for example, Patent Document 1 and Patent Document 2).
  • a partition wall also referred to as a rib
  • a method of adding a gelling agent to a ferroelectric liquid crystal composition see Patent Document 3
  • a method of adding a curable resin to a ferroelectric liquid crystal composition and ferroelectricity
  • a method of adding a thermoplastic resin to a liquid crystal composition see Patent Document 4
  • a method using a ferroelectric polymer liquid crystal having a ferroelectric liquid crystal structure in a side chain, a liquid crystal polymer compound and a low molecular ferroelectric liquid crystal A method of mixing compounds has been proposed.
  • these methods have a problem that the drive voltage becomes high.
  • the regularity of the molecular orientation is less likely to be disturbed to a certain degree of weak impact, but the orientation regularity is disturbed by a strong impact.
  • the essential problem that it is difficult to return to the original state has not been solved.
  • Patent Document 6 when a ferroelectric liquid crystal composition containing a chiral compound having a predetermined structure in which four benzene rings are directly bonded is used, the contrast ratio is good even after an impact is applied. It has been reported that On the other hand, Patent Document 6 discloses a chiral compound having a predetermined structure in which three or five benzene rings are directly bonded, but there is no detailed description of impact resistance. Furthermore, it was reported that when a ferroelectric liquid crystal composition containing a chiral compound having a predetermined structure in which three benzene rings were directly bonded was used, the contrast ratio deteriorated when an impact was applied. There is room for improvement in impact resistance.
  • the present invention has been made in view of the above circumstances, and has as its main object to provide a ferroelectric liquid crystal composition exhibiting excellent impact resistance when used in a liquid crystal display device.
  • the present inventors have made various studies on the impact resistance of a liquid crystal display device using a ferroelectric liquid crystal composition, and as a result, in addition to a chiral compound having a predetermined structure in which four benzene rings are directly bonded. It has been found that when a ferroelectric liquid crystal composition containing a chiral compound having a predetermined structure in which three benzene rings and one cyclohexane ring are directly bonded is used, the impact resistance is further improved. The present invention has been completed based on such findings.
  • the present invention provides a ferroelectric liquid crystal composition
  • a ferroelectric liquid crystal composition comprising a chiral compound A represented by the following general formula (1) and a chiral compound B represented by the following general formula (2). To do.
  • R 1 is a saturated or unsaturated alkyl or alkoxyalkyl group having 4 to 18 carbon atoms which may be substituted with a halogen atom.
  • R 2 is a chiral group and is represented by the following general formula (3).
  • R 3 is a saturated or unsaturated alkyl group or alkoxyalkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom.
  • Y 1 represents a methyl group or a fluorine atom.
  • m and n are each independently 0 or 1. * Indicates an asymmetric carbon atom.
  • X 1 to X 8 each independently represents a methyl group, a methyl fluoride group, a halogen atom, or a hydrogen atom. However, one or more of X 1 to X 8 are each independently a methyl group, a methyl fluoride group, or a halogen atom.
  • R 4 is a linear saturated or unsaturated alkyl or alkoxyalkyl group having 4 to 18 carbon atoms which may be substituted with a halogen atom.
  • R 5 is a chiral group and is a substituent represented by the general formula (3).
  • X 9 to X 20 each independently represents a methyl group, a methyl fluoride group, a halogen atom, or a hydrogen atom. However, one or more of X 9 to X 20 are each independently a methyl group, a methyl fluoride group, or a halogen atom.
  • K represents a single bond or a cyclohexane ring.
  • the ferroelectric liquid crystal contains the chiral compound A represented by the above formula (1) and the chiral compound B represented by the above formula (2) in the ferroelectric liquid crystal composition.
  • the composition is used for a liquid crystal display element, it is possible to improve impact resistance.
  • the content of the chiral compound B is preferably not less than the content of the chiral compound A.
  • the tilt angle of liquid crystal molecules can be increased and the driving performance can be improved due to the large content of the chiral compound B. It is.
  • the total content of the chiral compound A and the chiral compound B is preferably in the range of 5% by mass to 35% by mass. This is because when the ferroelectric liquid crystal composition is used in a liquid crystal display element, excellent impact resistance can be obtained.
  • the present invention includes a first alignment substrate having a first substrate, a first electrode layer formed on the first substrate, a first alignment layer formed on the first electrode layer, 2 substrate, a second electrode layer formed on the second substrate, a second alignment treatment substrate having a second alignment layer formed on the second electrode layer, the first alignment layer and A liquid crystal display element having a liquid crystal layer formed between the second alignment layers, wherein the liquid crystal layer contains the ferroelectric liquid crystal composition.
  • liquid crystal display element having excellent impact resistance can be obtained.
  • the constituent material of the first alignment layer and the constituent material of the second alignment layer have different compositions. This is because the alignment defects of the liquid crystal display element are reduced and the contrast can be improved.
  • the ferroelectric liquid crystal composition contains the chiral compound A represented by the above formula (1) and the chiral compound B represented by the above formula (2), thereby being used for a liquid crystal display element. In this case, there is an effect that the impact resistance can be improved.
  • ferroelectric liquid crystal composition and the liquid crystal display element of the present invention will be described in detail.
  • ferroelectric liquid crystal composition of the present invention comprises a chiral compound A represented by the above formula (1) and a chiral compound B represented by the above formula (2). To do.
  • the ferroelectric liquid crystal composition In a liquid crystal display device using a ferroelectric liquid crystal composition, if the ferroelectric liquid crystal composition is easily crystallized, it is difficult to return to its original state when liquid crystal molecules move due to an impact, and the It is considered that the impact property is inferior.
  • the benzene ring has a planar structure, whereas the cyclohexane ring has a three-dimensional structure. Therefore, the chiral compound A in which the three benzene rings represented by the above formula (1) and one cyclohexane ring are directly bonded has a bent structure due to the cyclohexane ring.
  • the chiral compound B in which the four benzene rings represented by the above formula (2) are directly bonded has a rod-like structure when K is a single bond, and when K is a cyclohexane ring. It has a bent structure.
  • the chiral compound A having a bent structure and the chiral compound B having a rod-like structure in which K is a single bond are contained, when the liquid crystal display element is used, the chiral compound A and the chiral compound B Due to the difference in structure flexibility, the regularity of the liquid crystal molecules is lost, and the crystallization of the ferroelectric liquid crystal composition is hindered.
  • the chiral compound A having a bent structure and the chiral compound B having a bent structure in which K is a cyclohexane ring are contained, when the liquid crystal display device is formed, the chiral compound A and the chiral compound The regularity of the liquid crystal molecules is lost due to the difference in the flexibility of the structure of chiral compound A and chiral compound B due to the difference in the number of benzene rings of B, that is, the length of the core, and the crystallization of the ferroelectric liquid crystal composition is inhibited. Is done.
  • the ferroelectric liquid crystal composition of the present invention contains a chiral compound A represented by the above formula (1) and a chiral compound B represented by the above formula (2), thereby being used for a liquid crystal display device. In such a case, excellent impact resistance can be achieved.
  • R 1 is a saturated or unsaturated alkyl group or alkoxyalkyl group having 4 to 18 carbon atoms which may be substituted with a halogen atom.
  • the number of carbon atoms may be 4 to 18, but 6 to 18 is preferable and 6 to 12 is more preferable. This is because when the number of carbon atoms is larger than the above range, the synthesis of the chiral compound becomes difficult and the cost increases. On the other hand, when the number of carbon atoms is less than the above range, the ferroelectric liquid crystal composition of the present invention may not exhibit a smectic phase.
  • the ferroelectric liquid crystal composition of the present invention may exhibit a smectic phase with a relatively small number of carbon atoms.
