WO2020095499A1 - Composition de cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

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

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Publication number
WO2020095499A1
WO2020095499A1 PCT/JP2019/030968 JP2019030968W WO2020095499A1 WO 2020095499 A1 WO2020095499 A1 WO 2020095499A1 JP 2019030968 W JP2019030968 W JP 2019030968W WO 2020095499 A1 WO2020095499 A1 WO 2020095499A1
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carbons
liquid crystal
diyl
compound
fluorine
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PCT/JP2019/030968
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English (en)
Japanese (ja)
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真依子 松隈
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Jnc株式会社
Jnc石油化学株式会社
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Priority to JP2020556602A priority Critical patent/JP7342880B2/ja
Publication of WO2020095499A1 publication Critical patent/WO2020095499A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/16—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon double bonds, e.g. stilbenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells

Definitions

  • the present invention relates to a liquid crystal composition, a liquid crystal display device containing this composition, and the like.
  • the present invention relates to a liquid crystal composition having a positive dielectric anisotropy, and an AM (active matrix) device containing this composition and having a mode of TN, ECB, OCB, IPS, FFS, or FPA.
  • classification based on the operation mode of liquid crystal molecules is performed by PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), and IPS.
  • the modes include (in-plane switching), VA (vertical alignment), FFS (fringe field switching), and FPA (field-induced photo-reactive alignment).
  • the classification based on the driving method of the element is PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into TFT (thin film transistor), MIM (metal insulator metal), and the like.
  • the TFTs are classified into amorphous silicon and polycrystal silicon. The latter is classified into a high temperature type and a low temperature type according to the manufacturing process.
  • the light source-based classification is a reflective type that uses natural light, a transmissive type that uses a backlight, and a semi-transmissive type that uses both natural light and a backlight.
  • the liquid crystal display element contains a liquid crystal composition having a nematic phase.
  • This composition has suitable properties. By improving the properties of this composition, an AM device having good properties can be obtained.
  • the relationships in these properties are summarized in Table 1 below. The characteristics of the composition will be further described based on a commercially available AM device.
  • the temperature range of the nematic phase is related to the temperature range in which the device can be used.
  • a preferable upper limit temperature of the nematic phase is about 70 ° C. or higher, and a preferable lower limit temperature of the nematic phase is about ⁇ 10 ° C. or lower.
  • the viscosity of the composition is related to the response time of the device. A short response time is preferable for displaying a moving image on the device.
  • the elastic constant of the composition is related to the contrast of the device. In order to increase the contrast in the device, a large elastic constant in the composition is more preferable.
  • the optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large optical anisotropy or a small optical anisotropy, that is, a suitable optical anisotropy is required.
  • the product ( ⁇ n ⁇ d) of the optical anisotropy ( ⁇ n) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio.
  • the appropriate value of the product depends on the type of operating mode. For a TN-like mode device, a suitable value is about 0.45 ⁇ m. In this case, a composition having a large optical anisotropy is preferable for a device having a small cell gap.
  • a large dielectric anisotropy in the composition contributes to a low threshold voltage, a small power consumption and a large contrast ratio in the device. Therefore, large dielectric anisotropy is preferable.
  • the large specific resistance in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, in the initial stage, a composition having a large specific resistance at room temperature as well as at a temperature close to the maximum temperature of the nematic phase is preferable.
  • a composition having a large specific resistance not only at room temperature but also at a temperature close to the maximum temperature of the nematic phase after being used for a long time is preferable.
  • the stability of the composition against ultraviolet rays and heat is related to the life of the liquid crystal display device. When their stability is high, the lifetime of this device is long. Such characteristics are preferable for AM devices used for liquid crystal monitors, liquid crystal televisions, and the like.
  • a composition having a positive dielectric anisotropy is used in an AM device having a TN mode.
  • a composition having a negative dielectric anisotropy is used in an AM device having a VA mode.
  • a composition having a positive or negative dielectric anisotropy is used in an AM device having an IPS mode or an FFS mode.
  • a composition having a positive or negative dielectric anisotropy is used in a polymer-sustained alignment (PSA) type AM device.
  • PSA polymer-sustained alignment
  • the arrangement of some liquid crystal molecules is not parallel to the panel substrate due to the oblique electric field. Therefore, in order to suppress the tilt-up of these liquid crystal molecules, the dielectric constant ( ⁇ It is preferable that ⁇ ) is large. By suppressing the tilt-up of the liquid crystal molecules, the transmittance of the FFS mode element can be increased, which contributes to a large contrast ratio (for example, see Non-Patent Document 1).
  • An object of the present invention is to provide a liquid crystal composition having a large dielectric constant ( ⁇ ) in the short axis direction of liquid crystal molecules.
  • Other issues are high nematic phase upper temperature limit, nematic phase lower temperature limit, small viscosity, suitable optical anisotropy, large dielectric anisotropy, large resistivity, high heat stability, high UV stability.
  • a liquid crystal composition satisfying at least one of properties such as a large elastic constant is Another object is to provide a liquid crystal composition having a suitable balance between at least two of these properties.
  • Another object is to provide a liquid crystal display device containing such a composition.
  • Another object is to provide a liquid crystal display device having a high transmittance and a large contrast ratio.
  • Another object is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage and long life.
  • the present invention contains at least one compound selected from the compounds represented by formula (1) as the first component, and at least one compound selected from the compounds represented by formula (2) as the second component
  • the liquid crystal composition has a positive dielectric anisotropy.
  • R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons
  • R 2 and R 3 are hydrogen.
  • ring A and ring B are 1,4-cyclohexylene.
  • ring C and ring E are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene , 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2 , 6-diyl, or chroman-2,6-diyl in which at least one hydrogen has been replaced by fluorine or chlorine, but at least one of ring C and ring E has at least one hydrogen replaced by flu
  • the advantage of the present invention is a liquid crystal composition having a large dielectric constant ( ⁇ ) in the short axis direction of liquid crystal molecules.
