WO2020158211A1 - Composite de cristaux liquides, élément de gradation de lumière à cristaux liquides, et fenêtre de gradation de lumière - Google Patents

Composite de cristaux liquides, élément de gradation de lumière à cristaux liquides, et fenêtre de gradation de lumière Download PDF

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WO2020158211A1
WO2020158211A1 PCT/JP2019/048908 JP2019048908W WO2020158211A1 WO 2020158211 A1 WO2020158211 A1 WO 2020158211A1 JP 2019048908 W JP2019048908 W JP 2019048908W WO 2020158211 A1 WO2020158211 A1 WO 2020158211A1
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liquid crystal
compound
carbons
replaced
hydrogen
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Japanese (ja)
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将之 齋藤
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JNC Corp
JNC Petrochemical Corp
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JNC Corp
JNC Petrochemical Corp
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Priority to JP2020569429A priority Critical patent/JPWO2020158211A1/ja
Priority to CN201980069694.5A priority patent/CN112912467B/zh
Publication of WO2020158211A1 publication Critical patent/WO2020158211A1/fr
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
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    • 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
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    • C09K19/00—Liquid crystal materials
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    • 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
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    • 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
    • C09K19/18—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 triple bonds, e.g. tolans
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/60—Pleochroic dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals

Definitions

  • the present invention mainly relates to a liquid crystal light control device. More specifically, it relates to a liquid crystal light control device having a liquid crystal composite in which a polymer and a liquid crystal composition are combined.
  • liquid crystal light control device There are methods such as using light scattering for the liquid crystal light control device.
  • Such elements are used in building materials such as window panes and room dividers, in-vehicle parts, etc.
  • a soft substrate such as a plastic film is used.
  • the alignment of liquid crystal molecules is changed by adjusting the applied voltage. Since light transmitted through the liquid crystal composition can be controlled by this method, the liquid crystal light control device is widely used in displays, optical shutters, light control windows (Patent Document 1), smart windows (Patent Document 2), and the like. Has been done.
  • a liquid crystal light control device is a polymer dispersion type device in a light scattering mode.
  • the liquid crystal composition is dispersed in the polymer.
  • This element has the following features.
  • the device is easy to manufacture. Since it is easy to control the film thickness over a wide area, it is possible to manufacture a device having a large screen. Since no polarizing plate is required, bright display is possible. Wide viewing angle because light scattering is used. Since this element has such excellent properties, it is expected to be used as a light control glass, a projection type display, a large area display and the like.
  • liquid crystal light control device Another example is a polymer network type liquid crystal light control device.
  • the liquid crystal composition is present in a three-dimensional network of polymers.
  • This composition differs from the polymer dispersion type in that it is continuous.
  • This type of device also has the same characteristics as the polymer-dispersed device.
  • a liquid crystal composition having appropriate characteristics is used for the liquid crystal light control device. By improving the characteristics of this composition, a device having good characteristics can be obtained.
  • the relationship between the two properties is summarized in Table 1 below.
  • the characteristics of the composition will be further described based on the device.
  • the temperature range of the nematic phase is related to the temperature range in which the device can be used.
  • the preferred maximum temperature of the nematic phase is about 70° C. or higher, and the preferred minimum temperature of the nematic phase is about ⁇ 20° C. or lower.
  • the viscosity of the composition is related to the response time of the device. A short response time is preferable to control the light transmittance. A response time of 1 millisecond is shorter than that of other devices.
  • the elastic constant of the composition is related to the response time of the device. In order to achieve a short response time in the device, a large elastic constant in the composition is more preferable.
  • the optical anisotropy of the composition is related to the haze ratio of the liquid crystal light control device.
  • the haze ratio is the ratio of diffused light to the total transmitted light. A large haze ratio is preferred when blocking light. A large optical anisotropy is preferable for a large haze ratio.
  • a large dielectric anisotropy in the composition contributes to a low threshold voltage and a small power consumption in the device. Therefore, large dielectric anisotropy is preferable.
  • a large specific resistance in the composition contributes to a large voltage holding ratio in the device. Therefore, a composition having a large specific resistance in the initial stage is preferable. A composition having a large specific resistance after being used for a long time is preferable.
  • the stability and weather resistance of a composition against light and heat are related to the life of the device. When the stability and weather resistance are good, the life is long. Display defects such as afterimages and drop marks are also related to the life of the device. There is a demand for an element that has high weather resistance and is resistant to display defects.
  • the liquid crystal light control device has a normal mode and a reverse mode.
  • the element In the normal mode, the element is opaque when no voltage is applied and becomes transparent when a voltage is applied.
  • In the reverse mode, the element In the reverse mode, the element is transparent when no voltage is applied and becomes opaque when a voltage is applied.
  • a normal mode element is widely used, and this element has advantages that it is inexpensive and easy to manufacture.
  • Patent documents 3 to 6 To improve the liquid crystal light control device, the patent documents are helpful (Patent documents 3 to 6).
  • Patent Document 7 a device having a black liquid crystal composition prepared by adding at least three dichroic dyes was produced.
  • Patent Document 8 a liquid crystal material containing a dichroic dye is used for a switch layer.
  • Patent Document 9 a dichroic dye is used in a guest-host type liquid crystal display device. We tried to use such a dichroic dye in a liquid crystal light control device.
  • the object of the present invention is to increase the maximum temperature of a nematic phase, the minimum temperature of a nematic phase, a small viscosity, a large optical anisotropy, a large positive dielectric anisotropy, a large specific resistance, a high stability against light, and a high heat resistance. It is intended to provide a liquid crystal composite which contains a liquid crystal composition satisfying at least one of properties such as high stability and a large elastic constant and is suitable for light control. Another object is to provide a liquid crystal composite that contains a liquid crystal composition having an appropriate balance between at least two of these properties and is suitable for dimming. Another object is to provide a liquid crystal light control device having such a liquid crystal composite. Another object is to provide a liquid crystal light control device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large haze ratio, high weather resistance and long life.
  • the present invention contains a liquid crystal composition and a polymer, and the liquid crystal composition has at least one compound selected from the compounds represented by the formula (1) as a first component and a dichroic compound as a first additive.
  • the present invention relates to a liquid crystal composite containing a dye, a liquid crystal light control device containing the liquid crystal composite, and the like.
  • R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons;
  • ring A is 1,4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3- Dioxane-2,5-diyl or tetrahydropyran-2,5-diyl;
  • Z 1 is a single bond, ethylene, vinylene, ethynylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy;
  • X 1 and X 2 is hydrogen or fluorine;
  • Y 1 is fluorine, chlorine, cyano, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, at least one hydrogen is replaced by flu
  • the advantages of the present invention are: a high maximum temperature of a nematic phase, a low minimum temperature of a nematic phase, a small viscosity, a large optical anisotropy, a large positive dielectric anisotropy, a large specific resistance, a high stability against light, and a high heat resistance
  • Another advantage is to provide a liquid crystal composite that contains a liquid crystal composition having a suitable balance between at least two of these properties and is suitable for dimming.
  • Another advantage is to provide a liquid crystal light control device having such a liquid crystal composite.
  • Another advantage is to provide a liquid crystal light control device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large haze ratio, high weather resistance, and long life.
  • liquid crystal compound is a compound having a liquid crystal phase such as a nematic phase or a smectic phase and a liquid crystal phase, but it is a composition for the purpose of adjusting properties such as temperature range, viscosity and dielectric anisotropy of the nematic phase. It is a general term for compounds added to things. This compound has a 6-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-like.
  • the “polymerizable compound” is a compound added for the purpose of forming a polymer in the liquid crystal 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, an antioxidant, an ultraviolet absorber, a quencher, a dye, a defoaming agent, and a polar 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 liquid crystal composition containing no additive even when the additive is added.
  • the ratio of the additive is expressed as a mass percentage based on 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 amount of the liquid crystal compound.
  • the "mass" of "mass%” may be omitted.
