WO2019138791A1 - Composition de cristaux liquides et dispositif d'affichage à cristaux liquides - Google Patents

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

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Publication number
WO2019138791A1
WO2019138791A1 PCT/JP2018/046348 JP2018046348W WO2019138791A1 WO 2019138791 A1 WO2019138791 A1 WO 2019138791A1 JP 2018046348 W JP2018046348 W JP 2018046348W WO 2019138791 A1 WO2019138791 A1 WO 2019138791A1
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liquid crystal
hydrogen
carbons
replaced
compound
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PCT/JP2018/046348
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English (en)
Japanese (ja)
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崇徳 森
利樹 朝倉
将之 齋藤
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Jnc株式会社
Jnc石油化学株式会社
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Priority to JP2019564358A priority Critical patent/JPWO2019138791A1/ja
Publication of WO2019138791A1 publication Critical patent/WO2019138791A1/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
    • C09K19/20—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
    • C09K19/38—Polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • 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 element containing the composition, and the like.
  • the present invention relates to a liquid crystal composition having a negative dielectric anisotropy, and a liquid crystal display device containing the composition and having a mode such as IPS, VA, FFS, or FPA.
  • the present invention also relates to a polymer supported alignment type liquid crystal display device.
  • phase change PC
  • TN twisted nematic
  • STN super twisted nematic
  • EOB electrically controlled birefringence
  • OCB optically compensated bend
  • IPS modes are modes such as (in-plane switching), VA (vertical alignment), FFS (fringe field switching), and FPA (field-induced photo-reactive alignment).
  • PM passive matrix
  • AM active matrix
  • PM is classified into static, multiplex, etc.
  • AM is classified into thin film transistor (TFT), metal insulator metal (MIM), etc.
  • TFT thin film transistor
  • MIM metal insulator metal
  • the classification of TFT is amorphous silicon and polycrystal silicon. The latter are classified into high temperature type and low temperature type according to the manufacturing process.
  • Source based classifications are reflective based on natural light, transmissive based on back light, and semi-transmissive based on both natural light and back light.
  • the liquid crystal display element contains a liquid crystal composition having a nematic phase.
  • This composition has suitable properties. By improving the properties of this composition, an AM element having good properties can be obtained.
  • the associations in these properties are summarized in Table 1 below. The characteristics of the composition will be further described based on commercially available AM devices.
  • the temperature range of the nematic phase is related to the usable temperature range of the device.
  • the preferred upper temperature limit of the nematic phase is about 70 ° C. or higher, and the preferred lower temperature limit of the nematic phase is about -10 ° C. or lower.
  • the viscosity of the composition is related to the response time of the device. Short response times are preferred for displaying motion pictures on the device. Even shorter response times of 1 millisecond are desirable. Thus, low viscosity in the composition is preferred. Small viscosities at low temperatures are more preferred.
  • the optical anisotropy of the composition is related to the contrast ratio of the device.
  • a large or small optical anisotropy ie a suitable optical anisotropy
  • the product ( ⁇ n ⁇ d) of the optical anisotropy ( ⁇ n) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio.
  • the appropriate value of the product depends on the type of operating mode. This value is in the range of about 0.30 ⁇ m to about 0.40 ⁇ m in the VA mode device and in the range of about 0.20 ⁇ m to about 0.30 ⁇ m in the IPS mode or FFS mode device. In these cases, compositions with large optical anisotropy are preferred for small cell gap devices.
  • the large dielectric anisotropy in the composition contributes to low threshold voltage, low power consumption and high contrast ratio in the device. Therefore, large dielectric anisotropy is preferred.
  • the large resistivity in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a large specific resistance at the initial stage is preferred. After prolonged use, compositions having high specific resistance are preferred.
  • the stability of the composition to ultraviolet light and heat is related to the lifetime of the device. When this stability is high, the lifetime of the device is long. Such characteristics are preferable for an AM element used for a liquid crystal monitor, a liquid crystal television or the like.
  • a polymer is combined with an alignment film.
  • a composition to which a small amount of a polymerizable compound is added is injected into the device.
  • the composition is irradiated with ultraviolet light while applying a voltage between the substrates of the device.
  • the polymerizable compound polymerizes to form a polymer network in the composition.
  • the polymer can control the alignment of liquid crystal molecules, thereby reducing the response time of the device and improving the image sticking.
  • Such an effect of the polymer can be expected to devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
  • an AM device having a TN mode a composition having positive dielectric anisotropy is used.
  • a composition having negative dielectric anisotropy is used.
  • an AM device having an IPS mode or an FFS mode a composition having positive or negative dielectric anisotropy is used.
  • a composition having positive or negative dielectric anisotropy is used in an AM element of a polymer sustained alignment (PSA) type.
  • PSA polymer sustained alignment
  • One object of the present invention is: high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, suitable optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability to light It is an object of the present invention to provide a liquid crystal composition satisfying at least one of properties such as high stability to heat. Another object is to provide a liquid crystal composition having a proper 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 an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long lifetime.
  • the present invention provides at least one compound selected from a compound represented by the formula (S) as a first additive and a compound in which at least one hydrogen of the compound represented by the formula (S) is replaced with a monovalent group. And a liquid crystal composition having a nematic phase and negative dielectric anisotropy, and a liquid crystal display device containing the composition.
  • the advantages of the present invention are: high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, appropriate optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability to light, thermal It is to provide a liquid crystal composition satisfying at least one of the properties such as high stability to. Another advantage is to provide a liquid crystal composition having a suitable balance between at least two of these properties. Another advantage is to provide a liquid crystal display device containing such a composition. Another advantage is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long lifetime.
  • liquid crystal composition and “liquid crystal display element” may be abbreviated as “composition” and “element”, respectively.
  • “Liquid crystal display element” is a generic term for liquid crystal display panels and liquid crystal display modules.
  • the “liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase or a smectic phase and has no liquid crystal phase, but for the purpose of adjusting properties such as temperature range of the nematic phase, viscosity and dielectric anisotropy. It is a general term for compounds mixed in a composition.
  • This compound has, for example, a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecule (liquid crystal molecule) is rod like.