  • Other advantages are high upper temperature of nematic phase, low lower temperature of nematic phase, small viscosity, proper optical anisotropy, large dielectric anisotropy, large specific resistance, high heat stability, high UV stability.
  • a liquid crystal composition satisfying at least one of properties such as a large elastic constant is a liquid crystal composition that has a suitable balance between at least two of these properties.
  • Another advantage is a liquid crystal display device containing such a composition.
  • Another advantage is a liquid crystal display device having a high transmittance and a large contrast ratio.
  • Another advantage is an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, and long life.
  • liquid crystal composition and “liquid crystal display device” may be abbreviated as “composition” and “device”, respectively.
  • “Liquid crystal display element” is a general term for liquid crystal display panels and liquid crystal display modules.
  • the “liquid crystalline compound” is a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and does not have a liquid crystal phase, but for the purpose of adjusting properties such as temperature range, viscosity and dielectric anisotropy of the nematic phase. It is a general term for the compounds mixed in the composition.
  • This compound has a 6-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecule (liquid crystal molecule) is rod-like.
  • the “polymerizable compound” is a compound added for the purpose of forming a polymer in the composition. Liquid crystal compounds having alkenyl are not classified as polymerizable compounds in that sense.
  • the liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as an optically active compound and a polymerizable compound are added to the liquid crystal composition as needed.
  • the proportion of the liquid crystal compound is represented by a mass percentage (mass%) based on the mass of the liquid crystal composition containing no additive even when the additive is added.
  • the ratio of the additive is represented by a mass percentage (mass%) based on the mass of the liquid crystal composition containing no additive. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total mass of the liquid crystal compound.
  • the ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the mass of the polymerizable compound.
  • the maximum temperature of the nematic phase may be abbreviated as “maximum temperature”.
  • the “minimum temperature of the nematic phase” may be abbreviated as “minimum temperature”.
  • the expression “increasing the dielectric anisotropy” means that, in the case of a composition having a positive dielectric anisotropy, that value increases positively, and a composition having a negative dielectric anisotropy. When it is a thing, it means that its value increases negatively.
  • “High voltage retention” means that the device has a large voltage retention not only at room temperature but also at a temperature close to the upper limit temperature at the initial stage, and after a long time use, it has a large voltage not only at room temperature but also at a temperature close to the upper limit temperature. Means to have a retention rate.
  • the properties of the compositions and devices may be examined by aging tests.
  • symbols ⁇ and ⁇ surrounded by hexagons correspond to the ring ⁇ and the ring ⁇ , respectively, and represent rings such as a 6-membered ring and a condensed ring.
  • the subscript'x 'is 2 there are two rings ⁇ .
  • the two groups represented by the two rings ⁇ may be the same or different.
  • This rule applies to any two rings ⁇ when the subscript'x 'is greater than 2.
  • This rule also applies to other symbols, such as the linking group Z.
  • a diagonal line crossing one side of the ring ⁇ represents that any hydrogen on the ring ⁇ may be replaced with a substituent (—Sp—P).
  • the subscript'y ' indicates the number of substituents replaced. When the subscript'y 'is 0, there is no such replacement. When the subscript'y 'is 2 or more, there are plural substituents (-Sp-P) on the ring ⁇ . Also in this case, the rule of "may be the same or different" may be applied. This rule also applies when the Ra symbol is used for a plurality of compounds.
  • Ra and Rb are alkyl, alkoxy, or alkenyl
  • Ra and Rb are independently selected from the group of alkyl, alkoxy, and alkenyl.
  • the group represented by Ra and the group represented by Rb may be the same or different.
  • At least one compound selected from the compounds represented by formula (1z) may be abbreviated as “compound (1z)”.
  • “Compound (1z)” means one compound represented by formula (1z), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas.
  • the expression "at least one compound selected from the compounds represented by formula (1z) and formula (2z)” means at least one compound selected from the group consisting of compound (1z) and compound (2z). ..
  • the expression "at least one'A '” means that the number of'A's is arbitrary.
  • the expression “at least one'A 'may be replaced by'B'” means that when the number of'A 'is one, the position of'A' is arbitrary and the number of'A 'is two. If there are more than one, those positions can be selected without restriction.
  • the phrase “at least one —CH 2 — may be replaced with —O—” is sometimes used. In this case, —CH 2 —CH 2 —CH 2 — may be converted to —O—CH 2 —O— by replacing non-adjacent —CH 2 — with —O—. However, adjacent --CH 2 --is not replaced with --O--. This is because this replacement produces —O—O—CH 2 — (peroxide).
  • alkyl is linear or branched and does not include cyclic alkyl.
  • Straight-chain alkyl is preferred over branched alkyl.
  • terminal groups such as alkoxy and alkenyl.
  • trans is preferable to cis for increasing the maximum temperature.
  • 2-fluoro-1,4-phenylene is asymmetrical to the left and right, there are leftward (L) and rightward (R) directions.
  • divalent groups such as tetrahydropyran-2,5-diyl.
  • a linking group such as carbonyloxy (-COO- or -OCO-).
  • the present invention includes the following items.
  • Item 1 Positive dielectric containing at least one compound selected from compounds represented by formula (1) as a first component and at least one compound selected from compounds represented by formula (2) as a second component A liquid crystal composition having refractive index anisotropy.
  • R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons
  • R 2 and R 3 are hydrogen.
  • ring A and ring B are 1,4-cyclohexylene.
  • ring C and ring E are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene , 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2 , 6-diyl, or chroman-2,6-diyl in which at least one hydrogen has been replaced by fluorine or chlorine, but at least one of ring C and ring E has at least one hydrogen replaced by flu
  • Item 2. The liquid crystal composition according to item 1, containing at least one compound selected from compounds represented by formulas (1-1) to (1-14) as a first component.