  • the polymerizable composition is prepared by mixing a polymerizable compound with the liquid crystal composition. That is, the polymerizable composition is a mixture of at least one polymerizable compound and the liquid crystal composition. If necessary, additives such as a polymerization initiator and a polymerization inhibitor are added to the polymerizable compound. The ratio of the polymerization initiator and the polymerization inhibitor is represented by the mass percentage based on the polymerizable compound. The proportion of the polymerizable compound or the liquid crystal composition contained in the polymerizable composition is expressed by the mass percentage based on the polymerizable composition containing no additive even when the additive is added.
  • the “liquid crystal composite” is produced by the polymerization treatment of the polymerizable composition.
  • Liquid crystal light control device is a device having a liquid crystal composite and is a general term for liquid crystal panels and liquid crystal modules used for light control.
  • 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.
  • 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 limitation.
  • 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).
  • the alkyl of the liquid crystal compound is linear or branched and does not include cyclic alkyl. Straight-chain alkyls are preferred over branched alkyls. The same applies to terminal groups such as alkoxy and alkenyl. Regarding the configuration of 1,4-cyclohexylene, trans is preferable to cis for increasing the maximum temperature. Since 2-fluoro-1,4-phenylene is asymmetrical to the left and right, there are leftward (L) and rightward (R) directions. The same applies to divalent groups such as tetrahydropyran-2,5-diyl. The same applies to a linking group such as carbonyloxy (-COO- or -OCO-).
  • the present invention includes the following items.
  • a liquid crystal composition and a polymer are contained, and the liquid crystal composition contains at least one compound selected from the compounds represented by the formula (1) as a first component and a dichroic dye as a first additive. , Liquid crystal composites.
  • R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons;
  • ring A is 1,4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3- Dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl;
  • Z 1 is a single bond, ethylene, vinylene, ethynylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy;
  • Item 2 The liquid crystal composite according to item 1, wherein the liquid crystal composition contains, as a first component, at least one compound selected from compounds represented by formulas (1-1) to (1-47).
  • R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons, and X 1 and X 2 is hydrogen or fluorine;
  • Y 1 is fluorine, chlorine, cyano, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, at least one hydrogen is replaced by fluorine or chlorine Alkoxy having 1 to 12 carbons, or alkenyloxy having 2 to 12 carbons in which at least one hydrogen has been replaced by fluorine or chlorine.
  • Item 3. The liquid crystal composite according to item 1 or 2, wherein the ratio of the first component is in the range of 5% to 90% based on the liquid crystal composition.
  • Item 4. The liquid crystal composite according to any one of items 1 to 3, wherein the liquid crystal composition contains at least one compound selected from the compounds represented by formula (2) as the second component.
  • R 2 and R 3 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 with fluorine or chlorine.
  • Ring B and Ring C are 1,4-cyclohexylene, 1,3-phenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5- Difluoro-1,4-phenylene, or pyrimidine-2,5-diyl;
  • Z 2 is a single bond, ethylene, vinylene, ethynylene, methyleneoxy, or carbonyloxy;
  • b is 1, 2, or 3 Is.
  • Item 5. The liquid crystal composition according to any one of items 1 to 4, wherein the second component contains at least one compound selected from compounds represented by formula (2-1) to formula (2-23). Liquid crystal composite.
  • 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 at least one It is alkenyl having 2 to 12 carbons in which hydrogen is replaced by fluorine or chlorine.
  • Item 6. The liquid crystal composite according to item 4 or 5, wherein the ratio of the second component is in the range of 5% to 90% based on the liquid crystal composition.
  • Item 7. The liquid crystal composite according to any one of items 1 to 6, wherein the liquid crystal composition contains at least one compound selected from the compounds represented by formula (3) as the third component.
  • R 4 and R 5 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 D and ring F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen being 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 Chroman-2,6-diyl replaced by chlorine;
  • Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro -5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-
  • Item 8 The liquid crystal composition according to any one of items 1 to 7, wherein the liquid crystal composition contains at least one compound selected from compounds represented by formulas (3-1) to (3-35) as a third component. Liquid crystal composite.
  • R 4 and R 5 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 9 The liquid crystal composite according to item 7 or 8, wherein the ratio of the third component is in the range of 3% to 25% based on the liquid crystal composition.
  • Item 10 The liquid crystal composite according to any one of items 1 to 9, wherein the polymer is derived from a mixture of polymerizable compounds, and the mixture contains the compound represented by formula (4) as a main component.
  • P 1 and P 2 are polymerizable groups;
  • Z 5 is alkylene having 1 to 20 carbons, and in this alkylene, at least one hydrogen is alkyl having 1 to 5 carbons, fluorine. , Chlorine, or P 3 , and at least one —CH 2 — is —O—, —CO—, —COO—, —OCO—, —NH—, or —N(R 6 )—.
  • At least one —CH 2 —CH 2 — may be replaced with —CH ⁇ CH— or —C ⁇ C—, and at least one —CH 2 — is a carbocyclic group.
  • Saturated aliphatic compound, heterocyclic saturated aliphatic compound, carbocyclic unsaturated aliphatic compound, heterocyclic unsaturated aliphatic compound, carbocyclic aromatic compound, or heterocyclic aromatic compound May be replaced by a divalent group formed by removing two hydrogens from, in which the carbon number is from 5 to 35, and at least one hydrogen is replaced by R 6 or P 3.
  • R 6 is alkyl having 1 to 12 carbons, and in this alkyl, at least one —CH 2 — is —O—, —CO—, —COO—, or —OCO—. It may be replaced and P 3 is a polymerizable group.
  • Item 11 The liquid crystal composite according to item 10, wherein P 1 , P 2 and P 3 are groups selected from the polymerizable groups represented by formulas (P-1) to (P-6).
  • P 1 , P 2 and P 3 are groups selected from the polymerizable groups represented by formulas (P-1) to (P-6).
  • M 1 , M 2 and M 3 are each hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced with fluorine or chlorine.
  • alkyl having 1 to 5 carbon atoms are each hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced with fluorine or chlorine.
  • Item 12. The liquid crystal composite according to item 10, wherein at least one of P 1 , P 2 and P 3 is acryloyloxy or methacryloyloxy.
  • Item 13 The liquid crystal composite according to any one of items 1 to 9, wherein the polymer is derived from a mixture of polymerizable compounds, and the mixture contains the compound represented by the formula (5) as a main component.
  • M 4 and M 5 are hydrogen or methyl;
  • Z 6 is alkylene having 21 to 80 carbons, and in this alkylene, at least one hydrogen is alkyl having 1 to 20 carbons, May be replaced by fluorine or chlorine, and at least one —CH 2 — is replaced by —O—, —CO—, —COO—, —OCO—, —NH—, or —N(R 6 )—
  • at least one —CH 2 —CH 2 — may be replaced by —CH ⁇ CH— or —C ⁇ C—, wherein R 6 is alkyl having 1 to 12 carbons.
  • at least one —CH 2 — may be replaced with —O—, —CO—, —COO—, or —OC
  • Item 14 The liquid crystal composite according to any one of items 1 to 9, wherein the polymer is derived from a mixture of polymerizable compounds, and the mixture contains a compound represented by the formula (6) as a main component.
  • M 6 is hydrogen or methyl
  • Z 7 is a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one hydrogen may be replaced by fluorine or chlorine.
  • At least one —CH 2 — may be replaced by —O—, —CO—, —COO—, or —OCO—;
  • R 7 is alkyl having 1 to 40 carbons, wherein At least one hydrogen may be replaced by fluorine or chlorine, and at least one —CH 2 — may be replaced by —O—, —CO—, —COO—, or —OCO—, at least 1 -CH 2 — is a carbocyclic saturated aliphatic compound, a heterocyclic saturated aliphatic compound, a carbocyclic unsaturated aliphatic compound, a heterocyclic unsaturated aliphatic compound, a carbocyclic aromatic compound.
