WO2020189209A1 - 液晶複合体および液晶調光素子 - Google Patents

液晶複合体および液晶調光素子 Download PDF

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WO2020189209A1
WO2020189209A1 PCT/JP2020/007804 JP2020007804W WO2020189209A1 WO 2020189209 A1 WO2020189209 A1 WO 2020189209A1 JP 2020007804 W JP2020007804 W JP 2020007804W WO 2020189209 A1 WO2020189209 A1 WO 2020189209A1
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liquid crystal
carbon atoms
compound
replaced
hydrogen
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French (fr)
Japanese (ja)
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将之 齋藤
藤田　浩章
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Jnc株式会社
Jnc石油化学株式会社
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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
    • C09K19/12—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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    • C09K19/06—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
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    • 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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    • C09K19/06—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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    • C09K19/06—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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    • C09K19/06—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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    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
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    • C09K19/00—Liquid crystal materials
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    • 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
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    • 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 dimming element. More specifically, the present invention relates to a liquid crystal dimming device having a liquid crystal composite in which a polymer and a liquid crystal composition having positive dielectric anisotropy are combined.
  • the liquid crystal dimming element has a method such as using light scattering. Such elements are used in building materials such as windowpanes and room partitions, and in-vehicle parts. For these elements, a soft substrate such as a plastic film is used in addition to a hard substrate such as a glass substrate. In the liquid crystal composition sandwiched between these substrates, the arrangement of the liquid crystal molecules is changed by adjusting the applied voltage. Since the light transmitted through the liquid crystal composition can be controlled by this method, the liquid crystal dimming element is widely used in displays, optical shutters, dimming windows (Patent Document 1), smart windows (Patent Document 2), and the like. Has been done.
  • liquid crystal dimming element is a polymer dispersion type element in a light scattering mode.
  • the liquid crystal composition is dispersed in the polymer.
  • This device has the following features.
  • the device is easy to manufacture. Since the film thickness can be easily controlled over a wide area, it is possible to manufacture an element having a large screen. Since no polarizing plate is required, bright display is possible. Since it uses light scattering, it has a wide viewing angle. Since this device has such excellent properties, it is expected to be used for dimming glass, projection display, large area display and the like.
  • liquid crystal composition is present in the three-dimensional network of polymers.
  • This composition differs from the polymer dispersed type in that it is continuous.
  • This type of device also has the same characteristics as the polymer dispersion type device.
  • liquid crystal dimming device in which a polymer network type and a polymer dispersion type are mixed.
  • a liquid crystal composition having appropriate characteristics is used for the liquid crystal dimming element. By improving the characteristics of this composition, an element having good characteristics can be obtained.
  • the relationship between the two characteristics is summarized in Table 1 below.
  • the properties 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 upper limit temperature of the nematic phase is about 70 ° C. or higher, and the preferred lower limit 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 preferred to control the light transmittance. Even 1 millisecond is desirable for a shorter response time than other devices.
  • the elastic constant of the composition is related to the response time of the device. Large elastic constants in the composition are preferred in order to achieve short response times in the device.
  • the optical anisotropy of the composition is related to the haze rate of the liquid crystal light control element.
  • the haze ratio is the ratio of diffused light to total transmitted light. A large haze rate is preferred when blocking light. Large optical anisotropy is preferred for large haze rates.
  • the large dielectric anisotropy in the composition contributes to the low threshold voltage and low power consumption in the device. Therefore, large dielectric anisotropy is preferred.
  • the large resistivity in the composition contributes to the large voltage retention in the device. Therefore, a composition having a large resistivity in the initial stage is preferable. A composition having a large specific resistance after long-term use is preferable.
  • the stability and weather resistance of the composition against light and heat are related to the life of the device. When this stability and weather resistance are good, the life is long. Display defects such as afterimages and dripping marks are also related to the life of the device. An element having high weather resistance and less likely to cause display defects is desired.
  • the liquid crystal dimming element has a normal mode and a reverse mode.
  • normal mode the element is opaque when no voltage is applied and becomes transparent when a voltage is applied. This mode is suitable for partitioning rooms.
  • reverse mode the element is transparent when no voltage is applied and becomes opaque when a voltage is applied. This mode is suitable for automobile windows as it becomes transparent when the element fails.