  • R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 14 carbons
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , X 9 , X 10 , X 11 , X 12 , X 13 , and X 14 are hydrogen or fluorine
  • Y 1 is Fluorine, chlorine, an alkyl having 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine, an alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine, or at least one hydrogen
  • It is an alkenyloxy having 2 to 12 carbons, which is replaced by fluorine or chlorine.
  • Item 3. The liquid crystal composition according to item 1 or 2, containing at least one compound selected from the compounds represented by formulas (2-1) to (2-38) as the second component.
  • R 2 and R 3 are each alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 carbons. To 12 alkenyloxy.
  • Item 4. The liquid crystal according to any one of items 1 to 3, wherein the ratio of the first component is in the range of 5% by mass to 50% by mass, and the ratio of the second component is in the range of 2% by mass to 50% by mass. Composition.
  • Item 5. The liquid crystal composition according to any one of items 1 to 4, containing at least one compound selected from the compounds represented by formula (3) as the third component.
  • R 4 and R 5 are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen is replaced by fluorine or chlorine.
  • C2-C12 alkenyl; ring F and ring G are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4 -Phenylene;
  • Z 5 is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; e is 1, 2, or 3.
  • Item 6. The liquid crystal composition according to any one of items 1 to 5, containing at least one compound selected from compounds represented by formulas (3-1) to (3-13) as a third component.
  • R 4 and R 5 are each an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or at least one of It is alkenyl having 2 to 12 carbons in which hydrogen is replaced by fluorine or chlorine.
  • Item 7. The liquid crystal composition according to item 5 or 6, wherein the ratio of the third component is in the range of 10% by mass to 90% by mass.
  • Item 8. The liquid crystal composition according to any one of items 1 to 7, containing at least one compound selected from the compounds represented by formula (4) as the fourth component.
  • R 6 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons;
  • ring J is 1,4-cyclohexylene, 1,4 -Phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane -2,5-diyl, or tetrahydropyran-2,5-diyl;
  • Z 6 is a single bond, ethylene, or carbonyloxy;
  • X 15 and X 16 are hydrogen or fluorine;
  • Y 2 is , Fluorine, chlorine, alkyl having 1 to 12 carbons in which at least one
  • Item 9 The liquid crystal composition according to any one of items 1 to 8, which contains, as a fourth component, at least one compound selected from compounds represented by formulas (4-1) to (4-16).
  • R 6 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons.
  • Item 10 The liquid crystal composition according to item 8 or 9, wherein the ratio of the fourth component is in the range of 5% by mass to 40% by mass.
  • Item 11 The liquid crystal composition according to any one of items 1 to 10, containing at least one compound selected from the compounds represented by formula (5) as the fifth component.
  • R 7 and R 8 are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons.
  • Ring K and ring M are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen Is naphthalene-2,6-diyl substituted with fluorine or chlorine, chroman-2,6-diyl, or chroman-2,6-diyl substituted with at least one hydrogen with fluorine or chlorine;
  • ring L is , 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1, -Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-d
  • Item 12. The liquid crystal composition according to any one of items 1 to 11, containing at least one compound selected from compounds represented by formulas (5-1) to (5-31) as a fifth component.
  • R 7 and R 8 are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon It is an alkenyloxy of the numbers 2 to 12.
  • Item 13 The liquid crystal composition according to item 11 or 12, wherein the ratio of the fifth component is in the range of 2% by mass to 50% by mass.
  • the maximum temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C.) is 0.07 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C.) is 2 14.
  • the liquid crystal composition according to any one of items 1 to 13, which is the above.
  • Item 15 A liquid crystal display device containing the liquid crystal composition according to any one of items 1 to 13.
  • Item 16 The liquid crystal display element according to item 15, wherein the operation mode of the liquid crystal display element is the FFS mode and the driving method of the liquid crystal display element is the active matrix method.
  • Item 17 The liquid crystal display element according to item 15, wherein the operation mode of the liquid crystal display element is a TN mode, an ECB mode, an OCB mode, an IPS mode, or an FPA mode, and the driving method of the liquid crystal display element is an active matrix method.
  • Item 18 Use of the liquid crystal composition according to any one of items 1 to 14 in a liquid crystal display device.
  • the present invention also includes the following items.
  • A One compound selected from additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a quencher, a dye, a defoaming agent, a polymerizable compound, a polymerization initiator and a polymerization inhibitor, and two compounds.
  • B An AM device containing the above composition.
  • C The above composition further containing a polymerizable compound, and a polymer-supported alignment (PSA) type AM device containing this composition.
  • D A polymer-supported alignment (PSA) type AM device containing the composition described above and in which the polymerizable compound in the composition is polymerized.
  • (E) A device containing the above composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA.
  • (F) A transmissive element containing the above composition.
  • (G) Use of the above composition as a composition having a nematic phase.
  • (H) Use of an optically active composition obtained by adding an optically active compound to the above composition.
  • composition of the present invention will be described in the following order. First, the constitution of the component compounds in the composition will be explained. Second, the main characteristics of the component compounds and the main effects of the compounds on the composition will be explained. Thirdly, the combination of components in the composition, the preferable ratio of the components and the basis thereof will be described. Fourthly, a preferred form of the component compound will be described. Fifth, preferable component compounds are shown. Sixth, the additives that may be added to the composition will be described. Seventh, a method of synthesizing the component compounds will be described. Finally, the use of the composition will be explained.
  • This composition contains a plurality of liquid crystal compounds.
  • the composition may contain additives. Additives are optically active compounds, antioxidants, ultraviolet absorbers, quenchers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like.
  • This composition is classified into composition A and composition B from the viewpoint of the liquid crystal compound.
  • the composition A is a liquid crystal compound selected from the compound (1), the compound (2), the compound (3), the compound (4), and the compound (5), as well as other liquid crystal compounds and additives. May be further contained.