  • It may be replaced by a divalent group formed by removing two hydrogens from a group compound or a heterocyclic aromatic compound, and in these divalent groups, the number of carbon atoms is 5 to 35 and at least one Hydrogen may be replaced by alkyl having 1 to 12 carbons, in which at least one —CH 2 — is replaced by —O—, —CO—, —COO—, or —OCO—. Good.
  • M 6 is hydrogen or methyl
  • Z 7 is a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one hydrogen may be replaced by fluorine or chlorine.
  • At least one —CH 2 — may be replaced with —O—, —CO—, —COO—, or —OCO—
  • R 7 is alkyl having 1 to 40 carbons, wherein Item 14.
  • the at least one hydrogen may be replaced by fluorine or chlorine, and the at least one —CH 2 — may be replaced by —O—, —CO—, —COO—, or —OCO—.
  • the liquid crystal composite according to item 1.
  • ring G, ring I, ring J, ring K, ring L, and ring M are 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexenylene, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, or fluorene-2,7-diyl, where: At least one hydrogen is fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 2 to 5 carbons.
  • Z 8 , Z 10 , Z 12 , Z 13 , and Z 17 are single bonds, —O—, —COO—, —OCO—, or — OCOO—;
  • Cyano alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, alkoxy having 1 to 20 carbons, or alkoxycarbonyl having 2 to 20 carbons; f and h are integers from 1 to 4 Yes; k and m are integers from 0 to 3; the sum of k and m is 1 to 4; e, g, i, j, l, and n are integers from 0 to 20; M 7 to M 12 are hydrogen or methyl.
  • the first additive is at least one dichroic dye selected from benzothiadiazoles, diketopyrrolopyrroles, azo compounds, and anthraquinones. 17.
  • the liquid crystal composite according to any one of 1 to 16.
  • Item 18 The liquid crystal composite according to any one of items 1 to 17, wherein the ratio of the first additive is in the range of 0.03% to 25% based on the liquid crystal composition.
  • Item 19 The method according to any one of Items 1 to 18, wherein the ratio of the liquid crystal composition is in the range of 50% to 95% and the ratio of the polymer is in the range of 5% to 50% based on the liquid crystal composite. Liquid crystal composite.
  • the liquid crystal composite is obtained by using as a precursor a polymerizable composition containing a liquid crystal composition and a polymerizable compound, and the polymerizable composition contains a photopolymerization initiator as an additive. Liquid crystal composite.
  • Item 21 A liquid crystal light control device in which the light control layer is the liquid crystal composite according to any one of items 1 to 20, the light control layer is sandwiched by a pair of transparent substrates, and the transparent substrate has a transparent electrode.
  • Item 22 The liquid crystal light control device according to item 21, wherein the transparent substrate is a glass plate or an acrylic plate.
  • Item 23 The liquid crystal light control device according to item 21, wherein the transparent substrate is a plastic film.
  • Item 24 A light control window using the liquid crystal light control device according to any one of items 21 to 23.
  • Item 25 A smart window using the liquid crystal light control device according to any one of items 21 to 23.
  • Item 26 Use of the liquid crystal composite according to any one of items 1 to 20 for a liquid crystal light control device.
  • Item 27 Use of the liquid crystal composite according to any one of items 1 to 20 for a liquid crystal light control device in which the transparent substrate is a plastic film.
  • Item 28 Use of the liquid crystal composite according to any one of items 1 to 20 for a light control window.
  • Item 29 Use of the liquid crystal composite according to any one of items 1 to 20 for a smart window.
  • the present invention also includes the following items.
  • the present invention also includes the following items.
  • the liquid crystal composition has, as the first component, the compound (1-1), the compound (1-2), the compound (1-3), the compound (1-9) or the compound (1- 13), compound (1-16), compound (1-21), compound (1-22), compound (1-23), compound (1-24), compound (1-27), compound (1-28) ), compound (1-33), compound (1-36), compound (1-41), and at least one compound selected from compound (1-42).
  • the present invention also includes the following items.
  • the liquid crystal composition comprises, as the second component, the compound (2-1), the compound (2-2), the compound (2-3), the compound (2-4) and the compound (2- 6), compound (2-9), compound (2-10), compound (2-12), compound (2-13), compound (2-14), compound (2-16), compound (2-17) ), the compound (2-19), and at least one compound selected from the compound (2-21).
  • the present invention also includes the following items.
  • the present invention also includes the following items.
  • the present invention also includes the following items.
  • K A liquid crystal composite as described above, wherein the proportion of the liquid crystal composition is in the range of 85% to 95% and the proportion of the polymer is in the range of 5% to 15% based on the liquid crystal composite.
  • the present invention also includes the following items.
  • the liquid crystal light control device of the present invention will be described in the following order. First, the structure of the liquid crystal composite will be described. Secondly, the constitution of the liquid crystal composition will be explained. Thirdly, the main characteristics of the liquid crystal compound and the main effects of the compound on the liquid crystal composition and the device will be described. Fourth, the combination of components in the liquid crystal composition, the preferable ratio of the components and the basis thereof will be described. Fifth, a preferable form of the liquid crystal compound will be described. Sixth, preferable liquid crystal compounds are shown. Seventh, preferred forms of the polymerizable compound and one example thereof will be described. Eighth, a preferable form of the dichroic dye and an example thereof will be described. Ninth, the method of synthesizing the component compounds will be described. Tenth, an additive that may be added to the polymerizable composition will be described. Finally, liquid crystal composites and devices will be described.
  • the liquid crystal composite is obtained by polymerizing the polymerizable composition.
  • the polymerizable composition is a mixture of the liquid crystal composition and the polymerizable compound.
  • the dielectric anisotropy of this liquid crystal composition is positive.
  • the polymerizable composition gives a liquid crystal composite because the polymer produced by polymerization undergoes phase separation. That is, a liquid crystal composite in which a polymer and a liquid crystal composition are combined is produced.
  • This liquid crystal composite is opaque when no voltage is applied and is suitable for a normal mode element which becomes transparent when a voltage is applied.
  • the optical anisotropy of the liquid crystal composition and the refractive index of the polymer are related to the transparency of the liquid crystal light control device. Generally, the optical anisotropy ( ⁇ n) of the liquid crystal composition is preferably large.
  • the optical anisotropy is preferably 0.15 or more, more preferably 0.18 or more.
  • the liquid crystal composition is dispersed like droplets in the polymer. Each of the droplets is separate and not continuous.
  • the polymer network type device the polymer has a three-dimensional network structure, and the liquid crystal composition is surrounded by the networks but is continuous.
  • the proportion of the liquid crystal composition based on the liquid crystal composite is preferably large in order to efficiently scatter light.
  • the driving voltage is low when the droplets and meshes are large. Therefore, the proportion of the polymer is preferably small from the viewpoint of low driving voltage.
  • the response time is short when the droplets and meshes are small. Therefore, it is preferable that the proportion of the polymer is large from the viewpoint of short response time.
  • a preferable ratio of the liquid crystal composition is in the range of about 50% to about 95% based on the liquid crystal composite. This preferred percentage is also in the range of about 50% to about 90%. A more desirable ratio is in the range of approximately 50% to approximately 85%. A particularly desirable ratio is in the range of approximately 60% to approximately 80%. A particularly desirable ratio is in the range of approximately 70% to approximately 80%. Since the total amount of the liquid crystal composition and the polymer is 100%, the ratio of the polymer can be easily calculated. The ratio of the polymer based on the liquid crystal composite is the same as the ratio of the polymerizable compound based on the polymerizable composition.
  • a preferred ratio of the liquid crystal composition is in the range of about 75% to about 97% based on the liquid crystal composite in order to efficiently scatter light or block sunlight.
  • a more desirable ratio is in the range of approximately 80% to approximately 96%.
  • a particularly desirable ratio is in the range of approximately 85% to approximately 95%.
  • the polymer adjusts the pretilt angle of liquid crystal molecules.
  • the liquid crystal molecules are stabilized by optimizing the pretilt angle, and the response time of the device is shortened.
  • the refractive index of the polymer and the refractive index of the liquid crystal molecules are different, light scattering occurs and the element becomes opaque.