  • An object of the present invention is to provide a liquid crystal composite suitable for dimming by combining an optically active compound with a liquid crystal composition. Another challenge is the high upper limit temperature of the nematic phase, the lower lower limit temperature of the nematic phase, the small viscosity, the large optical anisotropy, the very large dielectric anisotropy, the large specific resistance, the high stability to light, and the high heat. It is to provide a liquid crystal composite suitable for dimming, which contains a liquid crystal composition satisfying at least one of characteristics such as stability, a large elastic constant, and a small spiral pitch. Another challenge 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 dimming element having such a liquid crystal composite.
  • Another challenge is to provide a liquid crystal dimming device having characteristics such as short response time, high voltage retention, low threshold voltage, high haze rate, high weather resistance, and long life.
  • the present invention is a liquid crystal containing a liquid crystal composition and a polymer, wherein the liquid crystal composition contains at least one compound selected from the compounds represented by the formula (1) as component A and an optically active compound as additive A.
  • the present invention relates to a composite, a liquid crystal dimming element having the liquid crystal composite, and the like.
  • R 1 is an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, or an alkenyl having 2 to 12 carbon atoms;
  • ring A is 1,4-cyclohexylene, 1, 4-Phenylene, 2-Fluorine-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 carbon atoms in which at least one
  • An advantage of the present invention is to provide a liquid crystal composite suitable for dimming by combining an optically active compound with a liquid crystal composition.
  • Other advantages are high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, large optical anisotropy, very large dielectric anisotropy, large specific resistance, high stability to light, high resistance to heat. It is to provide a liquid crystal composite suitable for dimming, which contains a liquid crystal composition satisfying at least one of characteristics such as stability, a large elastic constant, and a small spiral pitch.
  • Another advantage is to provide a liquid crystal composite suitable for dimming, which contains a liquid crystal composition having an appropriate balance between at least two of these properties.
  • Another advantage is to provide a liquid crystal dimming device having such a liquid crystal composite.
  • Another advantage is to provide a liquid crystal dimming device having characteristics such as short response time, high voltage retention, low threshold voltage, high haze rate, 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 compound having no liquid crystal phase, but is composed for the purpose of adjusting properties such as temperature range, viscosity, and dielectric constant anisotropy of the nematic phase. It is a general term for compounds added to a product. This compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecule (liquid crystal molecule) is rod-like.
  • the "polymerizable compound” is a compound added for the purpose of forming a polymer in the 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 optically active compounds, antioxidants, UV absorbers, quenchers, dyes, defoamers, and polar compounds are added to the liquid crystal composition as needed.
  • the proportion of the liquid crystal compound is expressed as a mass percentage (mass%) based on the liquid crystal composition containing no additive even when the additive is added.
  • the ratio of additives is expressed as a mass percentage based on the liquid crystal composition containing no additives. That is, the ratio of the liquid crystal compound and the additive is calculated based on the total amount of the liquid crystal compound.
  • “mass%” may be abbreviated as "%".
  • 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 a liquid crystal composition. Additives such as a polymerization initiator and a polymerization inhibitor are added to the polymerizable compound as needed. The ratio of the polymerization initiator and the polymerization inhibitor is expressed as a mass percentage based on the total amount of the polymerizable compound. The proportion of the polymerizable compound or the liquid crystal composition contained in the polymerizable composition is expressed as a mass percentage based on the polymerizable composition containing no additive even when the additive is added.
  • the “liquid crystal composite” is produced by a polymerization treatment of a polymerizable composition.
  • the “liquid crystal dimming element” is an element having a liquid crystal composite, and is a general term for a liquid crystal panel and a liquid crystal module used for dimming.
  • the “upper limit temperature of the nematic phase” may be abbreviated as the “upper limit temperature”.
  • the “lower limit temperature of the nematic phase” may be abbreviated as the “lower limit temperature”.
  • the expression “increase the dielectric anisotropy” means that when the composition has a positive dielectric anisotropy, its value increases positively, and the composition has a negative dielectric anisotropy. When it is a thing, it means that its value increases negatively.
  • “Large voltage retention” means that the element 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 long-term use, the element has a large voltage retention not only at room temperature but also at a temperature close to the upper limit temperature. It means that it has a large voltage holding ratio.
  • the properties of the composition or device 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 the formula (1z) may be abbreviated as "compound (1z)".