  • the "other liquid crystal compound” is a liquid crystal compound different from the compound (1), the compound (2), the compound (3), the compound (4), and the compound (5). Such compounds are mixed into the composition for the purpose of further adjusting the properties.
  • Composition B consists essentially of liquid crystalline compounds selected from compound (1), compound (2), compound (3), compound (4) and compound (5). “Substantially” means that the composition B may contain an additive, but contains no other liquid crystal compound. Composition B has fewer components than composition A. From the viewpoint of cost reduction, the composition B is preferable to the composition A. The composition A is preferable to the composition B from the viewpoint that the characteristics can be further adjusted by mixing the other liquid crystal compounds.
  • the main effects of the component compounds are as follows.
  • the compound (1) increases the dielectric anisotropy and lowers the minimum temperature.
  • the compound (2) increases the dielectric constant of the liquid crystal in the short axis direction and lowers the minimum temperature.
  • the compound (3) lowers the viscosity or raises the maximum temperature.
  • the compound (4) increases the dielectric anisotropy and lowers the minimum temperature.
  • the compound (5) increases the dielectric constant in the minor axis direction and lowers the minimum temperature.
  • Preferred combinations of the component compounds in the composition are compound (1) + compound (2), compound (1) + compound (2) + compound (3), compound (1) + compound (2) + compound (4), Compound (1) + Compound (2) + Compound (5), Compound (1) + Compound (2) + Compound (3) + Compound (4), Compound (1) + Compound (2) + Compound (3) + The compound (5) or the compound (1) + the compound (2) + the compound (3) + the compound (4) + the compound (5).
  • More preferred combinations are compound (1) + compound (2), compound (1) + compound (2) + compound (3), compound (1) + compound (2) + compound (3) + compound (4), Compound (1) + Compound (2) + Compound (3) + Compound (5), or Compound (1) + Compound (2) + Compound (3) + Compound (4) + Compound (5).
  • the preferable ratio of the compound (1) is about 5% by mass or more for increasing the dielectric anisotropy, and about 50% by mass or less for decreasing the minimum temperature.
  • a more desirable ratio is in the range of approximately 10% by mass to approximately 45% by mass.
  • a particularly desirable ratio is in the range of approximately 10% by mass to approximately 40% by mass.
  • the preferable ratio of the compound (2) is about 2% by mass or more for increasing the dielectric constant in the short axis direction of liquid crystal molecules, and about 50% by mass or less for decreasing the minimum temperature.
  • a more desirable ratio is in the range of approximately 2% by mass to approximately 30% by mass.
  • a particularly desirable ratio is in the range of approximately 2% by mass to approximately 20% by mass.
  • the preferable ratio of the compound (3) is about 10% by mass or more for decreasing the viscosity or increasing the maximum temperature, and about 90% by mass or less for increasing the dielectric anisotropy.
  • a more desirable ratio is in the range of approximately 15% by mass to approximately 80% by mass.
  • a particularly desirable ratio is in the range of approximately 20% by mass to approximately 70% by mass.
  • the preferable ratio of the compound (4) is about 5% by mass or more for increasing the dielectric anisotropy, and about 40% by mass or less for decreasing the minimum temperature.
  • a more desirable ratio is in the range of approximately 5% by mass to approximately 35% by mass.
  • a particularly desirable ratio is in the range of approximately 10% by mass to approximately 30% by mass.
  • a preferable ratio of the compound (5) is about 2% by mass or more for increasing the dielectric constant in the minor axis direction and about 50% by mass or less for decreasing the minimum temperature.
  • a more desirable ratio is in the range of approximately 4% by mass to approximately 40% by mass.
  • a particularly desirable ratio is in the range of approximately 4% by mass to approximately 30% by mass.
  • R 1 and R 6 are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, Alternatively, it is alkenyl having 2 to 12 carbons.
  • Preferred R 1 and R 6 are alkyl having 1 to 12 carbons for the purpose of increasing stability to light or heat.
  • R 2 , R 3 , R 7 , and R 8 are each hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons. Is.
  • Desirable R 2 , R 3 , R 7 , and R 8 are alkyl having 1 to 12 carbons for increasing the stability to light or heat, and for increasing the maximum temperature and increasing the refractive index anisotropy.
  • R 4 and R 5 are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. It is alkenyl.
  • Desirable R 4 and R 5 are alkenyl having 2 to 12 carbons for decreasing the viscosity and alkyl having 1 to 12 carbons for increasing the stability to light or heat.
  • Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More desirable alkyl is methyl, ethyl, propyl, butyl, or pentyl for decreasing the viscosity.
  • Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. More desirable alkoxy is methoxy or ethoxy for decreasing the viscosity.
  • Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, It is 3-hexenyl, 4-hexenyl, or 5-hexenyl. More desirable alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for decreasing the viscosity.
  • Trans is preferable in the alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity.
  • Cis is preferable in the alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl.
  • Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. More desirable alkenyloxy is allyloxy or 3-butenyloxy for decreasing the viscosity.
  • alkyl in which at least one hydrogen is replaced by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl. , Or 8-fluorooctyl.
  • a more preferable example is 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl for increasing the dielectric anisotropy.
  • alkenyl in which at least one hydrogen has been replaced by fluorine or chlorine include 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro. -4-pentenyl or 6,6-difluoro-5-hexenyl.
  • a more preferred example is 2,2-difluorovinyl or 4,4-difluoro-3-butenyl for decreasing the viscosity.
  • Ring A and ring B are 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine, pyrimidine-2,5-diyl, 1,3-dioxane- It is 2,5-diyl or tetrahydropyran-2,5-diyl.
  • Preferred ring A and ring B are 1,4-phenylene or 2-fluoro-1,4-phenylene for increasing the optical anisotropy.
  • Ring J is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4- It is phenylene, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl.
  • Preferred ring J is 1,4-phenylene or 2-fluoro-1,4-phenylene for increasing the optical anisotropy. Tetrahydropyran-2,5-diyl is Or And preferably Is.