  • the "polymerizable compound” is a compound to be 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 optically active compounds and polymerizable compounds are added to the liquid crystal composition as needed.
  • the proportion of the liquid crystal compound is represented by mass percentage (mass%) based on the mass of the liquid crystal composition not including the additive even when the additive is added.
  • the proportion of the additive is represented by mass percentage (mass%) based on the mass of the liquid crystal composition containing no additive. That is, the proportions of the liquid crystal compound and the additive are calculated based on the total mass of the liquid crystal compound.
  • the “upper limit temperature of the nematic phase” may be abbreviated as the “upper limit temperature”.
  • the “lower limit temperature of the nematic phase” may be abbreviated as the “lower limit temperature”.
  • the expression "increase the dielectric anisotropy” means that in the case of a composition having a positive dielectric anisotropy, the value increases positively, and a composition having a negative dielectric anisotropy. In the case of goods, it means that the value increases negatively.
  • the "high voltage holding ratio” means that the device has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit at the initial stage, and after a long period of use it shows a large voltage not only at room temperature but also at a temperature near the upper limit. It means having a retention rate.
  • the characteristics of the composition or the device may be examined by a time-dependent change test.
  • Formula (1z) is taken as an example. At least one compound selected from the compounds represented by formula (1z) may be abbreviated as “compound (1z)”.
  • the “compound (1z)” means one compound represented by the 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 compounds represented by the formula (1z) and the formula (2z)” means at least one compound selected from the group of the compound (1z) and the compound (2z) .
  • Ra and Rb is alkyl, alkoxy or alkenyl
  • Ra and Rb are independently selected from the group of alkyl, alkoxy and alkenyl. That is, the group represented by Ra and the group represented by Rb may be the same or different. This rule is also applied when the symbol of Ra is used for a plurality of compounds.
  • symbols of ⁇ and ⁇ surrounded by a hexagon correspond to the ring ⁇ and the ring ⁇ , respectively, and represent a ring such as a 6-membered ring or a fused ring.
  • the index 'x' is 2, two rings ⁇ are present.
  • the two groups represented by the two rings ⁇ may be identical or different.
  • This rule applies to any two rings ⁇ when the index 'x' is greater than two.
  • the oblique lines crossing one side of the ring ⁇ indicate that any hydrogen on the ring ⁇ may be replaced with a substituent (—Sp—P).
  • the index 'y' indicates the number of substituted substituents. There is no such substitution when the index 'y' is zero.
  • a plurality of substituents (-Sp-P) are present on the ring ⁇ .
  • the rule "may be identical or different" applies also if the compounds have identical substituents.
  • the expression "at least one 'A'” means that the number of 'A' is arbitrary.
  • the expression "at least one -CH 2- may be replaced by -O-" may be 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 by -O-. This replacement is because -OO-CH 2- (peroxide) is formed.
  • the alkyl of the liquid crystal compound is linear or branched and does not contain cyclic alkyl. Linear alkyls are preferred over branched alkyls. The same is true for end groups such as alkoxy and alkenyl.
  • the configuration of 1,4-cyclohexylene is preferably trans rather than cis in order to increase the maximum temperature. Because 2-fluoro-1,4-phenylene is left-right asymmetrical, there are left (L) and right (R) orientations.
  • divalent groups such as tetrahydropyran-2,5-diyl.
  • linking groups (-COO- or -OCO-) such as carbonyloxy.
  • the present invention includes the following items.
  • Item 1 Containing at least one compound selected from a compound represented by the formula (S) as a first additive, and a compound in which at least one hydrogen of the compound represented by the formula (S) is replaced with a monovalent group Liquid crystal composition having a nematic phase and negative dielectric anisotropy.
  • Item 2. The liquid crystal composition according to item 1, containing at least one compound selected from the compounds represented by formula (1) as a first additive.
  • R 1a , R 1b and R 1c are hydrogen, alkyl having 1 to 20 carbon atoms, alicyclic hydrocarbon group having 3 to 20 carbon atoms, or aromatic carbon having 6 to 20 carbon atoms
  • a hydrogen group, in which at least one —CH 2 — may be replaced by —O—, —NH—, —CO—, —COO—, or —OCO—, at least one — CH 2 —CH 2 — may be replaced by —CH CH— or —C ⁇ C—, and in these groups, at least one hydrogen is an alkyl having 1 to 10 carbons, 1 to 10 carbons May be replaced by alkoxy or halogen; n is 1, 2, 3 or 4.
  • Item 3. The liquid crystal composition according to item 1 or 2, containing at least one compound selected from compounds represented by formula (1-1) to formula (1-10) as a first additive.
  • R 1d is hydrogen or alkyl having 1 to 15 carbon atoms, and in this alkyl, at least one —CH 2 — is —O—, —NH -, -CO-, -COO-, or -OCO- may be replaced;
  • R 1e and R 1f are hydrogen, alkyl having 1 to 15 carbons, or alkoxy having 1 to 15 carbons;
  • R 1 g is hydrogen or alkyl having 1 to 15 carbons;
  • R 1 h is hydrogen or alkyl having 1 to 15 carbons, and in this alkyl, at least one —CH 2 — is —O—, —NH -, - CO -, - COO- , or may be replaced by -OCO-;
  • R 1i is alkyl of 1 to 10 carbons, there 1 -C
  • Item 4. The liquid crystal composition according to any one of items 1 to 3, wherein the proportion of the first additive is in the range of 0.001% by mass to 2% by mass.
  • 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 (2) as a first component.
  • R 2a and R 2b are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or at least Ring A and ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-, wherein C 1-12 alkyl in which one hydrogen is replaced by fluorine or chlorine; 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, in which at least one hydrogen is replaced by fluorine or chlorine, 6-diyl, chroman-2, 6-diyl or a group in which at least one compound selected from
  • 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 formula (2-1) to formula (2-35) as a first component.
  • R 2a and R 2b are each hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, 2 to 12 alkenyloxy, or C 1 to C 12 alkyl in which at least one hydrogen is replaced by fluorine or chlorine.
  • Item 7. The liquid crystal composition according to item 5 or 6, wherein the proportion of the first 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 (3) as a second component.
  • R 3a and R 3b 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
  • Ring C and ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4;
  • Z 3a is a single bond, ethylene or carbonyloxy;
  • c is 1, 2 or 3.