  • the alkyl group or alkoxyalkyl group may be substituted with a halogen atom or may not be substituted with a halogen atom, but is preferably not substituted with a halogen atom.
  • the alkyl group or alkoxyalkyl group is linear or branched.
  • the alkyl group or alkoxyalkyl group may be saturated or unsaturated, but is preferably saturated.
  • R 1 may be an alkyl group or an alkoxyalkyl group, but is preferably an alkyl group.
  • R 2 is a chiral group having one or more chiral centers and is bonded via —O—. It is represented by the following general formula (3).
  • R 3 is a saturated or unsaturated alkyl group or alkoxyalkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom.
  • the alkyl group or alkoxyalkyl group may be linear, cyclic, or branched.
  • the alkyl group or alkoxyalkyl group may be substituted with a halogen atom or may not be substituted with a halogen atom.
  • R 3 may be an alkyl group or an alkoxyalkyl group, but is preferably an alkyl group.
  • Y 1 represents a methyl group or a fluorine atom.
  • the methyl group there is an advantage that the synthesis of the chiral compound A is easy.
  • fluorine atoms the spontaneous polarization of liquid crystal molecules increases, and there is an advantage that the response speed can be increased when the ferroelectric liquid crystal composition of the present invention is used in a liquid crystal display element.
  • Y 1 may be a methyl group or a fluorine atom, but is preferably a methyl group. As described above, the synthesis of the chiral compound A is easy, the chiral compound A can be produced stably, and the ferroelectric liquid crystal composition can be obtained at a low cost.
  • M and n are each independently 0 or 1.
  • the 1-position or 2-position is an asymmetric carbon atom.
  • the 1st or 2nd position is an asymmetric carbon atom having a chiral center, so that it has a sufficient impact resistance when used in a liquid crystal display device. Liquid crystal composition.
  • X 1 to X 8 each independently represents a methyl group, a methyl fluoride group, a halogen atom, or a hydrogen atom. However, one or more of X 1 to X 8 are each independently a methyl group, a methyl fluoride group or a halogen atom. When all of X 1 to X 8 are hydrogen atoms, the solubility of the chiral compound A is lowered, so that the synthesis and purification of the chiral compound A becomes difficult, the cost is increased, and the strength of the present invention is increased.
  • the dielectric liquid crystal composition is likely to be crystallized, and when used in a liquid crystal display element, the desired impact resistance may not be obtained.
  • any one or more of X 1 to X 3 and X 5 to X 7 are each independently a methyl group, a methyl fluoride group, or a halogen atom.
  • the chiral compound has better solubility than the X 4 and X 8 positions when it has a substituent at the X 1 to X 3 and X 5 to X 7 positions. This is presumably because the X 4 and X 8 positions are less distorted by substituents than the other positions.
  • the benzene ring having a substituent can have 1 to 4 substituents, and among them, it preferably has one substituent. . That is, when the benzene ring to which X 1 , X 2 , X 5 , and X 6 are bonded has a substituent, any one of X 1 , X 2 , X 5 , and X 6 is a methyl group, It is preferably a methyl fluoride group or a halogen atom.
  • any one of X 3 , X 4 , X 7 , and X 8 is a methyl group or a fluorine. It is preferably a methyl group or a halogen atom. In particular, it is preferable that only one of X 1 to X 8 is a methyl group, a methyl fluoride group or a halogen atom.
  • the benzene ring which has a substituent among two benzene rings has two substituents.
  • fluorine atoms are respectively substituted on adjacent carbon atoms of the benzene ring as in the case where, for example, X 1 and X 2 are fluorine atoms.
  • the rod-like structure of the chiral compound is not destroyed, so that the impact resistance can be maintained.
  • one benzene ring preferably has two substituents, and among them, X 1 , X 2 , X 5 , X 6
  • the benzene ring to which is bonded preferably has two substituents. This is because, among the three directly bonded benzene rings, the ferroelectric liquid crystal composition is difficult to crystallize because the middle benzene ring has a substituent.
  • X 1 and X 2 or X 5 and X 6 are preferably fluorine atoms.
  • the substituent that the benzene ring has is preferably a methyl group, a fluorine atom, or a chlorine atom, and particularly preferably a methyl group or a fluorine atom, when there is one substituent.
  • any substituent is a fluorine atom.
  • the two fluorine atoms are preferably substituted with adjacent carbon atoms.
  • chiral compound A represented by the above formula (1) examples include chiral compounds A represented by the following general formulas (1-1) to (1-2) and (1-3) to (1-4). Can be mentioned.
  • R 11 is a saturated or unsaturated alkyl group having 1 to 10 carbon atoms
  • i is In the above formulas (1-1) to (1-2), one of j and k is 0, the other is 1, p is 4 to 18, and X 11 and X 12 are respectively Independently represents a methyl group, a methyl fluoride group or a halogen atom, and the * mark indicates a chiral center.
  • R 11 is a saturated or unsaturated alkyl group having 1 to 10 carbon atoms.
  • the alkyl group is linear, branched or cyclic.
  • R 11 is preferably a linear or branched saturated alkyl group or a phenylalkyl group.
  • p is 4 to 18, preferably 6 to 18, and more preferably 6 to 12. .
  • the ferroelectric liquid crystal composition of the present invention may not exhibit a smectic phase.
  • X 11 and X 12 each independently represent a methyl group, a methyl fluoride group or a halogen atom. Of these, a methyl group, a fluorine atom or a chlorine atom is preferable, and a methyl group or a fluorine atom is particularly preferable.
  • the positions of X 11 and X 12 are the same as the positions of X 1 to X 8 described above.
  • chiral compound A represented by the above formulas (1-1) and (1-2) include a chiral compound A represented by the following formula.
  • chiral compound A represented by the above formulas (1-3) and (1-4) include a chiral compound A represented by the following formula.
  • the dextrorotatory property is indicated by (+) and the levorotatory property is indicated by ( ⁇ ).
  • chiral compound A one kind may be used alone, or two or more kinds may be mixed and used.
  • the chiral compound A has a bent structure by having three benzene rings and one cyclohexane ring.
  • the chiral compound A has a bent structure, high impact resistance is exhibited when used in a ferroelectric liquid crystal composition by mixing with the chiral compound B described later.
  • Chiral compound A can be synthesized, for example, by the method described in International Publication No. 2010/031431.
  • Chiral compound B The chiral compound used in the present invention is represented by the following general formula (2).
  • R 4 is a saturated or unsaturated alkyl or alkoxyalkyl group having 4 to 18 carbon atoms which may be substituted with a halogen atom.
  • the number of carbon atoms may be 4-18, but 6-18, especially 6-12 are preferred. This is because when the number of carbon atoms is larger than the above range, the synthesis of the chiral compound B becomes difficult and the cost increases. On the other hand, when the number of carbon atoms is less than the above range, the ferroelectric liquid crystal composition of the present invention may not exhibit a smectic phase.
  • the ferroelectric liquid crystal composition of the present invention may exhibit a smectic phase with a relatively small number of carbon atoms.
  • the alkyl group or alkoxyalkyl group may be substituted with a halogen atom or may not be substituted with a halogen atom, but is preferably not substituted with a halogen atom.
  • the alkyl group or alkoxyalkyl group is linear or branched.
  • the alkyl group or alkoxyalkyl group may be saturated or unsaturated, but is preferably saturated.
  • R 4 may be an alkyl group or an alkoxyalkyl group, but is preferably an alkyl group.
  • R 5 is a chiral group having a chiral center and is bonded via —O—. It is represented by the following general formula (3).
  • R 3 is a saturated or unsaturated alkyl group or alkoxyalkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom.
  • the alkyl group or alkoxyalkyl group may be linear, cyclic, or branched.
  • the alkyl group or alkoxyalkyl group may be substituted with a halogen atom or may not be substituted with a halogen atom.