  • Ring C and Ring E are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1 in which at least one hydrogen is replaced by fluorine or chlorine.
  • Preferred examples of “1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine” include 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene or 2-chloro- It is 3-fluoro-1,4-phenylene.
  • Preferred ring C and ring E are 1,4-cyclohexylene for decreasing the viscosity, tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and for increasing the optical anisotropy. It is 1,4-phenylene.
  • Ring K and ring M are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, naphthalene-2,6-diyl and at least one hydrogen.
  • Preferred examples of “1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine” include 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene or 2-chloro- It is 3-fluoro-1,4-phenylene.
  • Preferred ring K and ring M are 1,4-cyclohexylene for decreasing the viscosity, tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and for increasing the optical anisotropy. It is 1,4-phenylene.
  • Ring D and ring L are 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3 , 4,5-Trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl (FLF4), 4 , 6-difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2), or 1,1,6,7-tetrafluoroindane-2,5-diyl (InF4).
  • DBFF2 6-difluorodibenzofuran-3,7-diyl
  • DBTF2 4,6-difluorodibenzo
  • Preferred ring D and ring L are 2,3-difluoro-1,4-phenylene for decreasing the viscosity, and 2-chloro-3-fluoro-1,4-phenylene for decreasing the optical anisotropy. 7,8-difluorochroman-2,6-diyl for increasing the dielectric anisotropy.
  • Ring F and ring G are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene.
  • Preferred ring F or ring G is 1,4-cyclohexylene for decreasing the viscosity, or 1,4-phenylene for increasing the optical anisotropy.
  • Z 1 and Z 2 are single bonds, ethylene, vinylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy.
  • Preferred Z 2 is a single bond for decreasing the viscosity.
  • Z 3 , Z 4 , Z 7 , and Z 8 are single bonds, ethylene, vinylene, methyleneoxy, or carbonyloxy.
  • Preferred Z 3 , Z 4 , Z 7 , and Z 8 are single bonds for decreasing the viscosity, ethylene for decreasing the minimum temperature, and methyleneoxy for increasing the dielectric anisotropy.
  • Z 5 is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy.
  • Preferred Z 5 is a single bond for decreasing the viscosity.
  • X 1 and X 2 are hydrogen or fluorine. Preferred X 1 or X 2 is fluorine for increasing the dielectric anisotropy.
  • Y 1 and Y 2 are fluorine, chlorine, an alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, and an alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Or alkenyloxy having 2 to 12 carbons in which at least one hydrogen has been replaced by fluorine or chlorine.
  • Preferred Y 1 and Y 2 are fluorine for decreasing the minimum temperature.
  • a preferred example of alkyl in which at least one hydrogen is replaced by fluorine or chlorine is trifluoromethyl.
  • a preferred example of alkoxy in which at least one hydrogen has been replaced by fluorine or chlorine is trifluoromethoxy.
  • a preferred example of alkenyloxy in which at least one hydrogen has been replaced with fluorine or chlorine is trifluorovinyloxy.
  • A is 1, 2, 3, or 4, b is 0, 1, 2, or 3, and the sum of a and b is 4 or less.
  • Preferred a is 2 for lowering the minimum temperature and 3 for increasing the dielectric anisotropy.
  • Preferred b is 0 for increasing the maximum temperature and 1 for increasing the dielectric anisotropy.
  • c and g are 0, 1, 2, or 3, d and h are 0 or 1, the sum of c and d is 1, 2, or 3, and the sum of g and h is 3 It is below.
  • Preferred c or g is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.
  • Preferred d or h is 0 for decreasing the viscosity and 1 for decreasing the minimum temperature.
  • e is 1, 2, or 3.
  • Preferred e is 1 for decreasing the viscosity and 2 or 3 for increasing the maximum temperature.
  • f is 1, 2, 3, or 4.
  • Preferred f is 2 for decreasing the minimum temperature and 3 for increasing the dielectric
  • Preferred compound (1) includes compounds (1-1) to (1-14) described in item 2.
  • at least one of the first components is compound (1-2), compound (1-3), compound (1-4), compound (1-7), compound (1-8), compound ( 1-9), compound (1-10), or compound (1-12) are preferred.
  • Preferred compounds (2) are compounds (2-1) to (2-38) described in item 3.
  • at least one of the second components is compound (2-1), compound (2-2), compound (2-3), compound (2-4), compound (2-7), compound ( 2-8), compound (2-14), compound (2-15), compound (2-16), compound (2-17), compound (2-22), compound (2-32), compound (2 It is preferably -34), compound (2-35), compound (2-37), or compound (2-38).
  • At least two of the second components are preferably a combination of compound (2-1) and compound (2-3).
  • Preferred compounds (3) are the compounds (3-1) to (3-13) described in item 6.
  • at least one of the third components is compound (3-1), compound (3-2), compound (3-3), compound (3-5), compound (3-6), compound ( It is preferably 3-7), compound (3-8), compound (3-11), or compound (3-13).
  • At least two of the third components are compound (3-1) and compound (3-5), compound (3-1) and compound (3-6), compound (3-1) and compound (3-7), Compound (3-1) and compound (3-8), compound (3-1) and compound (3-13), compound (3-3) and compound (3-5), compound (3-3) and compound (3-6), compound (3-3) and compound (3-7), compound (3-3) and compound (3-8), or combination of compound (3-3) and compound (3-13) Is preferred.
  • Preferred compounds (4) are the compounds (4-1) to (4-16) described in item 9.
  • at least one of the fourth components is compound (4-4), compound (4-7), compound (4-8), compound (4-11), compound (4-12), compound ( It is preferably 4-13), the compound (4-14), or the compound (4-16).
  • At least two of the fourth components are compound (4-11) and compound (4-12), compound (4-11) and compound (4-13), compound (4-11) and compound (4-16), Alternatively, a combination of compound (4-12) and compound (4-13) is preferable.