  • the liquid crystal molecules are aligned perpendicular to the substrate and the element becomes transparent. Therefore, unlike the PSA element, the polymer network type element does not require a polarizing plate.
  • 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, 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 may further contain other liquid crystal compounds, additives, etc. in addition to the liquid crystal compounds selected from the compound (1), the compound (2), and the compound (3).
  • the "other liquid crystal compound” is a liquid crystal compound different from the compound (1), 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 liquid crystal compounds selected from compound (1), compound (2), and compound (3). “Substantially” means that the composition B may contain an additive, but does not contain any 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 with other liquid crystal compounds.
  • the main effects of the component compounds on the properties of the composition are as follows.
  • the compound (1) increases the dielectric anisotropy.
  • the compound (2) increases the maximum temperature or decreases the minimum temperature.
  • the compound (3) increases the dielectric constant in the short axis direction of liquid crystal molecules.
  • a preferred combination of components in the composition is the first component+second component, the first component+third component, or the first component+second component+third component.
  • a more preferable combination is the first component+second component or the first component+second component+third component.
  • the preferable ratio of the first component is about 5% or more for increasing the dielectric anisotropy, and about 90% or less for decreasing the minimum temperature.
  • a more desirable ratio is in the range of approximately 10% to approximately 85%.
  • a particularly desirable ratio is in the range of approximately 20% to approximately 80%.
  • the preferable ratio of the second component is about 5% or more for increasing the maximum temperature or decreasing the minimum temperature, and about 90% or less for increasing the dielectric anisotropy.
  • a more desirable ratio is in the range of approximately 10% to approximately 85%.
  • a particularly desirable ratio is in the range of approximately 20% to approximately 80%.
  • the preferable ratio of the third component is about 3% or more for increasing the dielectric constant in the short axis direction of the liquid crystal molecule, and about 25% or less for decreasing the minimum temperature.
  • a more desirable ratio is in the range of approximately 5% to approximately 20%.
  • a particularly desirable ratio is in the range of approximately 5% to approximately 15%.
  • R 1 is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons.
  • Preferred R 1 is alkyl having 1 to 12 carbons in order to improve stability to light and heat.
  • R 2 and R 3 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 2 or R 3 is alkenyl having 2 to 12 carbons for increasing the maximum temperature or decreasing the minimum temperature, and alkyl for having 1 to 12 carbons for increasing the stability against light or heat.
  • R 4 and R 5 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. Desirable R 4 or R 5 is alkyl having 1 to 12 carbons for increasing stability to light or heat, and alkoxy having 1 to 12 carbons for increasing dielectric constant in the short axis direction of liquid crystal molecules. ..
  • 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 include 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 is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene , Pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl.
  • Preferred ring A is 1,4-phenylene or 2-fluoro-1,4-phenylene for increasing the optical anisotropy.
  • trans is preferable to cis for increasing the maximum temperature.
  • Tetrahydropyran-2,5-diyl is Or And preferably Is.
  • Ring B and Ring C are 1,4-cyclohexylene, 1,3-phenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, or pyrimidine. It is -2,5-diyl.
  • Preferred ring B or ring C is 1,4-cyclohexylene for increasing the maximum temperature or decreasing the minimum temperature, and 1,4-phenylene for decreasing the minimum temperature.
  • Ring D and ring F 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. ,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 Is chroman-2,6-diyl replaced by.
  • Preferred ring D or ring F is 1,4-cyclohexylene for decreasing the minimum temperature or increasing the maximum temperature, and 1,4-phenylene for decreasing the minimum temperature.
  • Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4.
  • Preferred ring E is 2,3-difluoro-1,4-phenylene for decreasing the viscosity, and 4,6-difluorodibenzothiophene-3,7-diyl for increasing the dielectric constant in the short axis direction of liquid crystal molecules. Is.
  • Z 1 is a single bond, ethylene, vinylene, ethynylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy.
  • Preferred Z 1 is a single bond for increasing the maximum temperature and difluoromethyleneoxy for increasing the dielectric anisotropy.
  • a particularly preferred Z 1 is a single bond.
  • Z 2 is a single bond, ethylene, vinylene, ethynylene, methyleneoxy, or carbonyloxy.
  • Preferred Z 2 is a single bond in order to improve stability against light and heat.
  • Z 3 and Z 4 are single bonds, ethylene, vinylene, methyleneoxy, or carbonyloxy. Desirable Z 3 or Z 4 is a single bond for decreasing the minimum temperature, and methyleneoxy for increasing the dielectric constant in the short axis direction of liquid crystal molecules.
  • Particularly preferred Z 3 or Z 4 is a single bond.
  • A is 1, 2, 3, or 4.
  • Preferred a is 2 for lowering the minimum temperature and 3 for increasing the dielectric anisotropy.
  • b is 1, 2, or 3.
  • Preferred b is 1 for decreasing the minimum temperature and 2 or 3 for increasing the maximum temperature.
  • c is 0, 1, 2, or 3; d is 0 or 1; the sum of c and d is 3 or less.
  • Preferred c is 1 for decreasing the minimum temperature and 2 or 3 for increasing the maximum temperature.
  • Preferred d is 0 for increasing the dielectric constant of the liquid crystal molecule in the minor axis direction, and 1 for decreasing the minimum temperature.
  • X 1 and X 2 are hydrogen or fluorine.
  • Preferred X 1 or X 2 is hydrogen for increasing the maximum temperature and fluorine for increasing the dielectric anisotropy.
  • Y 1 is fluorine, chlorine, cyano, an alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, an alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, Alternatively, it is alkenyloxy having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.
  • Preferred Y 1 is fluorine for decreasing the viscosity and cyano for increasing the dielectric anisotropy.
  • 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.
  • Preferred compound (1) includes compounds (1-1) to (1-47) described in item 2.
  • at least one of the first components is compound (1-1), compound (1-2), compound (1-7), compound (1-9), compound (1-13), compound ( 1-16), compound (1-17), compound (1-23), compound (1-24), compound (1-28), compound (1-29), compound (1-30), compound (1 It is preferably -33), compound (1-34), compound (1-41), or compound (1-42).
  • At least two of the first components are compound (1-1) and compound (1-2), compound (1-1) and compound (1-9), compound (1-2) and compound (1-9), Compound (1-1) and compound (1-16), compound (1-2) and compound (1-16), compound (1-9) and compound (1-16), compound (1-9) and compound (1-16), compound (1-9) and compound (1-24), compound (1-16) and compound (1-24), compound (1-9) and compound (1-41), compound (1-16) and compound (1-41), compound ( 1-9) and compound (1-42), or a combination of compound (1-16) and compound (1-42) is preferable.
  • Preferred compounds (2) are the compounds (2-1) to (2-23) described in item 5.
  • at least one of the second components is compound (2-1), compound (2-2), compound (2-3), compound (2-6), compound (2-9), compound ( 2-10), compound (2-11), compound (2-12), compound (2-13), compound (2-16), compound (2-20), or compound (2-21) Is preferred.
  • At least two of the second components are compound (2-2) and compound (2-9), compound (2-2) and compound (2-10), compound (2-2) and compound (2-12), The compound (2-9) and the compound (2-10), the compound (2-9) and the compound (2-12), or the combination of the compound (2-10) and the compound (2-12) is preferable.
  • Preferred compounds (3) are the compounds (3-1) to (3-35) described in item 8.
  • at least one of the third components is compound (3-1), compound (3-3), compound (3-6), compound (3-8), compound (3-10), compound ( 3-14) or the compound (3-34) is preferable.
  • At least two of the third components are compound (3-1) and compound (3-8), compound (3-1) and compound (3-14), compound (3-3) and compound (3-8), Compound (3-3) and compound (3-14), compound (3-3) and compound (3-34), compound (3-6) and compound (3-8), compound (3-6) and compound It is preferably (3-10) or a combination of compound (3-6) and compound (3-14).
  • a polymer is derived from the polymerizable compound.