  • R 3 may be an alkyl group or an alkoxyalkyl group, but is preferably an alkyl group.
  • Y 1 represents a methyl group or a fluorine atom.
  • a methyl group there is an advantage that a chiral compound can be easily synthesized.
  • fluorine atoms the spontaneous polarization of liquid crystal molecules increases, and there is an advantage that the response speed can be increased when the ferroelectric liquid crystal composition of the present invention is used in a liquid crystal display element.
  • Y 1 may be a methyl group or a fluorine atom, but is preferably a methyl group. This is because the chiral compound B can be easily synthesized as described above, the chiral compound B can be stably produced, and a ferroelectric liquid crystal composition can be obtained at a low cost.
  • M and n are each independently 0 or 1.
  • the 1-position or 2-position is an asymmetric carbon atom.
  • the 1st or 2nd position is an asymmetric carbon atom having a chiral center, so that it has a sufficient impact resistance when used in a liquid crystal display device. Liquid crystal composition.
  • X 9 to X 20 each independently represents a methyl group, a methyl fluoride group, a halogen atom, or a hydrogen atom. However, one or more of X 9 to X 20 are each independently a methyl group, a methyl fluoride group, or a halogen atom. When all of X 9 to X 20 are hydrogen atoms, the solubility of the chiral compound B decreases, so that the synthesis and purification of the chiral compound B becomes difficult, the cost increases, and the strength of the present invention is increased. The dielectric liquid crystal composition is likely to be crystallized, and when used in a liquid crystal display element, the desired impact resistance may not be obtained.
  • X 9 to X 20 are a methyl group, a methyl fluoride group or a halogen atom as in the present invention
  • the solubility of the chiral compound B in the solvent increases, Synthesis and purification become possible.
  • the steric structure of the chiral compound B is distorted and the crystallization of the ferroelectric liquid crystal composition is inhibited by the distortion, it is considered that high impact resistance can be obtained.
  • any one or more of X 9 to X 13 and X 15 to X 19 are preferably each independently a methyl group, a methyl fluoride group, or a halogen atom. This is because the chiral compound has better solubility than the X 14 and X 20 positions when it has a substituent at the X 9 to X 13 and X 15 to X 19 positions. This is presumably because the X 14 and X 20 positions are less distorted by substituents than the other positions.
  • the benzene ring having a substituent can have 1 to 4 substituents, and among them, it preferably has one substituent. . That is, when the benzene ring to which X 9 , X 10 , X 15 , and X 16 are bonded has a substituent, any one of X 9 , X 10 , X 15 , and X 16 is a methyl group, It is preferably a methyl fluoride group or a halogen atom.
  • any one of X 11 , X 12 , X 17 , and X 18 is a methyl group or a fluorine. It is preferably a methyl group or a halogen atom.
  • any one of X 13 , X 14 , X 19 , and X 20 is a methyl group or a fluorine group. It is preferably a methyl group or a halogen atom.
  • X 9 to X 20 is a methyl group, a methyl fluoride group, or a halogen atom, or any one of X 11 , X 12 , X 17 , X 18 and X Any one of 13 , X 14 , X 19 and X 20 is preferably a methyl group, a methyl fluoride group or a halogen atom. That is, the total number of substituents of the three benzene rings to which X 9 to X 20 are bonded is preferably 1 or 2.
  • the benzene ring which has a substituent has two substituents.
  • the position of the two substituents is such that, for example, when X 9 and X 10 are fluorine atoms, the adjacent carbon atoms of the benzene ring are each substituted with a fluorine atom. It is preferable. Further, it is preferable that one of the three benzene rings to which X 9 to X 20 are bonded has one substituent.
  • the total number of substituents of the three benzene rings to which X 9 to X 20 are bonded is two, and that one benzene ring has two substituents.
  • the benzene ring to which X 9 , X 10 , X 15 , X 16 or X 11 , X 12 , X 17 , X 18 is bonded has two substituents. This is because, among the four directly bonded benzene rings, the ferroelectric liquid crystal composition is difficult to crystallize because the middle benzene ring has a substituent.
  • X 9 and X 10 , X 11 and X 12 , X 15 and X 16 , or X 17 and X 18 are preferably fluorine atoms.
  • the substituent that the benzene ring has is preferably a methyl group, a fluorine atom, or a chlorine atom, and particularly preferably a methyl group or a fluorine atom, when there is one substituent.
  • any substituent is a fluorine atom.
  • the two fluorine atoms are preferably substituted with adjacent carbon atoms.
  • the total number of substituents on the three benzene rings to which X 9 to X 20 are bonded is preferably 3 to 8. This is because when the total number of substituents is large, crystallization of the ferroelectric liquid crystal composition can be suppressed.
  • the total number of substituents is preferably 3 to 5, more preferably 3.
  • Benzene ring having two substituents benzene ring to which X 9 , X 10 , X 15 , and X 16 are bonded, and X 13 , X 14 , X 19 , and X 20 are bonded to each other
  • Each of the benzene rings preferably has 0 to 3 substituents in total, 1 to 6 substituents.
  • crystallization of the ferroelectric liquid crystal composition can be effectively suppressed, and the liquid crystal display element can be driven stably at a low temperature. Moreover, it can prevent that content of the chiral compound in a ferroelectric liquid-crystal composition is restrict
  • the benzene ring to which X 11 , X 12 , X 17 and X 18 are bonded has two substituents, and the benzene ring to which X 9 , X 10 , X 15 and X 16 are bonded is 1 It preferably has ⁇ 3 substituents. This is because, among the directly bonded benzene rings, the benzene ring located in the middle has a substituent, so that the crystallization of the ferroelectric liquid crystal composition is effectively suppressed.
  • the benzene ring to which X 11 , X 12 , X 17 and X 18 are bonded has two substituents, and X 9 , X
  • the benzene ring to which 10 , X 15 , and X 16 are bonded, or the benzene ring to which X 13 , X 14 , X 19 , and X 20 are bonded preferably has one substituent.
  • the benzene ring to which X 11 , X 12 , X 17 and X 18 are bonded has two substituents, and the benzene ring to which X 9 , X 10 , X 15 and X 16 are bonded.
  • the benzene ring having one substituent has one substituent. This is because, as described above, when the benzene ring located in the middle has a substituent, crystallization of the ferroelectric liquid crystal composition is effectively suppressed.
  • examples of the substituent that the benzene ring has include a benzene ring to which X 9 , X 10 , X 15 and X 16 are bonded, and a benzene ring to which X 13 , X 14 , X 19 and X 20 are bonded.
  • the substituent possessed by is preferably a methyl group, a methyl fluoride group or a halogen atom, and more preferably a methyl group.
  • X 11, X 12, X 17 , substituent group of the benzene ring X 18 is attached is a fluorine atom.
  • X 9 or X 10 is preferably a methyl group, and X 11 and X 12 are preferably fluorine atoms.
  • K represents a single bond or a cyclohexane ring. Among these, a single bond is preferable.
  • R 12 is a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, z is 0 or 1, and t is 4 to 18.
  • at least one of u, v and w is 1 or 2 is 1, and the rest is 0, and the above formulas (2-3) to (2-4)
  • X 20 to X 23 each independently represents a methyl group, a methyl fluoride group, or a halogen atom, and K represents a single bond or a cyclohexane ring.
  • * indicates a chiral center.
  • t is 4 to 18, preferably 6 to 18, and more preferably 6 to 12. This is because if t is larger than the above range, the synthesis of chiral compound B becomes difficult and the cost increases. On the other hand, if t is less than the above range, the ferroelectric liquid crystal composition of the present invention may not exhibit a smectic phase.
  • R 12 is a saturated or unsaturated alkyl group having 1 to 10 carbon atoms.