  • Item 9. The liquid crystal composition according to any one of items 1 to 8, containing at least one compound selected from the compounds represented by formulas (3-1) to (3-13) as a second component.
  • R 3a and R 3b are each an alkyl of 1 to 12 carbons, an alkoxy of 1 to 12 carbons, an alkenyl of 2 to 12 carbons, or at least one of Hydrogen is alkenyl having 2 to 12 carbon atoms replaced with fluorine or chlorine.
  • Item 10 The liquid crystal composition according to item 8 or 9, wherein the proportion of the second component is in the range of 10% by mass to 90% by mass.
  • Item 11 The liquid crystal composition according to any one of items 1 to 10, containing at least one compound selected from polymerizable compounds represented by formula (4) as a second additive.
  • ring F and ring I are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl Or pyridin-2-yl, in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is fluorine or chlorine And may be substituted by alkyl having 1 to 12 carbon atoms which is substituted with ring G: 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl
  • Item 12. The liquid crystal composition according to item 11, wherein in formula (4), P 4a , P 4b and P 4c are groups selected from the polymerizable groups represented by formulas (P-1) to (P-5) object.
  • P 4a , P 4b and P 4c are groups selected from the polymerizable groups represented by formulas (P-1) to (P-5) object.
  • M 1 , M 2 , and M 3 are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is replaced with fluorine or chlorine And alkyl having 1 to 5 carbon atoms.
  • Item 13 The liquid crystal according to any one of items 1 to 12, containing at least one compound selected from polymerizable compounds represented by formula (4-1) to formula (4-29) as a second additive: Composition.
  • P 4d , P 4e , and P 4f are each selected from the groups represented by formulas (P-1) to (P-3): A group wherein M 1 , M 2 and M 3 are hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine Yes:
  • Item 14 The liquid crystal composition according to any one of items 11 to 13, wherein the proportion of the second additive is in the range of 0.03% by mass to 10% by mass.
  • Item 15 A liquid crystal display device containing the liquid crystal composition according to any one of items 1 to 14.
  • Item 16 The liquid crystal display element according to item 15, wherein an operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and a driving method of the liquid crystal display element is an active matrix method.
  • Item 17 A polymer supported alignment type liquid crystal display device, comprising the liquid crystal composition according to any one of items 11 to 14, wherein a polymerizable compound in the liquid crystal composition is polymerized.
  • Item 18 Use of the liquid crystal composition according to any one of items 1 to 14 in a liquid crystal display device.
  • Item 19 Use of the liquid crystal composition according to any one of items 11 to 14 in a polymer supported alignment type liquid crystal display device.
  • the present invention also includes the following items.
  • A One compound, two compounds, or one compound selected from additives such as optically active compounds, antioxidants, ultraviolet light absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors A composition as described above containing three or more compounds.
  • B AM element containing the above composition.
  • C The above composition further containing a polymerizable compound, and an AM element of a polymer supported orientation (PSA) type containing this composition.
  • D An AM element of polymer supported orientation (PSA) type containing the above composition, and the polymerizable compound in this composition is polymerized.
  • (E) A device containing the composition described above and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA.
  • (F) A transmission type device containing the above composition.
  • (G) Use of the above composition as a composition having a nematic phase.
  • (H) Use as an optically active composition by adding an optically active compound to the above composition.
  • composition of the present invention will be described in the following order. First, the constitutions of component compounds in the composition will be described. Second, the main properties of the component compounds and the main effects of the compounds on the composition are explained. Third, the combination of components in the composition, the preferred ratio of the components and the basis thereof will be described. Fourth, the preferred embodiments of the component compounds are described. Fifth, preferred component compounds are shown. Sixth, additives that may be added to the composition will be described. Seventh, the synthesis methods of the component compounds will be described. Finally, the application of the composition is described.
  • This composition contains a plurality of liquid crystal compounds.
  • the composition may contain an additive.
  • the additive is an optically active compound, an antioxidant, an ultraviolet light absorber, a quencher, a pigment, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, a polar compound and the like.
  • This composition is classified into the composition A and the composition B from the viewpoint of the liquid crystal compound.
  • Composition A may further contain other liquid crystal compounds, additives, and the like in addition to the liquid crystal compound selected from compound (2) and compound (3).
  • the “other liquid crystal compound” is a liquid crystal compound different from the compound (2) and the compound (3). Such compounds are mixed into the composition for the purpose of further adjusting the properties.
  • Composition B consists essentially of the liquid crystal compound selected from compound (2) and compound (3). "Substantially" means that composition B may contain an additive, but does not contain any other liquid crystal compound. Composition B has a smaller number of components than composition A. Composition B is preferable to composition A in terms of cost reduction. Composition A is preferable to composition B from the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds.
  • the main properties of the component compounds are summarized in Table 2 based on the effects of the present invention.
  • L means large or high, M medium, and S small or low.
  • L, M, S are classifications based on qualitative comparisons among the component compounds, and 0 (zero) means smaller than S.
  • the main effects of the component compounds are as follows.
  • the first additive acts as an antioxidant and contributes to high heat or light stability.
  • Compound (1) does not affect properties such as the upper limit temperature, the optical anisotropy, and the dielectric anisotropy in many cases because the amount of addition is small.
  • Compound (2) raises the dielectric anisotropy and lowers the lower limit temperature.
  • the compound (3) lowers the viscosity or raises the upper limit temperature.
  • the compound (4) is polymerizable to give a polymer by polymerization. The polymer stabilizes the orientation of the liquid crystal molecules, thereby reducing the response time of the device and improving the image sticking.
  • Organic compounds are degraded by light and heat energy to generate radicals.
  • This radical acts as a chain carrier and further reacts with other organic compounds to generate a new radical, which is linked.
  • the antioxidant preferentially reacts with radicals present in the system to capture radicals generated as the product (organic compound) degrades, thereby suppressing chain reaction, that is, the progress of degradation.
  • Phenolic antioxidants such as 2,6-di-tert-butyl-4-methylphenol are used as general antioxidants, donate hydrogen of phenol moiety to radical, and are themselves steric hindrance It becomes a phenoxy radical with low activity, etc. Then, the radical is trapped and stabilized. This action suppresses the increase of radicals.