  • the polymerizable compound may be a single compound or a mixture of a plurality of compounds.
  • a preferable polymerizable compound is the compound (4), the compound (5), or the compound (6).
  • Preferred polymerizable compound is compound (7), compound (8), or compound (9).
  • the polymerizable compound may be a mixture of compounds selected from the compound (4) to the compound (9). This mixture may contain a polymerizable compound different from compounds (4) to (9). Such a mixture contains a compound selected from the compound (4) to the compound (9) as a main component.
  • the main component means a component that occupies the largest proportion in the mixture.
  • the main component is compound (4).
  • the compound (4) is called the main component.
  • Z 5 is alkylene having 1 to 20 carbons, and in this alkylene, at least one hydrogen may be replaced by alkyl having 1 to 5 carbons, fluorine, chlorine, or P 3.
  • At least one —CH 2 — may be replaced by —O—, —CO—, —COO—, —OCO—, —NH—, or —N(R 6 )—
  • at least one —CH 2 —CH 2 — may be replaced by —CH ⁇ CH— or —C ⁇ C—
  • at least one —CH 2 — is a carbocyclic saturated aliphatic compound, a heterocyclic saturated aliphatic Divalent compounds formed by removing two hydrogens from a compound, a carbocyclic unsaturated aliphatic compound, a heterocyclic unsaturated aliphatic compound, a carbocyclic aromatic compound, or a heterocyclic aromatic compound
  • a group may be substituted, and in these divalent groups, the number
  • divalent groups formed by removing two hydrogens from a carbocyclic or heterocyclic saturated aliphatic compound are 1,4-cyclohexylene, decahydronaphthalene-2,6-diyl and tetrahydropyran-2. ,5-diyl, 1,3-dioxane-2,5-diyl and the like.
  • divalent groups formed by removing two hydrogens from a carbocyclic or heterocyclic unsaturated aliphatic compound are 1,4-cyclohexenylene, dihydropyran-2,5-diyl and the like.
  • divalent groups formed by removing two hydrogens from a carbocyclic or heterocyclic aromatic compound are 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, naphthalene-1,2-diyl, pyrimidine-2,5-diyl and the like.
  • Preferred Z 5 is alkylene having 1 to 20 carbons, in which at least one hydrogen may be replaced by alkyl having 1 to 5 carbons, and at least one —CH 2 — is —O. At least one —CH 2 — is replaced by a divalent group formed by removing two hydrogens from a carbocyclic saturated aliphatic compound or a carbocyclic aromatic compound. Also, in these divalent groups, the number of carbon atoms is 5 to 35. More desirable Z 5 is alkylene having 1 to 20 carbons, in which at least one hydrogen may be replaced by alkyl having 1 to 5 carbons, and at least one —CH 2 — is — It may be replaced with O-.
  • Preferred Z 5 contains a ring structure such as 1,4-cyclohexylene and 1,4-phenylene in order to improve the compatibility with the liquid crystal composition.
  • Preferred Z 5 includes a chain structure such as alkylene for easily forming a network structure.
  • P 1 , P 2 , and P 3 are polymerizable groups.
  • Preferred polymerizable groups are formulas (P-1) to (P-6). In these formulas, the wavy line indicates the binding site. More preferred polymerizable groups are formulas (P-1) to (P-3).
  • P 1 , P 2 , and P 3 may be acryloyloxy or methacryloyloxy.
  • M 1 , M 2 and M 3 are each hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced with fluorine or chlorine. And alkyl having 1 to 5 carbon atoms.
  • Preferred M 1 , M 2 or M 3 is hydrogen or methyl for increasing the reactivity. More preferred M 1 is hydrogen or methyl, and more preferred M 2 or M 3 is hydrogen.
  • Examples of the compound (4) include the compounds (4-1) to (4-5).
  • p is an integer of 1 to 6
  • q is an integer of 5 to 20
  • r is 1 to 15 It is an integer.
  • the compound (4) when the number of polymerizable groups is large, the polymer surrounding the droplets becomes hard or the network becomes dense due to crosslinking.
  • Compound (4) gives the corresponding polymer by polymerization.
  • the compound (4) is volatile, its oligomer may be used.
  • the preferred polymer is colorless and transparent and is insoluble in the liquid crystal composition.
  • the preferred polymer has excellent adhesion to the substrate of the device and reduces the driving voltage.
  • a polymerizable compound different from the compound (4) may be used in combination.
  • M 4 and M 5 are hydrogen or methyl.
  • Preferred M 4 or M 5 is hydrogen for increasing the reactivity.
  • Z 6 is alkylene having 21 to 80 carbons, in which at least one hydrogen may be replaced by alkyl having 1 to 20 carbons, fluorine, or chlorine, and at least one —CH 2 — May be replaced by —O—, —CO—, —COO—, —OCO—, —NH—, or —N(R 6 )—, and at least one —CH 2 —CH 2 — is — CH ⁇ CH— or —C ⁇ C—, wherein R 6 is alkyl having 1 to 12 carbons, in which at least one —CH 2 — is —O— , -CO-, -COO-, or -OCO-.
  • Preferred Z 6 is alkylene having 21 to 60 carbon atoms for low voltage driving, in which at least one hydrogen may be replaced by alkyl having 1 to 20 carbons, and at least one- CH 2 — may be replaced with —O—, —COO—, or —OCO—.
  • More preferred Z 6 is alkylene in which at least one hydrogen has been replaced with alkyl for low voltage driving. It is preferred to prevent steric hindrance when the two hydrogens of the alkylene have been replaced by alkyl.
  • two alkyls are sufficiently separated, or one of the alkyls is an alkyl having 1 to 5 carbons. The same applies when at least three hydrogens are replaced by alkyl.
  • R 8 and R 10 are alkyl having 1 to 5 carbons
  • R 9 and R 11 are alkyl having 5 to 20 carbons
  • at least one- CH 2 — may be replaced by —O—, —CO—, —COO—, or —OCO—
  • Z 8 is alkylene having 10 to 30 carbons, and in this alkylene, at least one —CH 2- may be replaced by -O-, -CO-, -COO-, or -OCO-.
  • Examples of the compound (5-1) are the compound (5-1-1) and the compound (5-1-2).
  • R 8 and R 10 are ethyl
  • R 9 and R 11 are —CH 2 OCOC 9 H 19 , —CH 2.
  • the compound (5) is diacrylate or dimethacrylate. Since Z 6 in the formula (5) is alkylene or the like, the polymer easily forms a network structure. When the molecular chain of Z 6 is short, the crosslinked sites of the polymer are close to each other, resulting in a small mesh. When the molecular chain of Z 6 is long, the cross-linking site of the polymer is separated and the degree of freedom of molecular motion is improved, so that the driving voltage is lowered. When Z 6 is branched, the degree of freedom is further improved, and thus the driving voltage is further reduced. In order to improve this effect, a polymerizable compound different from the compound (5) may be used in combination.
  • M 6 is hydrogen or methyl.
  • Preferred M 6 is hydrogen for increasing the reactivity.
  • Z 7 is a single bond or alkylene having 1 to 5 carbons, and in this alkylene, at least one hydrogen may be replaced by fluorine or chlorine, and at least one —CH 2 — is —O—, — It may be replaced with CO-, -COO-, or -OCO-.
  • Preferred Z 7 is a single bond or alkylene having 1 to 5 carbons, in which at least one —CH 2 — is replaced with —O—, —CO—, —COO—, or —OCO—. May be.
  • R 7 is alkyl having 1 to 40 carbons, and in this alkyl, at least one hydrogen may be replaced by fluorine or chlorine, and at least one —CH 2 — is —O—, —CO—, It may be replaced by —COO— or —OCO—, and at least one —CH 2 — is a carbocyclic saturated aliphatic compound, a heterocyclic saturated aliphatic compound, a carbocyclic unsaturated aliphatic compound.
  • the divalent group it has 5 to 35 carbon atoms, and at least one hydrogen may be replaced by alkyl having 1 to 12 carbons, and in this alkyl, at least one —CH 2 — is —O— , -CO-, -COO-, or -OCO-.