  • the alkyl group is linear, branched or cyclic. Among them, R 12 is preferably a linear or branched saturated alkyl group or a phenylalkyl group.
  • X 20 to X 23 each independently represents a methyl group, a methyl fluoride group or a halogen atom. .
  • a methyl group, a fluorine atom or a chlorine atom is preferable, and a methyl group or a fluorine atom is particularly preferable.
  • the positions of X 20 to X 23 are the same as the positions of X 9 to X 20 described above.
  • K represents a single bond or a cyclohexane ring. Among these, a single bond is preferable.
  • chiral compound B represented by the above formula (2) examples include the chiral compound B represented by the following general formula.
  • chiral compound B represented by the above formulas (2-3) to (2-4) include chiral compounds represented by the following formula.
  • dextrorotatory property is indicated by (+)
  • levorotatory property is indicated by ( ⁇ ).
  • chiral compound B represented by the above formula (2-5) examples include a chiral compound represented by the following formula.
  • 1 type may be used independently and 2 or more types may be mixed and used.
  • the chiral compound B has at least four benzene rings.
  • K represented by the above formula (2) is a single bond, it forms a rod-like structure, while K is cyclohexane. If it is a ring, it has a bent structure.
  • the chiral compound B has such a structure, high impact resistance can be obtained when used by mixing with the chiral compound A described above.
  • Chiral compound B can be synthesized, for example, by the method described in International Publication No. 2010/031431.
  • Chiral compound A and chiral compound B are used as a mixture.
  • chiral compound A may be used individually by 1 type, and 2 or more types may be mixed and used for it.
  • the chiral compound B may be used alone or in combination of two or more.
  • the above-mentioned chiral compound A and chiral compound B to which different numbers of benzene rings are bonded are mixed and used as a ferroelectric liquid crystal composition, whereby high impact resistance is obtained when used in a liquid crystal display device. It is possible to achieve. That is, when a chiral compound A having a bent structure and a rod-like chiral compound B in which K is a single bond are mixed, the order of the liquid crystal molecules is determined by the difference in the flexibility of the structures of the chiral compound A and the chiral compound B. The properties are lost and the impact resistance is increased.
  • the number of benzene rings of the chiral compound A and the chiral compound B, that is, the length of the core is Due to the difference in flexibility due to the difference, the regularity of the liquid crystal molecules breaks down and the impact resistance becomes high.
  • the content of the chiral compound A in the ferroelectric liquid crystal composition is not particularly limited as long as an impact resistance effect is obtained.
  • the content of the chiral compound A is ferroelectric.
  • the total content of the two or more chiral compounds A is ferroelectric. It is preferable that it is 5 mass% or more in a crystalline liquid crystal composition.
  • the content of the chiral compound B in the ferroelectric liquid crystal composition is not particularly limited as long as an impact resistance effect is obtained.
  • the content of the chiral compound B is ferroelectric.
  • the total content of the two or more chiral compounds B is ferroelectric. It is preferable that it is 5 mass% or more in a crystalline liquid crystal composition.
  • the total content of chiral compound A and chiral compound B in the ferroelectric liquid crystal composition is not particularly limited as long as a desired effect is obtained, but is in the range of 5% by mass to 35% by mass. Is preferably within the range of 15% by mass to 30% by mass. This is because if the total content of the chiral compound A and the chiral compound B is less than the above range, desired impact resistance may not be obtained. On the other hand, if the total content of the chiral compound A and the chiral compound B is larger than the above range, the ferroelectric liquid crystal composition has a high viscosity and is easily crystallized, so that sufficient impact resistance is obtained. This is because the formation of a liquid crystal layer may be difficult when a liquid crystal display element is manufactured.
  • the chiral compound B is contained more than the chiral compound A.
  • the chiral compound A tends to reduce the tilt angle of liquid crystal molecules when a voltage is applied as compared with the chiral compound B.
  • the tilt angle of the liquid crystal molecules becomes small and there is a possibility that sufficient brightness cannot be obtained.
  • the chiral compound B is more contained than the chiral compound A, the tilt angle of the liquid crystal molecules can be increased when the ferroelectric liquid crystal composition is used in a liquid crystal display device. , Driving performance can be improved.
  • the ferroelectric liquid crystal composition of the present invention may contain a host liquid crystal in addition to the above chiral compound A and chiral compound B.
  • host liquid crystal those generally used as the host liquid crystal of the ferroelectric liquid crystal composition can be used, and examples thereof include a phenylpyrimidine compound.
  • a host liquid crystal may be used individually by 1 type, and 2 or more types may be mixed and used for it.
  • the phenylpyrimidine compound used as the host liquid crystal is preferably a phenyl group substituted with a fluorine atom, and more preferably a phenyl group substituted with one or two fluorine atoms. .
  • the phase transition temperature of the chiral smectic C phase of the ferroelectric liquid crystal composition of the present invention is widened, so that the ferroelectric liquid crystal composition of the present invention is liquid crystal This is because, when used in a display element, the liquid crystal display element can be driven stably at low and high temperatures.
  • the viscosity of the ferroelectric liquid crystal composition of the present invention is lowered, there is an advantage that the liquid crystal layer can be easily formed in the manufacturing process of the liquid crystal display element. Furthermore, when a ferroelectric liquid crystal composition is applied or dropped when a liquid crystal display device is produced by using a phenylpyrimidine compound in which the phenyl group is substituted with a fluorine atom, the coating mark and the dropping mark are not observed. Since it becomes difficult to occur, it is possible to prevent alignment disorder of liquid crystal molecules due to coating marks and dropping marks, and to suppress the occurrence of alignment defects.
  • phenylpyrimidine compounds include those represented by the following general formulas (4-1) to (4-4).
  • R 21 and R 22 are alkyl groups, and R 22 is an alkoxy group or a carboxyl group.
  • the phenylpyrimidine compound is a bicyclic compound having one pyrimidine ring and one benzene ring, a tricyclic compound having one pyrimidine ring and two benzene rings, one pyrimidine ring and 1 Any of a tricyclic compound having one benzene ring and one cyclohexane ring may be used. Especially, as a phenyl pyrimidine compound, it is preferable to mix the said tricyclic compound with the said bicyclic compound.
  • the phase transition temperature of the chiral smectic C phase of the ferroelectric liquid crystal composition of the present invention is higher when the tricyclic compound is mixed with the bicyclic compound than when the bicyclic compound is used alone. This is because the usable range is widened when used in a liquid crystal display element.
  • the content of the host liquid crystal in the ferroelectric liquid crystal composition is not particularly limited as long as the content of the chiral compound A and the chiral compound B can be within the above range.
  • the content of the phenyl pyrimidine compound in the ferroelectric liquid crystal composition is 10 mass. It is preferably in the range of from 30% to 30% by mass. This is because when the content of the phenylpyrimidine compound is small, the above effects may not be sufficiently obtained.
  • the ferroelectric liquid crystal composition is easily crystallized, so that the storage stability is deteriorated when used in a liquid crystal display element, and the ferroelectric liquid crystal composition This is because precipitation of the compounds contained in the product may occur and display quality may be deteriorated.
  • Ferroelectric liquid crystal composition The ferroelectric liquid crystal composition of the present invention is not particularly limited as long as it exhibits a chiral smectic C (SmC * ) phase.
  • As the phase series of the ferroelectric liquid crystal composition for example, a phase change between a nematic (N) phase, a cholesteric (Ch) phase, a chiral smectic C (SmC * ) phase and a nematic (N) phase-chiral in the temperature lowering process.
  • Phase change with smectic C (SmC * ) phase Phase change with smectic C (SmC * ) phase, Nematic (N) phase-Smectic A (SmA) phase-Chiral smectic C (SmC * ) phase change, Nematic (N) phase-Cholesteric (Ch) Phase-smectic A (SmA) phase-chiral smectic C (SmC * ) phase and the like.