  • Compound (1z) means one compound represented by the formula (1z), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas.
  • the expression “at least one compound selected from the compounds of formula (1z) and formula (2z)” means at least one compound selected from the group of compounds (1z) and compound (2z). ..
  • Principal component means the component that occupies the largest proportion in the mixture or composition. For example, in a mixture of 40% compound (1z), 35% compound (2z), and 25% compound (3z), the principal component is compound (1z).
  • the compound (1z) is also referred to as the principal component when the component is only the compound (1z). This compound is also referred to as the principal component when compound (1z) is a single compound.
  • 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'” is that when the number of'A's is 1, the position of the'A'is arbitrary and the number of'A's is 2.
  • their positions can be selected without limitation.
  • the expression "at least one -CH 2- may be replaced by -O-” may be used. In this case, -CH 2 -CH 2 -CH 2 - it is, -CH 2 nonadjacent - may be converted -O-CH 2 -O- to by is replaced by -O-. However, the adjacent -CH 2- is not replaced by -O-. This is because -O-O-CH 2- (peroxide) is produced by this replacement.
  • the alkyl of the liquid crystal compound is linear or branched and does not contain cyclic alkyl. Linear alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl.
  • the configuration for 1,4-cyclohexylene is preferably trans over cis in order to raise the upper temperature limit. Since 2-fluoro-1,4-phenylene is asymmetrical, there are leftward (L) and rightward (R). The same is true for divalent groups such as tetrahydropyran-2,5-diyl. The same is true for binding groups such as carbonyloxy (-COO- or -OCO-).
  • the present invention includes the following items.
  • Item 1 A liquid crystal composite containing a liquid crystal composition and a polymer, wherein the liquid crystal composition contains at least one compound selected from the compounds represented by the formula (1) as the component A and an optically active compound as the additive A. ..
  • R 1 is an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, or an alkenyl having 2 to 12 carbon atoms
  • ring A is 1,4-cyclohexylene, 1, 4-Phenylene, 2-Fluorine-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, carbony
  • Item 2 The liquid crystal complex according to Item 1, wherein the liquid crystal composition contains at least one compound selected from the compounds represented by the formulas (1-1) to (1-47) as the component A.
  • R 1 is an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, or an alkenyl having 2 to 12 carbon atoms, and is X 1 and X.
  • 2 is hydrogen or fluorine;
  • Y 1 is fluorine, chlorine, cyano, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, and at least one hydrogen is replaced by fluorine or chlorine.
  • It is an alkoxy having 1 to 12 carbon atoms, or an alkenyloxy having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine.
  • Item 3 The liquid crystal composite according to Item 1 or 2, wherein the proportion of component A is in the range of 5% to 90% based on the liquid crystal composition.
  • Item 4. The liquid crystal complex 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 the formula (2) as the component B.
  • R 2 and R 3 are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or at least one hydrogen being replaced with fluorine or chlorine. It is an alkenyl having 2 to 12 carbon atoms; rings B and C are 1,4-cyclohexylene, 1,3-phenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-.
  • Z 2 is single bond, ethylene, vinylene, ethynylene, methyleneoxy, or carbonyloxy;
  • b is 1, 2, or 3 Is.
  • Item 5 The liquid crystal according to any one of Items 1 to 4, wherein the liquid crystal composition contains at least one compound selected from the compounds represented by the formulas (2-1) to (2-23) as the component B. Complex.
  • R 2 and R 3 are alkyls having 1 to 12 carbon atoms, alkoxys having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or at least one. It is an alkenyl having 2 to 12 carbon atoms in which hydrogen is replaced with fluorine or chlorine.
  • Item 6 The liquid crystal composite according to Item 4 or 5, wherein the proportion of component B is in the range of 5% to 90% based on the liquid crystal composition.
  • Item 7. The liquid crystal complex 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 the formula (3) as the component C.
  • R 4 and R 5 are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or alkenyloxy having 2 to 12 carbon atoms.
  • Rings D and F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen replaced with fluorine or chlorine.
  • ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro.
  • Z 3 and Z 4 are single-bonded, ethylene, phenylene, methyleneoxy, or carbonyloxy; c is 0, 1, 2, or 3, and d is 0 or 1. , The sum of c and d is 3 or less.