  • Preferred R 7 is alkyl having 5 to 30 carbons. More desirable R 7 is branched alkyl having 5 to 30 carbons.
  • Examples of compound (6) are compound (6-1) to compound (6-6).
  • R 12 is alkyl having 5 to 20 carbon atoms, and in this alkyl, at least one —CH 2 — is —O—, —CO—, It may be replaced with —COO— or —OCO—
  • R 13 and R 14 are alkyl having 3 to 10 carbons, and in this alkyl, at least one —CH 2 — is —O—, — It may be replaced with CO-, -COO-, or -OCO-.
  • the compound (6) is acrylate or methacrylate.
  • R 7 in formula (6) has a cyclic structure, affinity with the liquid crystal composition is improved.
  • R 7 is alkylene, the polymer tends to form a network structure. In this polymer, alkylene improves the degree of freedom of molecular motion, so that the driving voltage is lowered.
  • a polymerizable compound different from the compound (6) may be used in combination.
  • ring G, ring I, ring J, ring K, ring L, and ring M are 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexenylene, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, or fluorene-2,7-diyl, where: At least one hydrogen is fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, alkoxycarbonyl having 2 to 5 carbons.
  • preferred rings are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-methyl-1, It is 4-phenylene, 2-methoxy-1,4-phenylene, or 2-trifluoromethyl-1,4-phenylene.
  • a more preferred ring is 1,4-cyclohexylene or 1,4-phenylene.
  • Z 8 , Z 10 , Z 12 , Z 13 , and Z 17 are single bonds, —O—, —COO—, —OCO—, or —OCOO—.
  • Z 9 , Z 11 , Z 14 and Z 16 are a single bond, —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —COS—, —SCO—, —OCOO—, —CONH.
  • Z 15 is a single bond, —O—, or —COO—.
  • Preferred Z 8 , Z 10 , Z 12 , Z 13 , or Z 17 is a single bond or —O—.
  • Preferred Z 9 , Z 11 , Z 14 or Z 16 is a single bond, —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —CH 2 CH 2 —, —CH 2 CH 2 COO. -Or -OCOCH 2 CH 2 -.
  • Y 2 is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, alkoxy having 1 to 20 carbons, or having 2 to 20 carbons. It is an alkoxycarbonyl. Preferred Y 2 is cyano, alkyl or alkoxy.
  • f and h are integers from 1 to 4; k and m are integers from 0 to 3; the sum of k and m is 1 to 4; e, g, i, j, l, and n are , An integer from 0 to 20.
  • M 7 to M 12 are hydrogen or methyl.
  • Examples of compound (7) are compound (7-1) to compound (7-24).
  • M 7 is hydrogen or methyl
  • e is an integer of 1 to 20.
  • Examples of compound (8) are compound (8-1) to compound (8-31).
  • M 8 and M 9 are hydrogen or methyl, and g and i are integers from 1 to 20.
  • Examples of compound (9) include compound (9-1) to compound (9-10).
  • M 10 , M 11 , and M 12 are hydrogen or methyl, and j, l, and n are integers from 1 to 20.
  • Liquid crystal compounds have mesogens (rigid sites that induce liquid crystallinity), but these compounds also have mesogens. Therefore, these compounds are aligned with the liquid crystal compound in the same direction by the action of the alignment film. This orientation is maintained after polymerization. Such a liquid crystal composite has high transparency.
  • a polymerizable compound different from the compound (7), the compound (8), and the compound (9) may be used in combination.
  • the liquid crystal light control device is sometimes used for partitioning a room.
  • one dichroic dye may be added to the liquid crystal composition.
  • a mixture of dyes may be added.
  • the liquid crystal light control device is sometimes used to block sunlight.
  • a black (or blackish) dichroic dye is added to the liquid crystal composition.
  • Black is prepared by mixing cyan, magenta and yellow dichroic dyes. At least two dyes are mixed. Preferably two, three, four, five or six dyes are mixed. Particularly preferably, 3 or 4 dyes are mixed.
  • Such dichroic dyes have at least some of the characteristics described below.
  • a) The dye molecule is linear.
  • a skeleton peculiar to dichroic dyes such as a benzothiadiazole ring and a diketopyrrolopyrrole ring exists in the center of the molecule.
  • c) The benzene ring and the thiophene ring which constitute the molecule together with the unique skeleton are located on the same plane.
  • the side chain is alkyl or alkoxy.
  • Examples of the skeleton peculiar to the dichroic dye are as follows. From the left, the compound names are benzothiadiazole, diketopyrrolopyrrole, azo compound, and perylene.
  • dichroic dyes examples include benzothiadiazoles, diketopyrrolopyrroles, azo compounds (azo compounds), azomethine compounds (methine compounds), methine compounds (anthraquinones). , Merocyanines, naphthoquinones, tetrazines, pyrromethenes, and rylenes such as perylenes and terrylenes.
  • Preferred dichroic dyes are benzothiadiazoles, diketopyrrolopyrroles, azo compounds, anthraquinones, and rylenes.
  • Particularly preferred dichroic dyes are benzothiadiazoles, diketopyrrolopyrroles, azo compounds, and rylenes.
  • benzothiadiazoles means a dichroic dye having a benzothiadiazole ring.
  • a preferable ratio of the dichroic dye is in the range of 0.03% to 25% based on the liquid crystal composition.
  • a more desirable ratio is in the range of 0.03% to 20%.
  • a particularly desirable ratio is in the range of 0.03% to 15%.
  • dichroic dye examples include compounds (10-1) to (10-110).
  • Et is ethyl
  • n-Bu and nBu are butyl
  • n-Pent is pentyl
  • n-Hex is hexyl
  • Examples of commercially available dichroic dyes are G-207, G-241, G-305, G-470, G-471, G-472, LSB-278, LSB-335, NKX- manufactured by Nagase & Co. 1366, NKX-3538, NKX-3540, NKX-3622, NKX-3739, NKX-3742, NKX-3773, NKX-4010, and NKX-4033; S-428, SI-426, SI- manufactured by Mitsui Chemicals Fine. 486, M-412, and M-483.
  • composition is prepared from the compounds thus obtained by known methods. For example, the component compounds are mixed and heated to dissolve each other.
  • additives are optically active compounds, antioxidants, ultraviolet absorbers, quenchers, dyes, defoamers, polymerization initiators, polymerization inhibitors, polar compounds and the like.
  • the additive may be added to the liquid crystal composition or the polymerizable compound instead of the polymerizable composition.
  • An optically active compound is added to a liquid crystal composition for the purpose of inducing a helical structure of liquid crystal molecules to give a twist angle.
  • examples of such compounds are compound (11-1) to compound (11-5).
  • a desirable ratio of the optically active compound is about 5% or less. A more desirable ratio is in the range of approximately 0.01% to approximately 2%.
  • an antioxidant such as compound (12-3) may be added to the composition.
  • a preferable ratio of the antioxidant is about 50 ppm or more to obtain the effect, and about 600 ppm or less so as not to lower the upper limit temperature or to raise the lower limit temperature.
  • a more desirable ratio is in the range of approximately 100 ppm to approximately 300 ppm.
  • Preferred examples of the ultraviolet absorber are benzophenone derivative, benzoate derivative, triazole derivative and the like.
  • Light stabilizers such as sterically hindered amines are also preferred.
  • Preferred examples of the light stabilizer include compounds (13-1) to (13-16).
  • a desirable ratio of these absorbers 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 to prevent the liquid crystal compound from decomposing.
  • Preferred examples of the quencher include compounds (14-1) to (14-7).
  • 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.
  • Defoaming agents such as dimethyl silicone oil and methylphenyl silicone oil are 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.
  • UV irradiation is preferred for the polymerization of the polymerizable compound.
  • the ultraviolet irradiation lamp are a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp and the like.
  • the wavelength of ultraviolet rays is preferably in the absorption wavelength region of the photopolymerization initiator. Avoid the absorption wavelength range of the liquid crystal composition.