  • any one showing bistability and one showing monostability can be used.
  • a ferroelectric liquid crystal composition exhibiting monostability is preferable.
  • gradation display is achieved by continuously changing the director of the liquid crystal (inclination of the molecular axis) by changing the voltage and analog-modulating the transmitted light intensity. This is because it becomes possible.
  • the liquid crystal display element is driven by a field sequential color system, it is preferable to use a ferroelectric liquid crystal composition exhibiting monostability.
  • ferroelectric liquid crystal composition exhibiting monostability, it becomes possible to drive by an active matrix method using TFTs, and also to control gradation by voltage modulation, so that high-definition and high-quality display is possible. This is because it can be realized.
  • “showing monostability” means a state where the state of liquid crystal molecules when no voltage is applied is stabilized in one state.
  • the liquid crystal molecules 25 are tilted from the layer normal z and rotate along a cone ridge having a bottom surface perpendicular to the layer normal z. .
  • the tilt angle of the liquid crystal molecules 25 with respect to the layer normal z is referred to as a tilt angle ⁇ .
  • the liquid crystal molecules 25 can operate on the cone between two states inclined by a tilt angle ⁇ ⁇ with respect to the layer normal z.
  • the expression of monostability refers to a state in which the liquid crystal molecules 25 are stabilized in any one state on the cone when no voltage is applied.
  • the ferroelectric liquid crystal composition only needs to exhibit monostability, and exhibits a half V-shaped switching characteristic in which liquid crystal molecules operate only when a positive or negative voltage is applied.
  • a V-shaped switching characteristic in which liquid crystal molecules operate to the same degree with respect to voltage, asymmetric switching in which the operation of liquid crystal molecules for either positive or negative voltage is larger than the operation of liquid crystal molecules for the other polarity voltage Any of those exhibiting properties can be used.
  • those exhibiting half V-shaped switching characteristics as exemplified in FIGS. 2A and 2B can increase the transmittance even if the cone angle is relatively small.
  • the V-shaped switching characteristics as illustrated in FIG. 2C make the operation of the liquid crystal molecules symmetric with respect to positive and negative voltages, electrical neutrality, and stability. This is preferable. Even asymmetric switching characteristics can be used by devising a driving method.
  • Such a ferroelectric liquid crystal composition can be variously selected from generally known liquid crystal materials according to required characteristics.
  • the ferroelectric liquid crystal composition that expresses the SmC * phase from the Ch phase without passing through the SmA phase is preferable because the change in the operating characteristics with respect to the voltage is small with respect to the temperature change.
  • the liquid crystal display element of this invention has the 1st base material, the 1st electrode layer formed on the said 1st base material, and the 1st orientation layer formed on the said 1st electrode layer.
  • FIG. 3 is a cross-sectional view showing an example of the liquid crystal display element of the present invention.
  • the liquid crystal display element 1 is formed on the first base material 2a, the first electrode layer 3a formed on the first base material 2a, and the first electrode layer 3a.
  • the first alignment processing substrate 11a having the first alignment layer 4a, the second base material 2b, the second electrode layer 3b formed on the second base material 2b, and the second electrode layer formed on the second electrode layer It has the 2nd alignment processing board
  • the liquid crystal layer contains the ferroelectric liquid crystal composition having the chiral compound A and the chiral compound B, a liquid crystal display element having high impact resistance can be obtained.
  • the liquid crystal layer in the present invention is formed between the first alignment layer of the first alignment treatment substrate and the second alignment layer of the second alignment treatment substrate, and contains the above-described ferroelectric liquid crystal composition. .
  • the ferroelectric liquid crystal composition has been described in detail in the above section “A. Ferroelectric liquid crystal composition”, and thus the description thereof is omitted here.
  • the thickness of the liquid crystal layer is preferably in the range of 1.0 ⁇ m to 10.0 ⁇ m, more preferably in the range of 1.3 ⁇ m to 5.0 ⁇ m, and still more preferably in the range of 1.4 ⁇ m to 3.0 ⁇ m. is there. This is because if the thickness of the liquid crystal layer is too thin, the contrast may be lowered. Conversely, if the thickness of the liquid crystal layer is too thick, the liquid crystal molecules may be difficult to align.
  • the thickness of the liquid crystal layer can be adjusted by a bead spacer, a columnar spacer, a partition wall, or the like.
  • a method for forming the liquid crystal layer a method generally used as a method for manufacturing a liquid crystal cell can be used.
  • a vacuum injection method, a liquid crystal dropping method, or the like can be used.
  • a ferroelectric liquid crystal composition that has been made isotropic liquid by heating a liquid crystal cell that has been prepared using a first alignment treatment substrate and a second alignment treatment substrate in advance is used by utilizing the capillary effect.
  • the liquid crystal layer can be formed by injecting and sealing with an adhesive.
  • the liquid crystal dropping method for example, first, a heated or room temperature ferroelectric liquid crystal composition is dropped or applied onto the second alignment layer of the second alignment processing substrate. Next, a sealant is applied to the peripheral portion of the first alignment processing substrate. Subsequently, a liquid crystal layer can be formed by stacking the first alignment treatment substrate and the second alignment treatment substrate under reduced pressure and bonding them with a sealant.
  • the liquid crystal layer forming method is preferably a liquid crystal dropping method. This is because the liquid crystal display element can be efficiently manufactured by shortening the tact time.
  • the ferroelectric liquid crystal composition when dropped or applied, it is preferably at room temperature. This is because deterioration of the ferroelectric liquid crystal composition due to heat can be prevented.
  • the ferroelectric liquid crystal composition When aligning the ferroelectric liquid crystal composition, it may be cooled, and it is not necessary to apply a voltage to the liquid crystal layer. In addition, when cooling, it is preferable to make it cool and orientate.
  • the 1st orientation processing board used for the present invention is the 1st base material, the 1st electrode layer formed on the 1st base material, and the 1st orientation formed on the 1st electrode layer. And a layer.
  • substrate is demonstrated.
  • the 1st alignment layer used for this invention will not be specifically limited if the alignment control of a ferroelectric liquid-crystal composition is possible,
  • a photo-alignment film, a rubbing alignment Examples thereof include a film and an oblique deposition alignment film.
  • these alignment films will be described.
  • Photo-alignment film is useful in that since the photo-alignment process is a non-contact alignment process, there is no generation of static electricity or dust, and the quantitative alignment process can be controlled.
  • the materials used for the photo-alignment film are large, photoreactive materials that impart anisotropy to the film by causing a photoreaction, and photoisomerism that imparts anisotropy to the film by causing a photoisomerization reaction. It can be divided into chemical materials. In the following, description will be made separately for photoreactive materials and photoisomerizable materials.
  • the photoreactive material may be a photodimerization material that imparts anisotropy to the film by causing a photodimerization reaction or a photodegradable material that imparts anisotropy to the film by causing a photodecomposition reaction. preferable. Among these, a photodimerization type material is more preferable because of high exposure sensitivity and wide range of material selection.
  • Examples of the photodimerization type material and the photolysis type material include those described in JP-A-2006-350322, JP-A-2006-323214, JP-A-2005-258429, JP-A-2005-258428, and the like. Can be used.
  • the photodimerization-reactive compound used for the photodimerization-type material is preferably a dimerization-reactive polymer containing cinnamate, coumarin or quinoline as a side chain.
  • photodimerization reactive compound various photodimerization reaction sites and substituents can be selected from the above compounds according to the required properties. Moreover, the photodimerization reactive compound can also be used individually by 1 type or in combination of 2 or more types.
  • the photodimerization type material may contain an additive in addition to the photodimerization reactive compound as long as the photoalignment of the alignment film is not hindered.
  • the additive include a polymerization initiator and a polymerization inhibitor.