  • the first additive of the present invention is at least one compound selected from a compound represented by the formula (S) and a compound represented by the formula (S) in which at least one hydrogen is replaced with a monovalent group. It is.
  • the OH group of this compound becomes a phenoxy radical, the conjugated system is expanded, and radical scavenging is performed more efficiently. For this reason, compared with the conventional antioxidant, high activity antioxidant effect
  • first additive + compound (2) first additive + compound (3)
  • first additive + compound (2) + compound (3) first additive + compound (2) + compound (3)
  • first additive + compound (2) + second additive first additive + compound (3) + second additive
  • first additive + compound (3) + second additive or first additive + compound (2) + compound (3) + second additive.
  • a further preferable combination is the first additive + compound (2) + compound (3) or the first additive + compound (2) + compound (3) + second additive.
  • the preferred proportion of the first additive is about 0.001% by mass or more to increase the stability to heat or light, and about 2% by mass or less to lower the lower limit temperature.
  • a further preferred ratio is in the range of about 0.01% by weight to about 1% by weight.
  • An especially desirable ratio is in the range of about 0.03% by mass to about 0.5% by mass.
  • the preferred proportion of the compound (2) is about 10% by mass or more in order to increase the dielectric anisotropy, and about 90% by mass or less in order to lower the lower limit temperature.
  • a further preferred ratio is in the range of about 20% by weight to about 80% by weight.
  • An especially desirable ratio is in the range of about 30% by weight to about 70% by weight.
  • the preferred proportion of the compound (3) is about 10% by mass or more to raise the upper limit temperature or to lower the viscosity, and about 90% by mass or less to raise the dielectric anisotropy.
  • a further preferred ratio is in the range of about 20% by weight to about 80% by weight.
  • An especially desirable ratio is in the range of about 30% by weight to about 70% by weight.
  • the second additive is added to the composition for the purpose of being adapted to a polymer-supported oriented device.
  • the preferred proportion of the second additive is about 0.03% by mass or more for aligning liquid crystal molecules, and about 10% by mass or less for preventing display defects of the device.
  • a further preferred ratio is in the range of about 0.1% by weight to about 2% by weight.
  • An especially desirable ratio is in the range of about 0.2% by mass to about 1.0% by mass.
  • R 1a , R 1b and R 1c are hydrogen, alkyl having 1 to 20 carbon atoms, alicyclic hydrocarbon group having 3 to 20 carbon atoms, or aromatic carbon having 6 to 20 carbon atoms
  • a hydrogen group, in which at least one —CH 2 — may be replaced by —O—, —NH—, —CO—, —COO—, or —OCO—, at least one — CH 2 —CH 2 — may be replaced by —CH CH— or —C ⁇ C—, and in these groups, at least one hydrogen is an alkyl having 1 to 10 carbons, 1 to 10 carbons May be replaced by alkoxy or halogen.
  • n is 1, 2, 3 or 4; Preferably n is 2 and the substitution position is preferably ortho or para to the OH group.
  • R 1d is hydrogen or alkyl having 1 to 15 carbon atoms, and in this alkyl, at least one —CH 2 — is —O—, —NH -, -CO-, -COO-, or -OCO- may be substituted.
  • Desirable R 1d is hydrogen or alkyl having 1 to 10 carbons.
  • R 1e and R 1f are hydrogen, alkyl having 1 to 15 carbons, or alkoxy having 1 to 15 carbons.
  • Desirable R 1e is alkyl having 1 to 15 carbons. Particularly preferred is a highly sterically hindered branched alkyl such as a tert-butyl group.
  • Desirable R 1f is alkyl having 1 to 10 carbons.
  • R 1g is hydrogen or alkyl having 1 to 15 carbons.
  • Desirable R 1g is alkyl having 1 to 10 carbons.
  • R 1h is hydrogen or alkyl having 1 to 15 carbons, and in this alkyl, at least one —CH 2 — is —O—, —NH—, —CO—, —COO—, or —OCO— It may be replaced.
  • Preferred R 1h is alkyl having 1 to 10 carbons, or alkyl having 1 to 10 carbons in which at least one —CH 2 — is replaced by —COO— or —OCO—.
  • R 1i is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, or halogen. Desirable R 1i is alkyl having 1 to 10 carbons.
  • Z 1a , Z 1b and Z 1c are a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one —CH 2 — may be replaced by —O—, and these groups And at least one hydrogen may be replaced by alkyl having 1 to 5 carbon atoms.
  • Preferred Z 1a , Z 1b or Z 1c is a single bond.
  • m is 0, 1, 2, 3, 4 or 5; Preferred m is 1, 2 or 3.
  • R 2a and R 2b are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and 2 to 12 carbons. It is alkenyloxy or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Desirable R 2a or R 2b is alkyl having 1 to 12 carbons to increase stability, and alkoxy having 1 to 12 carbons to increase dielectric anisotropy.
  • R 3a and R 3b are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine It is alkenyl. Desirable R 3a or R 3b is alkenyl having 2 to 12 carbons to lower the viscosity, and alkyl having 1 to 12 carbons to increase the stability.
  • Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More preferred alkyl is methyl, ethyl, propyl, butyl or pentyl to lower the viscosity.
  • Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. More desirable alkoxy is methoxy or ethoxy for decreasing the viscosity.
  • Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl. More preferred alkenyl is vinyl, 1-propenyl, 3-butenyl or 3-pentenyl to reduce viscosity.
  • Trans is preferable in the alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity and the like.
  • Cis is preferred for alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl.
  • alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy or 4-pentenyloxy. More preferable alkenyloxy is allyloxy or 3-butenyloxy to lower the viscosity.
  • Preferred examples of the alkyl in which at least one hydrogen is replaced by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl Or 8-fluorooctyl. Further preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl or 5-fluoropentyl to increase the dielectric anisotropy.
  • Preferred examples of the alkenyl in which at least one hydrogen is replaced by fluorine or chlorine are: 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro -4-pentenyl or 6,6-difluoro-5-hexenyl. Further preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl for decreasing the viscosity.