  • Preferred compounds (5) are the compounds (5-1) to (5-31) described in item 12.
  • at least one of the fifth components is compound (5-1), compound (5-2), compound (5-3), compound (5-6), compound (5-7), compound ( 5-8), compound (5-9), compound (5-13), compound (5-15), or compound 5-17) is preferred.
  • At least two of the fifth components are compound (5-1) and compound (5-4), compound (5-1) and compound (5-6), compound (5-1) and compound (5-7), Compound (5-1) and compound (5-9), compound (5-1) and compound (5-13), compound (5-1) and compound (5-15), compound (5-1) and compound (5-16), compound (5-7) and compound (5-8), compound (5-7) and compound (5-9), compound (5-7) and compound (5-13), compound ( 5-7) and compound (5-15), or a combination of compound (5-13) and compound (5-15) is preferable.
  • Such additives are optically active compounds, antioxidants, ultraviolet absorbers, quenchers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like.
  • An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules to give a twist angle. Examples of such compounds are compound (6-1) to compound (6-5).
  • a desirable ratio of the optically active compound is about 5% by mass or less. A more desirable ratio is in the range of approximately 0.01% by mass to approximately 2% by mass.
  • an antioxidant is used. Added to the composition.
  • An example of the antioxidant is a compound represented by the formula (7).
  • R 9 is alkyl having 1 to 12 carbons.
  • Preferred R 9 is methyl, propyl, pentyl, or heptyl.
  • Ring Q is 1,4-cyclohexylene, 1,4-phenylene, or 1,3-dioxane-2,5-diyl.
  • a preferred ring Q is 1,4-cyclohexylene.
  • j is 0, 1, or 2.
  • Preferred j is 0 or 1.
  • Preferred compound (7) includes compound (7-1) to compound (7-3).
  • Preferred examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like.
  • Light stabilizers such as sterically hindered amines are also preferred.
  • Preferred examples of the light stabilizer include compound (8-1) to compound (8-16).
  • the preferred ratio of these absorbents and stabilizers is about 50 ppm or more for obtaining the effect, and about 10,000 ppm or less for not lowering the upper limit temperature or for not raising the lower limit temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 10,000 ppm.
  • the quencher is a compound that receives the light energy absorbed by the liquid crystal compound and converts it into heat energy, thereby preventing decomposition of the liquid crystal compound.
  • the quencher include compounds (9-1) to (9-7).
  • a desirable ratio of these quenchers is about 50 ppm or more for obtaining the effect, and about 20,000 ppm or less for not raising the minimum temperature.
  • a more desirable ratio is in the range of approximately 100 ppm to approximately 10,000 ppm.
  • Dichroic dyes such as azo dyes and anthraquinone dyes are added to the composition in order to adapt to GH (guest host) mode devices.
  • the preferred proportion of dye is in the range of about 0.01% to about 10% by weight.
  • An antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is added to the composition to prevent foaming.
  • the preferable ratio of the defoaming agent is about 1 ppm or more to obtain the effect, and about 1000 ppm or less to prevent display defects. A more desirable ratio is in the range of approximately 1 ppm to approximately 500 ppm.
  • a polymerizable compound is used to adapt to a polymer-supported orientation (PSA) type device.
  • Preferred examples of such a polymerizable compound are compounds such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. Further preferred examples are acrylate or methacrylate derivatives.
  • a preferred ratio is 10% by mass or more based on the total mass of the polymerizable compound. A more desirable ratio is 50% by mass or more. A particularly desirable ratio is 80% by mass or more. The most preferable ratio is 100% by mass.
  • a polymerization inhibitor When storing a polymerizable compound, a polymerization inhibitor may be added to prevent polymerization.
  • the polymerizable compound is usually added to the composition without removing the polymerization inhibitor.
  • the polymerization inhibitor are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine and the like.
  • the polar compound is an organic compound having polarity.
  • a compound having an ionic bond is not included. Atoms such as oxygen, sulfur, and nitrogen are more electronegative and tend to have a partial negative charge. Carbon and hydrogen tend to be neutral or have a partial positive charge. Polarity arises from the uneven distribution of partial charges among different atoms in the compound.
  • the polar compound has at least one of the partial structures such as —OH, —COOH, —SH, —NH 2 ,>NH,> N—.
  • the compound (1-1) is obtained from Aldrich (Sigma-Aldrich Corporation) or is synthesized by the method described in US Pat. No. 3,660,505.
  • the compound (2-3 is synthesized by the method described in International Publication No. 1999/021816.
  • the compound (3-1) is synthesized by the method described in JP-A-59-176221.
  • -1) is synthesized by the method described in JP 2000-053602A.
  • composition is prepared from the compounds thus obtained by known methods. For example, the component compounds are mixed and dissolved by heating.
  • the composition mainly has a minimum temperature of about ⁇ 10 ° C. or lower, a maximum temperature of about 70 ° C. or higher, and an optical anisotropy in the range of about 0.07 to about 0.20.
  • a composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the ratio of component compounds or by mixing with other liquid crystal compounds.
  • Compositions having optical anisotropy in the range of about 0.10 to about 0.30 may be prepared by trial and error.
  • a device containing this composition has a large voltage holding ratio.
  • This composition is suitable for an AM device.
  • This composition is particularly suitable for a transmissive AM device.
  • This composition can be used as a composition having a nematic phase, or as an optically active composition by adding an optically active compound.
  • This composition can be used for AM devices. Further, it can be used for a PM element.
  • This composition can be used for AM and PM devices having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA and FPA.
  • the use in AM devices having TN, OCB, IPS mode or FFS mode is particularly preferable.
  • the liquid crystal molecules may be aligned in parallel with or perpendicular to the glass substrate.