  • photoisomerization type material As the photoisomerization type material, for example, those described in JP-A-2006-350322, JP-A-2006-323214, JP-A-2005-258429, JP-A-2005-258428, etc. may be used. it can.
  • the photoisomerization reaction that generates the photoisomerizable material is preferably a cis-trans isomerization reaction.
  • the photoisomerization reactive compound used for the photoisomerization type material is preferably a compound having an azobenzene skeleton in the molecule.
  • Examples of photoisomerization-reactive compounds include monomolecular compounds and polymerizable monomers. Among them, the anisotropy is stabilized by polymerizing after imparting anisotropy to the film by light irradiation. In view of this, a polymerizable monomer is preferable.
  • an acrylate monomer and a methacrylate monomer are preferable because they can be easily polymerized while anisotropy is imparted to the film and the anisotropy is maintained in a good state.
  • photoisomerization-reactive compounds From such photoisomerization-reactive compounds, various cis-trans isomerization-reactive skeletons and substituents can be selected according to required properties.
  • these photoisomerization reactive compounds can also be used individually by 1 type or in combination of 2 or more types.
  • the photoisomerization type material may contain an additive within a range that does not interfere with the photoalignment of the alignment film.
  • the additive include a polymerization initiator and a polymerization inhibitor.
  • the wavelength range of light in which the material used for the photo-alignment film undergoes a photoexcitation reaction is preferably in the ultraviolet range, that is, in the range of 10 nm to 400 nm, preferably from 250 nm to More preferably, it is in the range of 380 nm.
  • the thickness of the photo-alignment film is preferably in the range of 1 nm to 1000 nm, more preferably in the range of 3 nm to 100 nm. If the thickness of the photo-alignment film is smaller than the above range, sufficient optical alignment may not be obtained. Conversely, if the thickness of the photo-alignment film is larger than the above range, the cost may be disadvantageous. is there.
  • the rubbing alignment film is useful in that a relatively high pretilt angle can be realized.
  • materials and forming methods used for the rubbing alignment film general materials can be applied.
  • the thickness of the rubbing alignment film is set to about 1 nm to 1000 nm, and preferably in the range of 50 nm to 100 nm.
  • the oblique deposition alignment film is formed by an oblique deposition method.
  • the oblique deposition film is useful in that a relatively high pretilt angle can be realized.
  • materials and forming methods used for the oblique deposition alignment film general materials can be applied.
  • the oblique deposition alignment film “Liquid Crystal Handbook” edited by the Liquid Crystal Handbook Editorial Committee Maruzen Co., Ltd. October 30, 2000 p. Reference may be made to 229-230.
  • the thickness of the oblique deposition alignment film is set to about 10 nm to 500 nm, and preferably in the range of 30 nm to 200 nm.
  • the constituent materials of the first alignment layer and the second alignment layer have different compositions with the liquid crystal layer interposed therebetween.
  • the polarities of the first alignment layer surface and the second alignment layer surface can be made different depending on the respective materials.
  • the polar surface interaction of the ferroelectric liquid crystal composition and the first alignment layer is different from the polar surface interaction of the ferroelectric liquid crystal composition and the second alignment layer.
  • the generation of alignment defects such as zigzag defects, hairpin defects, and two types of domains having different stable states of liquid crystal molecules when no voltage is applied is suppressed. Because it can. As a result, contrast can be improved.
  • the alignment film the composition of the constituent materials of the oblique deposition alignment film may be different.
  • the composition can be changed by changing the amount of additive added or by the presence or absence of the additive.
  • the first alignment layer and the second alignment layer are photo-alignment films, for example, by using a photoisomerizable material for one photo-alignment film and a photo-reactive material for the other photo-alignment film,
  • the composition of the constituent material of the alignment film can be different.
  • first alignment layer and the second alignment layer are photo-alignment films using a photo-isomerization type material
  • cis-trans isomerization reactivity is selected from photo-isomerization reactive compounds according to required characteristics.
  • the composition of the constituent materials of the photo-alignment film can be made different. Further, the composition can be changed by changing the amount of additive added or by the presence or absence of the additive.
  • first alignment layer and the second alignment layer are photo-alignment films using a photo-dimerization-type material
  • various photo-dimerization reactive compounds for example, photo-dimerization-reactive polymers
  • the composition of the constituent materials can be different. Further, the composition can be changed by changing the amount of additive added or by the presence or absence of the additive.
  • Photo-alignment films using photodimerization materials tend to have a relatively positive polarity compared to photo-alignment films using photoisomerization-type materials.
  • the spontaneous polarization of the liquid crystal molecules tends to face the photo-alignment film side using the photoisomerizable material.
  • Photo-alignment films using photodimerized materials tend to have a relatively positive polarity relative to the rubbing alignment film, so the spontaneous polarization of the liquid crystal molecules tends to face the rubbing alignment film due to the polar surface interaction. It is in.
  • rubbing alignment films tend to have a relatively strong positive polarity compared to photo-alignment films using photoisomerizable materials, so that the spontaneous polarization of liquid crystal molecules is caused by the photoisomerization type due to the polar surface interaction. It tends to face the photo-alignment film side using the material.
  • the direction of spontaneous polarization of liquid crystal molecules can be controlled, and the occurrence of alignment defects can be effectively suppressed.
  • the second electrode layer when the second alignment layer tends to have a relatively positive polarity in the first alignment layer and the second alignment layer, the second electrode layer is negative. It is preferable to perform display when the above voltage is applied.
  • the second alignment layer tends to have a relatively strong positive polarity in the first alignment layer and the second alignment layer, the above-mentioned combinations can be mentioned, and specifically, the first alignment layer.
  • the second alignment layer is a photo-alignment film using a photo-dimerization material
  • the first alignment layer is a rubbing alignment film
  • the second alignment layer is a photo-dimerization type It is preferable that a photo-alignment film using a material is used; alternatively, the first alignment layer is a photo-alignment film using a photoisomerizable material, and the second alignment layer is a rubbing alignment film. Note that a method for driving the liquid crystal display element will be described later, and a description thereof will be omitted here.
  • the first electrode layer used in the present invention is not particularly limited as long as it is generally used as an electrode of a liquid crystal display element. At least one of the electrode layer and the second electrode layer of the second alignment treatment substrate is preferably formed of a transparent conductor. Preferred examples of the transparent conductor material include indium oxide, tin oxide, indium tin oxide (ITO), and the like.
  • one of the first alignment processing substrate and the second alignment processing substrate is provided with a whole surface common electrode formed of the transparent conductor.
  • a gate electrode and a source electrode are arranged in a matrix, and a TFT element and a pixel electrode are provided in a portion surrounded by the gate electrode and the source electrode.
  • Examples of the method for forming the first electrode layer include chemical vapor deposition (CVD), physical vapor deposition (PVD) such as sputtering, ion plating, and vacuum deposition.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • the 1st base material used for this invention will not be specifically limited if generally used as a base material of a liquid crystal display element, For example, a glass plate, a plastic plate, etc. are preferable. Can be mentioned.
  • partition walls or columnar spacers may be formed on the first base material.
  • the partition or columnar spacer is not formed on the first base material in the first alignment processing substrate. That is, partition walls or columnar spacers may be formed on the first alignment processing substrate, and partition walls or columnar spacers may be formed on the second alignment processing substrate.
  • partition walls and columnar spacers general partition walls and columnar spacers can be applied.
  • a colored layer may be formed on the first base material.
  • the coloring layer is not formed on the first base material in the first alignment processing substrate. That is, a colored layer may be formed on the first alignment processing substrate, and a coloring layer may be formed on the second alignment processing substrate.
  • a color filter type liquid crystal display element capable of realizing color display by the colored layer can be obtained.