  • a preferred wavelength is 330 nm or more.
  • a more preferable wavelength is 350 nm or more, for example 365 nm.
  • the reaction may be performed near room temperature or may be performed by heating.
  • a polymerization initiator such as a photopolymerization initiator.
  • a polymerization initiator such as a photopolymerization initiator.
  • suitable types and amounts of initiators are known to the person skilled in the art and are described in the literature.
  • the photoinitiators Irgacure 651 registered trademark; BASF
  • Irgacure 184 registered trademark; BASF
  • Darocur 1173 registered trademark; BASF
  • a polymerization inhibitor When storing a polymerizable compound, a polymerization inhibitor may be added to prevent polymerization.
  • the polymerizable compound is usually mixed with the liquid crystal composition without removing the polymerization inhibitor.
  • the polymerization inhibitor are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine and the like.
  • a polar compound is a polar organic compound.
  • 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 polar group has non-covalent interactions with the surface of the glass substrate, metal oxide film, etc. This compound is adsorbed on the substrate surface by the action of the polar group and controls the alignment of liquid crystal molecules.
  • the polar compound may control not only the liquid crystal molecule but also the polymerizable compound. Such effects are expected for polar compounds.
  • the method for preparing the liquid crystal composite from the polymerizable composition is as follows. First, the polymerizable composition is sandwiched between a pair of substrates. The sandwiching is performed by a vacuum injection method or a liquid crystal dropping method at a temperature higher than the upper limit temperature of the polymerizable composition. In the devices manufactured by these methods, display defects such as flow marks and drop marks may occur. The trace is a trace of the polymerizable composition flowing through the device. The drop mark is a mark on which the polymerizable composition is dropped. It is preferable to suppress such display defects. Next, the polymerizable compound is polymerized by heat or light. Ultraviolet irradiation is preferred for the polymerization.
  • Polymerization causes phase separation of the polymer from the polymerizable composition.
  • a light control layer liquid crystal composite
  • This light control layer is classified into a polymer dispersion type, a polymer network type, and a mixed type of both.
  • the Aging may cause a change over time.
  • the haze rate may change compared to the initial stage. The smaller the change in haze ratio, the better. When the haze change rate is small, good transparency and opacity are maintained.
  • the haze change rate is preferably 20% or less. A more preferable haze change rate is 10% or less or 5% or less.
  • flicker may occur on the display screen. It is presumed that this flicker is associated with image burn-in and is caused by a difference between the potential of the positive frame and the potential of the negative frame when driven by an alternating current.
  • the flicker rate (%) can be represented by (
  • the flicker rate of the element is preferably in the range of 0% to 1%. The occurrence of flicker can be suppressed by appropriately selecting the component compounds of the polymerizable composition contained in the device.
  • the brightness may partly decrease.
  • An example of such a display defect is a line afterimage. This is a phenomenon in which different voltages are repeatedly applied to two adjacent electrodes, so that the luminance between the electrodes decreases in a stripe shape. This phenomenon is presumed to be due to the accumulation of ionic impurities contained in the liquid crystal composition on the alignment film near the electrodes.
  • Such a light control element has a light control layer (liquid crystal composite) sandwiched by a pair of transparent substrates having transparent electrodes.
  • the substrate is a material that does not easily deform, such as a glass plate, a quartz plate, or an acrylic plate.
  • a flexible transparent plastic film such as an acrylic film or a polycarbonate film.
  • one of the substrates may be an opaque material such as silicone resin.
  • This substrate has a transparent electrode thereon. Examples of transparent electrodes are indium tin oxide (ITO) and conductive polymers.
  • the substrate may have an alignment film on the transparent electrode.
  • the alignment film a thin film such as polyimide or polyvinyl alcohol is suitable.
  • the polyimide alignment film can be obtained by applying a polyimide resin composition on a transparent substrate, thermally curing at a temperature of about 180° C. or higher, and rubbing with a cotton cloth or rayon cloth as needed.
  • the pair of substrates should face each other with the transparent electrode layer inside.
  • a spacer may be added to make the thickness between the substrates uniform. Examples of spacers are glass particles, plastic particles, alumina particles, photo spacers and the like.
  • the preferred thickness of the light control layer is about 2 ⁇ m to about 50 ⁇ m, more preferably about 5 ⁇ m to about 20 ⁇ m.
  • a general-purpose sealant can be used to bond the pair of substrates.
  • An example of the sealant is an epoxy thermosetting composition.
  • a light absorption layer, a diffuse reflection plate, etc. can be arranged on the back surface of the element, if necessary. It is also possible to add functions such as specular reflection, diffuse reflection, retroreflection, and hologram reflection.
  • Such an element has a function as a light control film or light control glass.
  • the element When the element is in the form of a film, it can be attached to an existing window or sandwiched between a pair of glass plates to form a laminated glass.
  • Such elements are used for windows installed on the outer wall or as a partition between the conference room and the corridor. That is, there are applications such as electronic blinds, dimming windows, and smart windows.
  • the function as an optical switch can be used for a liquid crystal shutter or the like.
  • the present invention will be described in more detail by way of examples. The invention is not limited to these examples.
  • the composition (M1), the composition (M2) and the like are described.
  • the mixture of composition (M1) and composition (M2) is not mentioned. However, we shall consider this mixture also disclosed.
  • a mixture of at least two compositions selected from the examples shall also be considered disclosed.
  • the synthesized compound was identified by a method such as NMR analysis. The characteristics of the compounds, compositions and devices were measured by the following methods.
  • NMR analysis For measurement, DRX-500 manufactured by Bruker BioSpin Co. was used. In the 1 H-NMR 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. In 19 F-NMR measurement, 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; nonpolar) manufactured by Agilent Technologies Inc. was used to separate the 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%), and 1 ⁇ L thereof was injected into the sample vaporization chamber.
  • the recorder is a C-R5A type Chromatopac manufactured by Shimadzu, or its equivalent.
  • the obtained gas chromatogram showed the retention time of peaks and the area 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 made 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 compound peaks from overlapping.
  • 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).
  • FID gas chromatography
  • the area ratio of the peaks in the gas chromatogram corresponds to the ratio of the liquid crystal compound.
  • the correction coefficient of each liquid crystal compound may be regarded as 1. Therefore, the ratio of the liquid crystal compound can be calculated from the peak area ratio.
  • Measurement sample When measuring the characteristics of the composition and the device containing this composition, the composition was directly used as a sample.
  • a sample for measurement was prepared by mixing this compound (15%) with a mother liquid crystal (85%).
  • the smectic phase (or crystal) was precipitated at 25° C. in this ratio, the ratios of the compound and the mother liquid crystal were changed in the order of 10%:90%, 5%:95%, 1%:99%. Values of maximum temperature, optical anisotropy, viscosity, and dielectric anisotropy of the compound were obtained by this extrapolation method.
  • 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 a method modified from this. Met. No thin film transistor (TFT) was attached to the TN (twisted nematic) element used for the measurement.
  • T C Minimum temperature of nematic phase
  • a sample having a nematic phase was placed in a glass bottle and placed in a 0°C, -10°C, -20°C, -30°C, and -40°C freezer 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): Measurement is performed according to the method described in M.Imai, et al.,Molecular Crystals and Liquid Crystals, Vol. 259,37 (1995). I obeyed. The sample was placed in a TN device having a twist angle of 0° and a distance (cell gap) between two glass substrates of 5 ⁇ m. A voltage of 0.5 V was applied stepwise in the range of 16 V to 19.5 V to this device. 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 and the 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 in the paper by M. Imai et al.
  • the value of the dielectric anisotropy necessary 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 into 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 device 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 light amount is maximum and the transmittance is 0% when the light amount is minimum was created.
  • the threshold voltage is represented by the voltage when the transmittance reaches 90%.
  • VHR Voltage holding ratio
  • the TN device used for the measurement had a polyimide alignment film, and the distance (cell gap) between the two glass substrates was 5 ⁇ m.