  • Ring A and ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is replaced by fluorine or chlorine 1 , 4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen is fluorine or chlorine It is chroman-2, 6-diyl replaced by.
  • Preferred examples of "1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine" are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene or 2-chloro- It is 3-fluoro-1,4-phenylene.
  • Preferred ring A or ring C is 1,4-cyclohexylene to lower viscosity, and tetrahydropyran-2,5-diyl to increase dielectric anisotropy, to increase optical anisotropy It is 1,4-phenylene. Tetrahydropyran-2,5-diyl is Or And preferably It is.
  • Ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,4, 5-trifluoronaphthalene-2,6-diyl, 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) It is.
  • Preferred ring B is 2,3-difluoro-1,4-phenylene to lower the viscosity, 2-chloro-3-fluoro-1,4-phenylene to lower the optical anisotropy, and the dielectric constant 7,8-Difluorochroman-2,6-diyl to increase anisotropy.
  • Ring D and ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene.
  • Preferred ring D or ring E is 1,4-cyclohexylene to lower the viscosity or to raise the upper temperature limit, and 1,4-phenylene to lower the lower temperature limit.
  • Z 2a and Z 2b are a single bond, ethylene, methyleneoxy or carbonyloxy. Desirable Z 2a or Z 2b is a single bond to lower the viscosity, ethylene to lower the lower limit temperature, and methyleneoxy to increase the dielectric anisotropy.
  • Z 3a is a single bond, ethylene or carbonyloxy. Preferred Z 3a is a single bond to lower the viscosity.
  • A is 0, 1, 2 or 3; b is 0 or 1; and the sum of a and b is 3 or less.
  • Preferred a is 1 to lower the viscosity and 2 or 3 to raise the upper temperature limit.
  • Desirable b is 0 to lower the viscosity and 1 to lower the lower limit temperature.
  • c is 1, 2 or 3; Preferred c is 1 to lower the viscosity and 2 or 3 to raise the upper temperature limit.
  • P 4a , P 4b and P 4c are polymerizable groups.
  • Preferable P 4a , P 4b or P 4c is a polymerizable group selected from the groups represented by Formula (P-1) to Formula (P-5).
  • Further preferred P 4a , P 4b or P 4c is a group (P-1) or a group (P-2).
  • the wavy lines in group (P-1) to group (P-5) indicate the binding site.
  • M 1 , M 2 and M 3 are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is replaced by fluorine or chlorine And alkyl having 1 to 5 carbon atoms.
  • Preferred M 1 , M 2 or M 3 is hydrogen or methyl to increase the reactivity. Further preferred M 1 is methyl and further preferred M 2 or M 3 is hydrogen.
  • P 4d , P 4e and P 4f are groups represented by formulas (P-1) to (P-3).
  • Preferred P 4d , P 4e or P 4f is a group (P-1) or a group (P-2).
  • the wavy lines in group (P-1) to group (P-3) indicate the binding site.
  • Ring F and ring I may be cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl or pyridine-2-
  • at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or the number of carbons in which at least one hydrogen is replaced by fluorine or chlorine. It may be substituted with 1 to 12 alkyl.
  • Preferred ring F or ring I is phenyl.
  • Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene -1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2 , 7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, At least one hydrogen is fluor
  • Preferred Z 4a or Z 4b is a single bond, -CH 2 CH 2- , -CH 2 O-, -OCH 2- , -COO-, or -OCO-. Further preferred Z 4a or Z 4b is a single bond.
  • D is 0, 1 or 2; Preferred d is 0 or 1.
  • e, f and g are 0, 1, 2, 3 or 4 and the sum of e, f and g is 1 or more.
  • Preferred e, f or g is 1 or 2.
  • the preferred compound (1) is the compound (1-1) to the compound (1-10) described in item 3. Among these compounds, the compound (1-2), the compound (1-3) or the compound (1-8) is preferable.
  • the preferred compound (2) is a compound (2-1) to a compound (2-35) described in item 6.
  • at least one of the first components is a compound (2-1), a compound (2-3), a compound (2-6), a compound (2-8), a compound (2-10), a compound (2 It is preferable that it is 2-14) or the compound (2-16).
  • At least two of the first components are the compound (2-1) and the compound (2-8), the compound (2-1) and the compound (2-14), the compound (2-3) and the compound (2-8), Compound (2-3) and Compound (2-14), Compound (2-3) and Compound (2-16), Compound (2-6) and Compound (2-8), Compound (2-6) and Compound
  • the combination of (2-10), compound (2-6) and compound (2-16), compound (2-10) and compound (2-16) is preferred.
  • the preferred compound (3) is the compound (3-1) to the compound (3-13) described in item 9.
  • at least one of the second components is a compound (3-1), a compound (3-3), a compound (3-5), a compound (3-6), a compound (3-8), or a compound (3-9) is preferred.
  • At least two of the second components are the compound (3-1) and the compound (3-3), the compound (3-1) and the compound (3-5), or the compound (3-1) and the compound (3-6) It is preferable that it is a combination of
  • the preferred compound (4) is a compound (4-1) to a compound (4-29) described in item 13.
  • at least one of the second additives is a compound (4-1), a compound (4-2), a compound (4-24), a compound (4-25), a compound (4-26), or It is preferably a compound (4-27).
  • At least two of the second additives are the compound (4-1) and the compound (4-2), the compound (4-1) and the compound (4-18), the compound (4-2) and the compound (4-24) , Compound (4-2) and Compound (4-25), Compound (4-2) and Compound (4-26), Compound (4-25) and Compound (4-26), or Compound (4-18) It is preferable that it is a combination of and a compound (4-24).
  • additives that may be added to the composition will be described.
  • Such additives include optically active compounds, antioxidants, ultraviolet light absorbers, quenchers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like.
  • An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules to give a twist angle.
  • examples of such compounds are compounds (5-1) to (5-5).
  • the preferred proportion of the optically active compound is about 5% by mass or less.
  • a further preferred ratio is in the range of about 0.01% by weight to about 2% by weight.
  • To compound (6-3) may be further added to the composition.
  • the compound (6-2) Since the compound (6-2) has low volatility, it is effective to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after using the device for a long time.