  • a method for forming a colored layer in a general color filter can be used.
  • a pigment dispersion method color resist method, etching method
  • a printing method an inkjet method, or the like
  • it can.
  • the second alignment treatment substrate used in the present invention includes a second base material, a second electrode layer formed on the second base material, and a second orientation formed on the second electrode layer. And a layer.
  • the liquid crystal display element of the present invention may have a polarizing plate.
  • the polarizing plate used in the present invention is not particularly limited as long as it transmits only a specific direction among the wave of light, and a polarizing plate generally used as a polarizing plate of a liquid crystal display element should be used. Can do.
  • the ferroelectric liquid crystal composition exhibits monostability, and the second alignment layer is relatively the first alignment layer and the second alignment layer.
  • display is preferably performed when a negative voltage is applied to the second electrode layer.
  • FIG. 4 is a schematic diagram showing an example of an alignment state of a ferroelectric liquid crystal composition showing monostability and showing a half V-shaped switching characteristic.
  • 4A shows a case where no voltage is applied
  • FIG. 4B shows a case where a negative voltage is applied to the second electrode layer
  • FIG. 4C shows a case where a positive voltage is applied to the second electrode layer.
  • Each is shown.
  • the liquid crystal molecules 25 are stabilized in one state on the cone (FIG. 4A).
  • a negative voltage is applied to the second electrode layer, the liquid crystal molecules 25 are inclined from the stabilized state (broken line) to one side (FIG. 4B).
  • the liquid crystal molecules 25 are tilted from the stabilized state (broken line) to the opposite side when a negative voltage is applied to the second electrode layer (see FIG. 4 (c)).
  • the inclination angle ⁇ when a negative voltage is applied to the second electrode layer is larger than the inclination angle ⁇ when a positive voltage is applied to the second electrode layer.
  • D indicates the alignment treatment direction of the first alignment layer and the second alignment layer
  • z indicates the layer normal.
  • the second alignment layer tends to have a relatively positive polarity
  • the inclination angle of the liquid crystal molecules from the mono-stabilized state when the negative voltage of the second electrode layer is applied is
  • the positive voltage of the second electrode layer is applied
  • the inclination angle of the liquid crystal molecules from the mono-stabilized state becomes larger. Therefore, when a negative voltage is applied to the second electrode layer, the amount of transmitted light is larger than when a positive voltage is applied to the second electrode layer. That is, when a positive voltage is applied to the second electrode layer, the amount of transmitted light is less than when a negative voltage is applied to the second electrode layer.
  • “Display when a negative voltage is applied to the second electrode layer” means that liquid crystal molecules are stabilized in one state on the cone when no voltage is applied, and the second electrode layer is negative.
  • the liquid crystal molecules tilt from the mono-stabilized state to one side on the cone, and the liquid crystal molecules maintain the mono-stabilized state when a positive voltage is applied to the second electrode layer.
  • tilted from the mono-stabilized state to the opposite side of the negative voltage applied to the second electrode layer and tilted from the mono-stabilized state of the liquid crystal molecules when a negative voltage is applied to the second electrode layer. It means that the angle is larger than the tilt angle from the mono-stabilized state of the liquid crystal molecules when a positive voltage is applied to the second electrode layer.
  • the alignment direction in the mono-stabilized state of the liquid crystal molecules and the polarization axis of one polarizing plate are made substantially parallel.
  • the spontaneous polarization Ps of the liquid crystal molecules 25 tends to be directed toward the first alignment layer 4a.
  • the liquid crystal molecules 25 are aligned along the alignment treatment direction D of the first alignment layer and the second alignment layer to be in a uniform alignment state.
  • the spontaneous polarization Ps of the liquid crystal molecules 25 is directed to the second alignment layer 4b side due to the influence of the polarity of the applied voltage, as illustrated in FIG. .
  • FIG. 8A when a negative voltage is applied to the second electrode layer 3b, the spontaneous polarization Ps of the liquid crystal molecules 25 is directed to the second alignment layer 4b side due to the influence of the polarity of the applied voltage, as illustrated in FIG. .
  • FIG. 8B is a schematic diagram showing the alignment state of the liquid crystal molecules from the upper surface of FIG.
  • FIG. 8B is a schematic diagram showing the alignment state of the liquid crystal molecules from the upper surface of FIG. 6, and the spontaneous polarization Ps is directed from the back of the page to the near side (the mark ⁇ in FIG. 8B). ).
  • the negative polarity of this applied voltage Due to the repulsion of the spontaneous polarization of the liquid crystal molecules with the negative polarity, as illustrated in FIG. That is, when a negative voltage is applied to the second electrode layer, the molecular direction of the liquid crystal changes approximately twice the tilt angle ⁇ of the liquid crystal in parallel to the first alignment treatment substrate surface.
  • the spontaneous polarization of the liquid crystal molecules tends to be directed to the first alignment layer side.
  • a liquid crystal display element using a ferroelectric liquid crystal composition exhibiting V-shaped switching characteristics or asymmetric switching characteristics can be driven by controlling the direction of spontaneous polarization of liquid crystal molecules in the same manner. .
  • the second electrode layer When a negative voltage is applied to the second electrode layer, there are preferably 70% or more, more preferably 80% or more, more preferably 90% or more, in which the molecular direction of the liquid crystal changes about twice the tilt angle. Most preferably, it is 95% or more. This is because a favorable contrast ratio can be obtained within the above range.
  • said ratio can be measured as follows.
  • polarizing plates 17a and 17b are provided outside the first alignment processing substrate 11a and the second alignment processing substrate 11b, respectively, and the two polarizing plates 17a and 17b have substantially vertical polarization axes.
  • a liquid crystal display element is used in which the polarization axis of the polarizing plate 17a and the rubbing treatment direction (the alignment direction of liquid crystal molecules) of the first alignment layer 4a are substantially parallel. A dark state is obtained when no voltage is applied, and a bright state is obtained when a voltage is applied.
  • the liquid crystal molecules When a negative voltage is applied to the second electrode layer, the liquid crystal molecules are inclined from the mono-stabilized state to one side on the cone at an angle corresponding to the magnitude of the applied voltage.
  • the position A direction of the liquid crystal molecules 25
  • the position B alignment processing direction D
  • the position C are not necessarily coincident. Do not mean. Therefore, as illustrated in FIG. 4B, the maximum tilt angle ⁇ when a negative voltage is applied to the second electrode layer is about twice the tilt angle ⁇ .
  • the angle at which the molecular direction of the liquid crystal changes parallel to the first alignment treatment substrate surface can be measured as follows. First, a polarizing microscope and a liquid crystal display element in which polarizing plates are arranged in crossed Nicols are arranged so that the polarization axis of one polarizing plate and the alignment direction of liquid crystal molecules in the liquid crystal layer are parallel, and this position is used as a reference. . When a voltage is applied, the liquid crystal molecules come to have a predetermined angle with the polarization axis, so that the polarized light transmitted through one polarizing plate is transmitted through the other polarizing plate to be in a bright state. With this voltage applied, the liquid crystal display element is rotated to a dark state. And the angle which rotated the liquid crystal display element at this time is measured. The angle by which the liquid crystal display element is rotated is an angle at which the molecular direction of the liquid crystal changes in parallel to the first alignment processing substrate surface.
  • the liquid crystal molecules are inclined from the mono-stabilized state to one side on the cone at an angle according to the magnitude of the applied voltage.
  • the direction of the liquid crystal molecules does not change about twice the tilt angle when a negative voltage is applied to the second electrode layer.
  • the amount of transmitted light depends on the tilt angle of liquid crystal molecules when a voltage is applied.
  • the liquid crystal molecules are tilted on the cone. Therefore, as shown in FIG. 2, for example, the tilt angle of the liquid crystal molecules changes according to the magnitude of the applied voltage, and the transmitted light amount changes.