  • a sample was put in this TN device, and the TN device was sealed with an adhesive curable by ultraviolet rays.
  • This TN device was placed in a constant temperature bath at 60° C. and charged by applying a pulse voltage (1 V, 60 microseconds, 3 Hz).
  • the decaying voltage was measured with a high-speed voltmeter for 166.6 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.
  • Voltage holding ratio (9) Voltage holding ratio (UV-VHR; measured at 25° C.; %): A TN device containing a sample was irradiated with 5 mmW of ultraviolet rays for 166.6 minutes using a black light as a light source. The voltage holding ratio was measured and the stability to ultraviolet rays was evaluated. The configuration of the TN device and the method of measuring the voltage holding ratio are described in item (8). A composition having a large UV-VHR has great stability to ultraviolet rays. UV-VHR is preferably 90% or more, more preferably 95% or more.
  • 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 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 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 formula (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.
  • Pretilt angle (degree) A spectroscopic ellipsometer M-2000U (manufactured by J. A. Woollam Co., Inc.) was used for measuring the pretilt angle.
  • Flicker rate (measured at 25° C.; %):
  • a multimedia display tester 3298F manufactured by Yokogawa Electric Co., Ltd. was used.
  • the light source was an LED.
  • the sample was put into a normally black mode device in which the distance (cell gap) between the two glass substrates was 3.5 ⁇ m and the rubbing direction was antiparallel.
  • the device was sealed with an adhesive that was cured with ultraviolet light. A voltage was applied to this element, and the voltage at which the amount of light transmitted through the element was maximized was measured. While applying this voltage to the element, the sensor part was brought close to the element and the displayed flicker rate was read.
  • Line afterimage (Line Image Sticking Parameter; LISP;%): A line afterimage was generated by applying electrical stress to the element. The luminance of the area having the line afterimage and the luminance of the remaining area (reference 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.
  • 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). An LED backlight having an average luminance of 3500 cd/m 2 was used as a light source.
  • a sample is put into an FFS element (16 cells of 4 cells in the vertical direction ⁇ 4 cells in the lateral direction) having a cell gap of 3.5 ⁇ m and 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. This device was irradiated with light and a voltage (rectangular wave, 60 Hz) was applied. The voltage was stepwise increased in the range of 0 V to 7.5 V in steps of 0.1 V, 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 luminance becomes 21.6% of V255 (that is, 127 gradations) is abbreviated as V127.
  • V255 (rectangular wave, 30 Hz) was applied to the stress region and 0.5 V (rectangular wave, 30 Hz) was applied to the stress region under the conditions of 60° C. and 23 hours to display a checker pattern.
  • V127 (rectangular wave, 0.25 Hz) was applied, and the luminance was measured under the condition that the exposure time was 4000 milliseconds.
  • Face afterimage (Face Image Sticking Parameter; FISP;%): A surface afterimage was generated by applying electrical stress to the element. The luminance of the area having the surface afterimage and the luminance of the remaining area were measured at 25°C. The ratio of the change in luminance due to the surface afterimage was calculated, and the size of the surface afterimage was expressed by this ratio.
  • Haze change rate (%): A weather resistance test of the device was performed. The haze was measured before and after the test, and the haze change rate was calculated. This test was conducted according to Japanese Industrial Standard (JIS) K5600-7-7, accelerated weather resistance and accelerated light resistance (xenon lamp method). The measurement conditions were illuminance (UVA; 180 W/m 2 ), irradiation time (100 hours), black panel temperature (63 ⁇ 2° C.), bath temperature (35° C.), bath relative humidity (40% RH). It was
  • Example of composition is shown below.
  • the liquid crystal compounds are represented by symbols based on the definition in Table 3 below.
  • Table 3 the configuration of 1,4-cyclohexylene is trans.
  • the number in parentheses after the symbolized compound represents the chemical formula to which the compound belongs.
  • the symbol ( ⁇ ) means other liquid crystal compound.
  • compositions are selected and used.
  • the black dichroic dye (A) is prepared according to Example 42 of Patent Document 9 by mixing the following four dyes.
  • the proportion and color of the dye are 56.3% (yellow), 12.6% (orange), 9.6% (red), and 21.5% (blue) in order from the top.
  • Example 1 Fabrication of liquid crystal light control device-1
  • the composition (M1) had a positive dielectric anisotropy.
  • a 60% composition (M1), 32% polymerizable compound (RM-1) and 8% polymerizable compound (RM-5) are mixed to prepare a polymerizable composition.
  • the above black dichroic dye (A) is added to this composition at a rate of 5% based on the composition (M1).
  • Irgacure 651 photopolymerization initiator; BASF
  • BASF photopolymerization initiator
  • This polymerizable composition is injected into a device in which the distance (cell gap) between two glass substrates is 3.5 ⁇ m. The temperature at the time of injection is 140°C.
  • This device is irradiated with 18 mW/cm 2 ultraviolet rays for 56 seconds with a high-pressure mercury lamp to produce a device having a liquid crystal composite.
  • This element is black. When a voltage of 45 V is applied to this element and it is irradiated with light, it becomes transparent. This indicates that the device is in normal mode.
  • the polymerizable composition is prepared without adding the black dichroic dye (A) to the composition.
  • a device having a liquid crystal composite is manufactured. This element is opaque. However, the surface of the device is bright. When a voltage of 45 V is applied to this element and light is irradiated, the element becomes transparent.
  • Example 2 Fabrication of liquid crystal light control device-2 Next, the two kinds of polymerizable compounds are combined. 90% of the composition (M1), 5% of the polymerizable compound (RM-8) and 5% of the polymerizable compound (RM-11) are mixed to prepare a polymerizable composition.
  • the above black dichroic dye (A) is added to this composition at a rate of 5% based on the composition (M1).
  • Irgacure 651 photopolymerization initiator; BASF
  • BASF photopolymerization initiator
  • This polymerizable composition is injected into a device in which the distance (cell gap) between two glass substrates is 3.5 ⁇ m. The temperature at the time of injection is 140°C.
  • This device is irradiated with 18 mW/cm 2 ultraviolet rays for 56 seconds with a high-pressure mercury lamp to produce a device having a liquid crystal composite.
  • This element is black. When a voltage of 45 V is applied to this element and it is irradiated with light, it becomes transparent. This indicates that the device is in normal mode.
  • Example 3 Measurement of Haze Change Rate
  • the elements manufactured in Examples 1 and 2 are placed in a haze meter so that the elements are perpendicular to incident light. A voltage in the range of 0V to 60V is applied to this element, and the haze ratio is measured. Next, the haze ratio after the weather resistance test performed under the condition described in Measurement (22) is measured, and the haze change ratio is calculated. The haze change rate is small. This indicates that the liquid crystal light control device has a small change with time.
  • the liquid crystal light control device containing the liquid crystal composite of the present invention can be used for light control windows, smart windows, and the like.

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Abstract

L'invention fournit un composite de cristaux liquides adapté à une gradation de lumière qui comprend une composition de cristaux liquides satisfaisant au moins une caractéristique telle qu'une température limite supérieure élevée, une température limite inférieure basse, une viscosité faible, une anisotropie optique importante, et une anisotropie de constante diélectrique positive importante, ou présentant un équilibre approprié entre au moins deux de ces caractéristiques. L'invention fournit en outre un élément de gradation de lumière à cristaux liquides possédant ce composite de cristaux liquides.　Plus précisément, l'invention concerne un composite de cristaux liquides qui comprend : la composition de cristaux liquides comprenant à son tour un composé spécifique possédant une anisotropie de constante diélectrique positive importante, et un colorant dichroïque; et un polymère. Ce composite de cristaux liquides peut également comprendre un composé spécifique possédant une température limite supérieure élevée ou une température limite inférieure basse.
PCT/JP2019/048908 2019-02-01 2019-12-13 Composite de cristaux liquides, élément de gradation de lumière à cristaux liquides, et fenêtre de gradation de lumière Ceased WO2020158211A1 (fr)

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