  • the preferred proportion of the antioxidant is about 50 ppm or more to obtain its effect, and is about 600 ppm or less so as not to lower the upper temperature limit or to raise the lower temperature limit.
  • a further preferred ratio is in the range of about 100 ppm to about 300 ppm.
  • UV absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like.
  • light stabilizers such as sterically hindered amines.
  • Preferred examples of the light stabilizer include compound (7-1) to compound (7-16). The preferred proportion of these absorbents and stabilizers is about 50 ppm or more to obtain the effect, and about 10000 ppm or less so as not to lower the upper temperature limit or to raise the lower temperature limit. A further preferred ratio is in the range of about 100 ppm to about 10000 ppm.
  • the quencher is a compound that receives the light energy absorbed by the liquid crystal compound and converts it into heat energy to prevent the decomposition of the liquid crystal compound.
  • Preferred examples of the quencher are compound (8-1) to compound (8-7).
  • the preferred proportion of these quenchers is about 50 ppm or more to obtain the effect, and about 20000 ppm or less in order not to raise the lower limit temperature.
  • a further preferred ratio is in the range of about 100 ppm to about 10000 ppm.
  • a dichroic dye such as an azo dye or an anthraquinone dye is added to the composition.
  • the preferred proportion of dye is in the range of about 0.01% by weight to about 10% by weight.
  • an antifoam agent such as dimethyl silicone oil, methylphenyl silicone oil or the like is added to the composition.
  • the preferable proportion of the antifoaming agent is about 1 ppm or more in order to obtain the effect, and is about 1000 ppm or less in order to prevent display defects.
  • a further preferred ratio is in the range of about 1 ppm to about 500 ppm.
  • Polymerizable compounds are used to make them compatible with polymer-supported oriented (PSA) type devices.
  • Compound (4) is suitable for this purpose.
  • a polymerizable compound different from the compound (4) may be added to the composition.
  • Preferred examples of such polymerizable compounds are compounds such as acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes) and vinyl ketones. Further preferred examples are derivatives of acrylate or methacrylate.
  • the preferred proportion of the compound (4) is 10% by mass or more based on the total mass of the polymerizable compound.
  • a further preferable ratio is 50% by mass or more.
  • An especially desirable ratio is 80% by mass or more. The most preferable ratio is 100% by mass.
  • the polymerizable compound such as the compound (4) is polymerized by ultraviolet irradiation. It may be polymerized in the presence of a suitable initiator such as a photoinitiator. Appropriate conditions for polymerization, appropriate types of initiators, and appropriate amounts are known to the person skilled in the art and are described in the literature. For example, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF), which are photoinitiators, are suitable for radical polymerization.
  • the preferred proportion of the photoinitiator is in the range of about 0.1 wt% to about 5 wt% based on the total weight of the polymerizable compound.
  • a further preferred ratio is in the range of about 1% by weight to about 3% by weight.
  • a polymerization inhibitor When storing a polymerizable compound such as compound (4), a polymerization inhibitor may be added to prevent polymerization.
  • the polymerizable compound is usually added to the composition without removing the polymerization inhibitor.
  • polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine and the like.
  • the synthesis methods of the component compounds will be described. These compounds can be synthesized by known methods. The synthesis method is illustrated.
  • the compound (1-2) is synthesized by the method described in JP-A-2010-120894.
  • the compound (2-1) is synthesized by the method described in JP-A-2000-053602.
  • the compound (3-1) is synthesized by the method described in JP-A-59-176221.
  • the compound (4-18) is synthesized by the method described in JP-A-7-101900.
  • Antioxidants are commercially available.
  • Compound (6-1) can be obtained from Aldrich (Sigma-Aldrich Corporation).
  • the compound (6-2) and the like are synthesized by the method described in US Pat. No. 3,660,505.
  • compositions are prepared from the compounds thus obtained by known methods. For example, the component compounds are mixed and dissolved together by heating.
  • the composition primarily has a lower temperature limit of about -10 ° C. or lower, an upper temperature limit 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 proportions of the component compounds, or by mixing other liquid crystal compounds. By trial and error, compositions having an optical anisotropy in the range of about 0.10 to about 0.30 may be prepared. Devices containing this composition have a large voltage holding ratio.
  • This composition is suitable for an AM device.
  • This composition is particularly suitable for transmissive AM devices.
  • This composition can be used as a composition having a nematic phase, or as an optically active composition by adding an optically active compound.
  • This composition can be used for an AM device. Furthermore, the use to PM element is also possible.
  • This composition can be used for AM devices and PM devices having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA.
  • the use for an AM device having a TN, OCB, IPS mode or FFS mode is particularly preferred.
  • the alignment of liquid crystal molecules may be parallel to or perpendicular to the glass substrate when no voltage is applied.
  • These elements may be reflective, transmissive or semi-transmissive. Its use for transmission type devices is preferred.
  • the use for amorphous silicon-TFT elements or polycrystalline silicon-TFT elements is also possible.
  • the composition can be used for an element of NCAP (nematic curvilinear aligned phase) type prepared by microencapsulation or a element of PD (polymer dispersed) type in which a three-dimensional network polymer is formed in the composition.
  • the present invention comprises a mixture of the composition of Example 1 and the composition of Example 2.
  • the present invention also includes a mixture of at least two of the compositions of the Examples.
  • the compound synthesized was identified by a method such as NMR analysis. The properties of the compounds, compositions, and devices were measured by the methods described below.
  • NMR analysis For measurement, DRX-500 manufactured by Bruker Biospin Ltd. was used. In the measurement of 1 H-NMR, the sample was dissolved in a deuterated solvent such as CDCl 3, and the measurement was performed at room temperature under conditions of 500 MHz and 16 integrations. Tetramethylsilane was used as an internal standard. In the 19 F-NMR measurement, CFCl 3 was used as an internal standard, and the integration was performed 24 times. In the description of nuclear magnetic resonance spectrum, s is singlet, d is doublet, t is triplet, q is quartet, quin is quintet, sex is sextet, m is multiplet, br is broad.
  • a GC-14B gas chromatograph made by Shimadzu Corporation was used for measurement.
  • the carrier gas is helium (2 mL / min).
  • the sample vaporization chamber was set at 280 ° C. and the detector (FID) was set at 300 ° C.