  • These elements may be reflective, transmissive or transflective. Use in a transmissive element is preferred. It can also be used for an amorphous silicon-TFT device or a polycrystalline silicon-TFT device. It can also be used for an NCAP (nematic curvilinear aligned phase) type device produced by microencapsulating this composition and a PD (polymer dispersed) type device in which a three-dimensional network polymer is formed in the composition.
  • NCAP non-curvilinear aligned phase
  • the present invention will be described in more detail by way of examples. The invention is not limited by these examples.
  • the present invention comprises a mixture of the composition of Example 1 and the composition of Example 2.
  • the present invention also includes a mixture of at least two of the example compositions.
  • the synthesized compound was identified by a method such as NMR analysis. The properties of the compounds, compositions, and devices were measured by the methods described below.
  • NMR analysis DRX-500 manufactured by Bruker BioSpin was used for the measurement.
  • the sample was dissolved in a deuterated solvent such as CDCl 3 and the measurement was performed at room temperature under the conditions of 500 MHz and 16 times of integration.
  • Tetramethylsilane was used as an internal standard.
  • CFCl 3 was used as an internal standard, and the number of times of integration was 24.
  • s means a singlet, d a doublet, t a triplet, q a quartet, quin a quintet, sex a sextet, m a multiplet, and br a broad.
  • a Shimadzu GC-14B gas chromatograph was used for the measurement.
  • the carrier gas is helium (2 mL / min).
  • the sample vaporization chamber was set at 280 ° C and the detector (FID) was set at 300 ° C.
  • a capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m; fixed liquid phase dimethylpolysiloxane; non-polar) made by Agilent Technologies Inc. was used for separation of component compounds.
  • the column was held at 200 ° C. for 2 minutes and then heated to 280 ° C. at a rate of 5 ° C./minute.
  • the sample was prepared in an acetone solution (0.1% by mass), and 1 ⁇ L thereof was injected into the sample vaporization chamber.
  • the recorder is a C-R5A type Chromatopac manufactured by Shimadzu Corporation or its equivalent.
  • the obtained gas chromatogram showed the retention times of peaks and the areas of peaks corresponding to the component compounds.
  • capillary column As the solvent for diluting the sample, chloroform, hexane, etc. may be used.
  • the following capillary column may be used to separate the component compounds.
  • HP-1 made by Agilent Technologies Inc. (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m), Rtx-1 made by Restek Corporation (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m), BP-1 manufactured by SGE International Pty. Ltd (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m).
  • a capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 ⁇ m) manufactured by Shimadzu Corporation may be used for the purpose of preventing overlapping of compound peaks.
  • the ratio of the liquid crystal compound contained in the composition may be calculated by the following method.
  • the mixture of liquid crystal compounds is analyzed by gas chromatography (FID).
  • the area ratio of the peaks in the gas chromatogram corresponds to the ratio of liquid crystal compounds.
  • the correction coefficient of each liquid crystal compound may be regarded as 1. Therefore, the ratio (mass%) of the liquid crystal compound can be calculated from the peak area ratio.
  • the following mother liquid crystals were used.
  • the ratio of the component compounds is shown by mass%.
  • Measurement method The characteristics were measured by the following methods. Most of these are the methods described in the JEITA standard (JEITA / ED-2521B), which is deliberated and established by the Japan Electronics and Information Technology Industries Association (JEITA), or methods modified from this. Met. No thin film transistor (TFT) was attached to the TN device used for the measurement.
  • JEITA Japan Electronics and Information Technology Industries Association
  • T C Minimum temperature of nematic phase
  • a sample having a nematic phase is put in a glass bottle and placed in a freezer at 0 ° C, -10 ° C, -20 ° C, -30 ° C, and -40 ° C for 10 days. After storage, the liquid crystal phase was observed.
  • T C was described as ⁇ 20 ° C. when the sample remained in the nematic phase at ⁇ 20 ° C. and changed to a crystalline or smectic phase at ⁇ 30 ° C.
  • the lower limit temperature of the nematic phase may be abbreviated as “lower limit temperature”.
  • Viscosity Bulk viscosity; ⁇ ; measured at 20 ° C .; mPa ⁇ s: An E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used for measurement.
  • Viscosity (rotational viscosity; ⁇ 1; measured at 25 ° C; mPa ⁇ s): The measurement is performed according to the method described in M.Imaietetal., Molecular Crystals and Liquid Crystals, Vol.259, 37, (1995). I obeyed. The sample was put in a TN device having a twist angle of 0 ° and a distance (cell gap) between two glass substrates of 5 ⁇ m. A voltage of 16V to 19.5V was applied to the device in steps of 0.5V. After 0.2 seconds of non-application, application was repeated under the conditions of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds).
  • the peak current (peak current) and the peak time (peak time) of the transient current generated by this application were measured.
  • the rotational viscosity value was obtained from these measured values and the calculation formula (10) described on page 40 of the paper by M. Imai et al.
  • the value of the dielectric anisotropy required for this calculation was determined by the method described below using the device whose rotational viscosity was measured.
  • Threshold voltage (Vth; measured at 25 ° C .; V): LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement.
  • the light source was a halogen lamp.
  • the sample was put in a normally white mode TN device in which the distance (cell gap) between two glass substrates was 0.45 / ⁇ n ( ⁇ m) and the twist angle was 80 degrees.
  • the voltage (32 Hz, rectangular wave) applied to this element was increased stepwise from 0 V to 10 V by 0.02 V.
  • the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured.
  • a voltage-transmittance curve in which the transmittance is 100% when the amount of light is maximum and the transmittance is 0% when the amount of light is minimum was created.
  • the threshold voltage is represented by the voltage when the transmittance reaches 90%.
  • VHR-9 Voltage holding ratio
  • the TN device used for measurement had a polyimide alignment film, and the distance (cell gap) between two glass substrates was 5 ⁇ m. .. This device was sealed with an adhesive which was cured by ultraviolet rays after the sample was put in.