  • the amount of transmitted light is maximized when the inclination angle of the liquid crystal molecules from the monostable state is 45 °. Therefore, in order to realize a high amount of transmitted light, a ferroelectric liquid crystal whose tilt angle from a monostable state of liquid crystal molecules can be 45 ° when a negative voltage is applied to the second electrode layer during actual driving.
  • a composition For example, when a ferroelectric liquid crystal composition having a maximum tilt angle ⁇ from the monostable state of liquid crystal molecules as shown in FIG. 4 is larger than 45 °, the liquid crystal display element is actually driven. At this time, when a negative voltage is applied to the second electrode layer, the tilt angle of the liquid crystal molecules from the monostable state can be set to 45 °. This is because, as described above, when a negative voltage is applied to the second electrode layer during actual driving, the direction of the liquid crystal molecules does not change approximately twice the tilt angle.
  • the high-speed response of the ferroelectric liquid crystal composition can be used.
  • it can be suitably used for a required field sequential color system.
  • the driving method of the liquid crystal display element of the present invention is not limited to the field sequential method, and may be a color filter method that performs color display using a colored layer.
  • an active matrix method using a thin film transistor is preferable. This is because by adopting an active matrix system using TFTs, the target pixel can be reliably turned on and off, and a high-quality display becomes possible.
  • the first alignment treatment substrate may be a TFT substrate
  • the second alignment treatment substrate may be a common electrode substrate
  • the first alignment treatment substrate is a common electrode substrate
  • the second alignment treatment substrate is a TFT substrate.
  • the first alignment processing substrate is common to the TFT substrate and the second alignment processing substrate.
  • An electrode substrate is preferred.
  • the TFT element 27 when the gate electrode 26x is set to a high potential of about 30 V, the TFT element 27 is switched on, and a signal voltage is applied to the ferroelectric liquid crystal composition by the source electrode 26y.
  • the electrode 26x is set to a low potential of about ⁇ 10V, the TFT element 27 is switched off.
  • the switch-off state as illustrated in FIG. 11, a voltage is applied between the common electrode (second electrode layer 3b) and the gate electrode 26x so that the common electrode (second electrode layer 3b) side is positive. .
  • the liquid crystal molecules do not operate, so that the pixel is in a dark state.
  • the spontaneous polarization of the liquid crystal molecules is caused by the polar surface interaction in the no-voltage applied state.
  • the spontaneous polarization Ps of the liquid crystal molecules 25 faces the TFT substrate (first alignment processing substrate 11a) side. Therefore, the direction of spontaneous polarization is not affected by the voltage applied between the common electrode (second electrode layer 3b) and the gate electrode 26x. Therefore, by controlling the direction of spontaneous polarization and using the first alignment processing substrate as the TFT substrate and the second alignment processing substrate as the common electrode substrate, light leakage near the gate electrode can be prevented.
  • the driving method of the liquid crystal display element of the present invention may be a segment method.
  • the present invention is not limited to the above embodiment.
  • the above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
  • Example 1 Ferroelectric liquid crystal composition
  • Ferroelectric liquid crystal compositions were prepared as shown in Tables 1 to 3 below using chiral compounds A a to j and chiral compounds B 1 to 15 shown below.
  • a solution of a photoisomerization type photo-alignment film material (LIA012: DIC Corporation) was spin-coated at 1500 rpm for 30 seconds on the glass substrate 2 coated with ITO. Thereafter, after drying in an oven at 100 ° C. for 3 minutes, 2J-polarized exposure processing was performed with a polarizing exposure machine.
  • LIA012 DIC Corporation
  • a sealing material was applied in a square frame shape on the substrate.
  • the above-mentioned ferroelectric liquid crystal composition was applied in the form of dots, and the two substrates were assembled and thermocompression bonded so that the rubbing treatment direction and the polarization treatment direction were perpendicular. Thereafter, the liquid crystal cell was cooled to align the ferroelectric liquid crystal composition.
  • a solution of a photoisomerization type photo-alignment film material (LIA012: DIC Corporation) was spin-coated at 1500 rpm for 30 seconds on the ITO-coated glass substrate 2 substrate. Thereafter, after drying in an oven at 100 ° C. for 3 minutes, 2J-polarized exposure processing was performed with a polarizing exposure machine.
  • LIA012 DIC Corporation
  • a sealing material was applied on the glass substrate 1 in a square frame shape so that there was no break.
  • the ferroelectric liquid crystal composition was applied to the substrate in the form of dots so as to be inside the sealing material, and the two substrates were assembled and thermocompression bonded so that the directions of polarization treatment were parallel. Thereafter, the liquid crystal cell was cooled to align the ferroelectric liquid crystal composition.
  • Ferroelectric liquid crystal compositions were prepared as shown in Table 8 below using k to p of chiral compound A shown in Table 6 and 16 to 21 of chiral compound B shown in Table 7 below.
  • a liquid crystal cell filled with a ferroelectric liquid crystal composition is placed between two polarizing plates set in a crossed Nicol state, and the positive voltage (+10 V) and negative voltage are based on the position of black display when no voltage is applied.
  • the angle of liquid crystal molecules that moved when (-10 V) was applied was measured.
  • the tilt angle is the sum of the angle of movement of the liquid crystal molecules when a positive voltage is applied and the angle of movement of the liquid crystal molecules when a negative voltage is applied.
  • at least one of the chiral compound A and the chiral compound B has two fluorine atoms in the substituent, compared to the case where both the chiral compound A and the chiral compound B do not have two fluorine atoms in the substituent.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Liquid Crystal Substances (AREA)
  • Liquid Crystal (AREA)

Abstract

La présente invention a pour but principal de proposer une composition de cristaux liquides ferroélectriques présentant une résistance supérieure au choc lorsqu'elle est utilisée dans un élément d'affichage à cristaux liquides. La présente invention concerne une composition de cristaux liquides ferroélectriques caractérisée par le fait qu'elle contient un composé chiral (A) représenté par la formule générale (1) et un composé chiral (B) représenté par la formule générale (2).
PCT/JP2012/072805 2011-09-07 2012-09-06 Composition de cristaux liquides ferroélectriques et dispositif d'affichage à cristaux liquides WO2013035811A1 (fr)

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CN109679666B (zh) * 2019-01-29 2021-09-17 武汉轻工大学 液晶化合物及其制备方法、液晶组合物以及微波通讯器件

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001500502A (ja) * 1996-09-12 2001-01-16 サムスン ディスプレー デバイシス カンパニー リミテッド 液晶化合物
JP2006503100A (ja) * 2002-10-18 2006-01-26 メルク　パテント　ゲゼルシャフト　ミット　ベシュレンクテル　ハフトング 側方にアルキル化されたフェニル構造要素を有するキラルドーパント
WO2010031431A1 (fr) * 2008-09-17 2010-03-25 Tetragon Lc Chemie Ag Composés chiraux, compositions de cristaux liquides cholestériques et ferroélectriques comprenant ces composés chiraux, et écrans à cristaux liquides comprenant ces compositions de cristaux liquides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001500502A (ja) * 1996-09-12 2001-01-16 サムスン ディスプレー デバイシス カンパニー リミテッド 液晶化合物
JP2006503100A (ja) * 2002-10-18 2006-01-26 メルク　パテント　ゲゼルシャフト　ミット　ベシュレンクテル　ハフトング 側方にアルキル化されたフェニル構造要素を有するキラルドーパント
WO2010031431A1 (fr) * 2008-09-17 2010-03-25 Tetragon Lc Chemie Ag Composés chiraux, compositions de cristaux liquides cholestériques et ferroélectriques comprenant ces composés chiraux, et écrans à cristaux liquides comprenant ces compositions de cristaux liquides

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