  • capillary columns DB-1 length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m; fixed liquid phase is dimethylpolysiloxane; nonpolar
  • the column was kept at 200 ° C. for 2 minutes and then heated to 280 ° C. at a rate of 5 ° C./minute.
  • the sample was prepared in an acetone solution (0.1% by mass), and 1 ⁇ L thereof was injected into the sample vaporization chamber.
  • the recorder is Model C-R5A Chromatopac manufactured by Shimadzu Corporation, or its equivalent.
  • the obtained gas chromatogram showed the retention time of the peak corresponding to the component compound and the area of the peak.
  • capillary column As a solvent for diluting the sample, chloroform, hexane or the like may be used.
  • the following capillary column may be used to separate the component compounds.
  • HP-1 (30 m in length, 0.32 mm in diameter, 0.25 ⁇ m in thickness) manufactured by Agilent Technologies Inc.
  • Rtx-1 (30 m in length, 0.32 mm in inside diameter, 0.25 ⁇ m in film thickness) manufactured by Restek Corporation
  • BP-1 (30 m in length, 0.32 mm in inner diameter, 0.25 ⁇ m in film thickness) manufactured by SGE International Pty. Ltd.
  • a capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 ⁇ m) manufactured by Shimadzu Corporation may be used for the purpose of preventing overlapping of compound peaks.
  • the proportion of the liquid crystal compound contained in the composition may be calculated by the following method.
  • the mixture of liquid crystalline compounds is analyzed by gas chromatography (FID).
  • FID gas chromatography
  • the area ratio of peaks in the gas chromatogram corresponds to the proportion of the liquid crystal compound.
  • 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 area ratio of the peaks.
  • Measurement sample When measuring the characteristics of the composition or element, the composition was used as it was as a sample.
  • a sample for measurement was prepared by mixing this compound (15% by mass) with the mother liquid crystal (85% by mass). The characteristic values of the compound were calculated by extrapolation from the values obtained by the measurement.
  • (Extrapolated value) ⁇ (measured value of sample) ⁇ 0.85 ⁇ (measured value of mother liquid crystal) ⁇ / 0.15.
  • the proportion of the compound and the base liquid crystal is 10 mass%: 90 mass%, 5 mass%: 95 mass%, 1 mass%: 99 mass% in this order. changed.
  • the values of the upper limit temperature, the optical anisotropy, the viscosity, and the dielectric anisotropy of the compound were determined by this extrapolation method.
  • Measurement method The measurement of the characteristics was performed by the following method. Many of these are the methods described in the JEITA standard (JEITA ED-2521B), which has been deliberated and enacted by the Japan Electronics and Information Technology Industries Association (JEITA), or a modified method thereof. Met. A thin film transistor (TFT) was not attached to the TN device used for the measurement.
  • Upper limit temperature of nematic phase (NI; ° C.): The sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarization microscope and heated at a rate of 1 ° C./min. The temperature was measured when part of the sample changed from the nematic phase to the isotropic liquid.
  • the upper limit temperature of the nematic phase may be abbreviated as "upper limit temperature”.
  • Lower limit temperature of nematic phase (T C ; ° C.): The sample having the nematic phase is put in a glass bottle, and placed in a freezer at 0 ° C., -10 ° C., -20 ° C., -30 ° C. After storage, the liquid crystal phase was observed. For example, the sample remained in the -20 ° C. in a nematic phase, when changed to -30 ° C. At crystals or a smectic phase was described as ⁇ -20 ° C.
  • the lower limit temperature of the nematic phase may be abbreviated as "lower limit temperature”.
  • Viscosity Bulk viscosity; ;; measured at 20 ° C .; mPa ⁇ s
  • E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used.
  • Viscosity (rotational viscosity; ⁇ 1; measured at 25 ° C .; mPa ⁇ s):
  • a rotational viscosity measurement system LCM-2 type manufactured by Toyo Technica Co., Ltd. was used for measurement.
  • the sample was injected into a VA device in which the distance between two glass substrates (cell gap) was 10 ⁇ m.
  • a rectangular wave (55 V, 1 ms) was applied to this element.
  • the peak current and peak time of transient current generated by this application were measured.
  • the values of rotational viscosity were obtained using these measured values and dielectric anisotropy.
  • the dielectric anisotropy was measured by the method described in the measurement (6).
  • the dielectric constants ( ⁇ and ⁇ ) were measured as follows. 1) Measurement of dielectric constant ( ⁇ ): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a well-cleaned glass substrate. The glass substrate was rotated by a spinner and then heated at 150 ° C. for 1 hour. A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 4 ⁇ m, and this device was sealed with an adhesive cured with ultraviolet light.
  • Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant ( ⁇ ) in the major axis direction of liquid crystal molecules was measured.
  • 2) Measurement of dielectric constant ( ⁇ ) A polyimide solution was applied to a well-cleaned glass substrate. After firing the glass substrate, the obtained alignment film was rubbed. The sample was placed in a TN device in which the distance between two glass substrates (cell gap) was 9 ⁇ m and the twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant ( ⁇ ) in the minor axis direction of liquid crystal molecules was measured.
  • Threshold voltage (Vth; measured at 25 ° C .; V): An LCD-5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement.
  • the light source was a halogen lamp.
  • a sample is placed in a normally black mode VA device in which the distance between two glass substrates (cell gap) is 4 ⁇ m and the rubbing direction is antiparallel, and an adhesive for curing this device with ultraviolet light is used. Used and sealed.
  • the voltage (60 Hz, rectangular wave) applied to this element was gradually increased by 0.02 V from 0 V to 20 V.
  • the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured.
  • a voltage-transmittance curve was created in which the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum.
  • the threshold voltage was represented by the voltage at 10% transmittance.
  • VHR-9 Voltage holding ratio
  • the TN device used for measurement had a polyimide alignment film, and the distance between two glass substrates (cell gap) was 5 ⁇ m. .
  • the element was sealed with an adhesive that cures with ultraviolet light after the sample was placed.
  • the TN device was charged by applying a pulse voltage (60 microseconds at 1 V).
  • 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 determined.
  • the area B was the area when it did not decay.
  • the voltage holding ratio was expressed as a percentage of the area A to the area B.