  • a pulse voltage 60 microseconds at 1 V was applied to the TN device to charge it.
  • the decaying voltage was measured with a high-speed voltmeter for 166.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit cycle was obtained.
  • Area B was the area when it was not attenuated.
  • the voltage holding ratio was expressed as a percentage of the area A with respect to the area B.
  • VHR-10 Voltage holding ratio (VHR-10; measured at 60 ° C .;%): The voltage holding ratio was measured by the same procedure as above except that it was measured at 60 ° C. instead of 25 ° C. The obtained value was represented by VHR-10.
  • VHR-11 Voltage holding ratio
  • the TN device used for the measurement had a polyimide alignment film, and the cell gap was 5 ⁇ m. A sample was injected into this device and was irradiated with 5 mW / cm 2 ultraviolet rays for 167 minutes.
  • the light source was a black light manufactured by Eye Graphics Co., Ltd., F40T10 / BL (peak wavelength 369 nm), and the distance between the element and the light source was 5 mm.
  • the VHR-11 measurement measured the decaying voltage for 166.7 milliseconds. Compositions with large VHR-11 have great stability to UV light.
  • VHR-12 Voltage holding ratio
  • the rise time ( ⁇ r: rise time; millisecond) is the time required for the transmittance to change from 90% to 10%.
  • the fall time ( ⁇ f: fall time; millisecond) is the time required to change the transmittance from 10% to 90%.
  • the response time was represented by the sum of the rise time and fall time thus obtained.
  • Elastic constant (K; measured at 25 ° C .; pN): An HP4284A type LCR meter manufactured by Yokogawa / Hewlett Packard Co. was used for the measurement. The sample was placed in a horizontal alignment device in which the distance (cell gap) between two glass substrates was 20 ⁇ m. A charge of 0 V to 20 V was applied to this device, and the electrostatic capacity and the applied voltage were measured. Fitting the measured capacitance (C) and applied voltage (V) values using the formula (2.98) and formula (2.101) on page 75 of "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun). Then, the values of K11 and K33 were obtained from the formula (2.99). Next, K22 was calculated by using the values of K11 and K33 obtained earlier in the equation (3.18) on page 171. The elastic constant was represented by the average value of K11, K22, and K33 thus obtained.
  • Dielectric constant in short axis direction ( ⁇ ; measured at 25 ° C.): A sample was put in a TN device in which a distance (cell gap) between two glass substrates was 9 ⁇ m and a twist angle was 80 degrees. .. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the dielectric constant ( ⁇ ) in the short axis direction of the liquid crystal molecule was measured.
  • Line Image Sticking Parameter (LISP;%): A line afterimage was generated by applying an electrical stress to the liquid crystal display device. The luminance of the area with the line afterimage and the luminance of the remaining area were measured. The ratio of the decrease in luminance due to the line afterimage was calculated, and the size of the line afterimage was expressed by this ratio. 17a) Luminance measurement: An image of the device was taken using an imaging color luminance meter (PM-1433F-0 manufactured by Radiant Zemax). The brightness of each region of the device was calculated by analyzing the image using software (Prometric 9.1, manufactured by Radiant Imaging).
  • a sample is put into an FFS element (16 cells of 4 cells in length ⁇ 4 cells in width) having a cell gap of 3.5 ⁇ m and having a matrix structure, and an adhesive agent that cures this element with ultraviolet rays is used. And sealed. Polarizing plates were arranged on the upper surface and the lower surface of the device so that the polarization axes were orthogonal to each other.
  • the device was irradiated with light and a voltage (rectangular wave, 60 Hz) was applied.
  • the voltage was increased stepwise in the range of 0V to 7.5V in steps of 0.1V, and the brightness of the transmitted light at each voltage was measured.
  • the voltage when the brightness becomes maximum is abbreviated as V255.
  • the voltage when the brightness becomes 21.6% of V255 (that is, 127 gradations) is abbreviated as V127.
  • V255 rectangular wave, 30 Hz
  • 0.5 V rectangular wave, 30 Hz
  • V127 rectangular wave, 0.25 Hz
  • Example of composition is shown below.
  • the component compounds are represented by symbols based on the definitions in Table 3 below.
  • Table 3 the configuration for 1,4-cyclohexylene is trans.
  • the number in parentheses after the symbol corresponds to the compound number.
  • the symbol ( ⁇ ) means other liquid crystal compound.
  • the ratio (percentage) of the liquid crystal compound is a mass percentage (mass%) based on the mass of the liquid crystal composition.
  • Example 1 Comparing Example 1 and Comparative Example 1, the value of ⁇ in Example 1 is larger and the dielectric constant in the minor axis direction of the liquid crystal molecules is larger. Further, comparing Example 2 and Comparative Example 2, the value of ⁇ in Example 2 is larger, and the dielectric constant in the minor axis direction of the liquid crystal molecules is larger. Therefore, it is concluded that the composition of the present invention has excellent properties.
  • the liquid crystal composition of the present invention can be used for liquid crystal monitors, liquid crystal televisions, and the like.

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  • Crystallography & Structural Chemistry (AREA)
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Abstract

La présente invention concerne une composition de cristaux liquides ayant une grande constante diélectrique (ε⊥) dans la direction d'axe mineur de molécules de cristaux liquides ; et un élément d'affichage à cristaux liquides qui contient cette composition et a un facteur de transmission élevé et un rapport de contraste élevé. Une composition de cristaux liquides qui contient, en tant que premier composant, au moins un composé qui est choisi parmi des composés représentés par la formule (1), tout en contenant en tant que second composant, au moins un composé qui est choisi parmi des composés représentés par la formule (2), et qui a une anisotropie diélectrique positive ; et un élément d'affichage à cristaux liquides qui contient cette composition de cristaux liquides.
PCT/JP2019/030968 2018-11-05 2019-08-06 Composition de cristaux liquides et élément d'affichage à cristaux liquides WO2020095499A1 (fr)

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