  • VHR-10 Voltage holding ratio (VHR-10; measured at 60 ° C .;%): The voltage holding ratio was measured in the same manner as described above except that the measurement was performed at 60 ° C. instead of 25 ° C. The obtained value is expressed as 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 irradiated with ultraviolet light of 5 mW / cm 2 for 167 minutes.
  • the light source was Blacklight 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 decaying voltage was measured for 166.7 milliseconds. Compositions having large VHR-11 have high stability to ultraviolet light.
  • VHR-12 Voltage holding ratio
  • the TN device injected with the sample is heated in a 120 ° C. constant temperature bath for 20 hours, and then the voltage holding ratio is measured and its stability to heat Was evaluated. In the measurement of VHR-12, the decaying voltage was measured for 166.7 milliseconds. Compositions having large VHR-12 have high thermal stability.
  • compositions are given below.
  • Component compounds are represented by symbols based on the definition of Table 3 below.
  • Table 3 the configuration for 1,4-cyclohexylene is trans.
  • the number in parenthesis after the symbolized compound represents the chemical formula to which the compound belongs.
  • the symbol (-) means other liquid crystal compounds.
  • the proportion (percentage) of the liquid crystal compound is a mass percentage (mass%) based on the mass of the liquid crystal composition not including the additive.
  • Example 1 A composition obtained by adding the compound (1-A) to the composition of Comparative Example 1 is referred to as Example 1.
  • Example 1 3-HB (2F, 3F) -O2 (2-1) 4% 2-BB (2F, 3F)-O2 (2-6) 8% 3-BB (2F, 3F)-O2 (2-6) 8% V2-BB (2F, 3F) -O2 (2-6) 2% V-HHB (2F, 3F) -O1 (2-8) 4% V-HHB (2F, 3F) -O2 (2-8) 10% V-HHB (2F, 3F) -O4 (2-8) 4% 2-HHB (2F, 3F) -O2 (2-8) 2% 3-HHB (2F, 3F) -O2 (2-8) 4% 5-HHB (2F, 3F) -O2 (2-8) 3% 3-HH2B (2F, 3F) -O2 (2-9) 10% 3-HD h B (2F, 3F)-O2 (2-13) 10% 3-dhBB (2F, 3F
  • VHR-11 voltage holding ratio after light irradiation of the composition of Comparative Example 1 was 74.3%.
  • VHR-11 of the compositions of Examples 1 to 14 was in the range of 80.1% to 97.3%. Therefore, it is concluded that the liquid crystal composition of the present invention has more excellent properties.
  • the liquid crystal composition of the present invention can be used for a liquid crystal monitor, a liquid crystal television and the like.

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  • Crystallography & Structural Chemistry (AREA)
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  • Organic Chemistry (AREA)
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  • General Physics & Mathematics (AREA)
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Abstract

La présente invention concerne une composition de cristaux liquides satisfaisant à au moins une propriété parmi les propriétés telles qu'une température limite supérieure élevée, une température limite inférieure basse, une faible viscosité, une anisotropie optique appropriée, une grande anisotropie diélectrique négative, une grande résistance spécifique, une stabilité élevée à la lumière et une stabilité élevée à la chaleur ; et un dispositif de matrice active comprenant ladite composition. La composition de cristaux liquides contient en tant que premier additif au moins un composé choisi parmi un composé représenté par la formule (S) et un composé obtenu par substitution par un groupe monovalent d'au moins un hydrogène dans le composé représenté par la formule (S), et peut contenir en tant que premier constituant un composé spécifique présentant une anisotropie diélectrique négative élevée, en tant que second constituant un composé spécifique ayant une température limite supérieure élevée ou une faible viscosité, et en tant que second additif un composé spécifique comportant un groupe polymérisable.
PCT/JP2018/046348 2018-01-10 2018-12-17 Composition de cristaux liquides et dispositif d'affichage à cristaux liquides WO2019138791A1 (fr)

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JPS53102357A (en) * 1977-02-17 1978-09-06 Adeka Argus Chem Co Ltd Stabilized halogen-containing resin compsition
JP2006124544A (ja) * 2004-10-29 2006-05-18 Dainippon Ink & Chem Inc ネマチック液晶組成物及びこれを用いた液晶表示素子
WO2009034867A1 (fr) * 2007-09-10 2009-03-19 Chisso Corporation Composé cristal liquide, composition de cristaux liquides et élément d'affichage à cristaux liquides
WO2009107405A1 (fr) * 2008-02-27 2009-09-03 コニカミノルタオプト株式会社 Film optique, procédé de production de film optique, écran polarisant comprenant le film optique, unité d'affichage à cristaux liquides et composé
JP2014091697A (ja) * 2012-11-02 2014-05-19 Dic Corp ヒンダードフェノールの製造方法

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Publication number Priority date Publication date Assignee Title
US3244668A (en) * 1961-01-23 1966-04-05 Ethyl Corp Stabilized plastic
JPS53102357A (en) * 1977-02-17 1978-09-06 Adeka Argus Chem Co Ltd Stabilized halogen-containing resin compsition
JP2006124544A (ja) * 2004-10-29 2006-05-18 Dainippon Ink & Chem Inc ネマチック液晶組成物及びこれを用いた液晶表示素子
WO2009034867A1 (fr) * 2007-09-10 2009-03-19 Chisso Corporation Composé cristal liquide, composition de cristaux liquides et élément d'affichage à cristaux liquides
WO2009107405A1 (fr) * 2008-02-27 2009-09-03 コニカミノルタオプト株式会社 Film optique, procédé de production de film optique, écran polarisant comprenant le film optique, unité d'affichage à cristaux liquides et composé
JP2014091697A (ja) * 2012-11-02 2014-05-19 Dic Corp ヒンダードフェノールの製造方法

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Publication number Priority date Publication date Assignee Title
WO2021075294A1 (fr) * 2019-10-17 2021-04-22 Ａｇｃ株式会社 Verre feuilleté, son procédé de fabrication et verre multi-couche
DE112020004198T5 (de) 2019-10-17 2022-05-19 AGC Inc. Laminiertes Glas, Verfahren zur Herstellung eines laminierten Glases und Isolierglaseinheit

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