  • Item 8. The liquid crystal according to any one of Items 1 to 7, wherein the liquid crystal composition contains at least one compound selected from the compounds represented by the formulas (3-1) to (3-35) as the component C. Complex.
  • R 4 and R 5 are hydrogen, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or carbon. Numbers 2 to 12 of alkoxyoxy.
  • Item 9 The liquid crystal composite according to Item 7 or 8, wherein the proportion of the component C is in the range of 3% to 25% based on the liquid crystal composition.
  • Item 10 The liquid crystal complex according to any one of Items 1 to 9, wherein the polymer is derived from the precursor, and the main component of the precursor is a compound represented by the formula (4).
  • P 1 and P 2 are polymerizable groups;
  • Z 5 is an alkylene with 1 to 20 carbon atoms, in which at least one hydrogen is an alkyl, fluorine with 1 to 5 carbon atoms.
  • heterocyclic saturated aliphatic compounds from aliphatic compounds, heterocyclic saturated aliphatic compounds, carbocyclic unsaturated aliphatic compounds, heterocyclic unsaturated aliphatic compounds, carbocyclic aromatic compounds, or heterocyclic aromatic compounds It may be replaced with divalent groups generated by removing two hydrogens, in which the carbon number is 5 to 35 and at least one hydrogen is replaced by R 6 or P 3.
  • R 6 is alkyl having 1 to 12 carbon atoms, in the alkyl, at least one of -CH 2 -, -O -, - CO -, - COO-, or substituted with -OCO- may be
  • P 3 is a polymerizable group.
  • Item 11 The liquid crystal complex according to Item 10, wherein P 1 , P 2 , and P 3 are groups selected from the polymerizable groups represented by the formulas (P-1) to (P-6).
  • P 1 , P 2 , and P 3 are groups selected from the polymerizable groups represented by the formulas (P-1) to (P-6).
  • M 1 , M 2 , and M 3 are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen replaced with fluorine or chlorine. It is an alkyl having 1 to 5 carbon atoms.
  • Item 12. The liquid crystal complex 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 complex according to any one of Items 1 to 9, wherein the polymer is derived from the precursor, and the main component of the precursor is a compound represented by the formula (5).
  • M 4 and M 5 are hydrogen or methyl;
  • Z 6 is an alkylene with 21 to 80 carbon atoms, in which at least one hydrogen is an alkyl with 1 to 20 carbon atoms.
  • Item 14 The liquid crystal complex according to any one of Items 1 to 9, wherein the polymer is derived from the precursor, and the main component of the precursor is a compound represented by the formula (6).
  • M 6 is hydrogen or methyl
  • Z 7 is a single bond or an alkylene with 1 to 5 carbon atoms, in which 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 an alkyl having 1 to 40 carbon atoms, in which in this alkyl At least one hydrogen may be replaced with fluorine or chlorine, and at least one -CH 2- may be replaced with -O-, -CO-, -COO-, or -OCO-, at least 1
  • One -CH 2- is a carbocyclic saturated aliphatic compound, a heterocyclic saturated aliphatic compound, a carbocyclic unsaturated aliphatic compound, a heterocyclic unsaturated aliphatic compound, and a carbocyclic aromatic.
  • It may be replaced with a divalent group produced by removing two hydrogens from a group compound or an heterocyclic aromatic compound, in which the divalent group has 5 to 35 carbon atoms and at least one.
  • hydrogen may be replaced by alkyl having 1 to 12 carbon atoms, in the alkyl, at least one of -CH 2 -, -O -, - CO -, - COO-, or -OCO- in replaced May be good.
  • M 6 is hydrogen or methyl
  • Z 7 is a single bond or an alkylene with 1 to 5 carbon atoms, in which at least one hydrogen may be replaced with fluorine or chlorine.
  • At least one -CH 2- may be replaced by -O-, -CO-, -COO-, or -OCO-; in this alkyl, R 7 is an alkyl having 1 to 40 carbon atoms.
  • At least one hydrogen may be replaced with fluorine or chlorine, and at least one -CH 2- may be replaced with -O-, -CO-, -COO-, or -OCO-, item 14.
  • the liquid crystal composite according to.
  • Item 16 The item 1 to 9, wherein the polymer is derived from the precursor, and the main component of the precursor is a compound represented by the formula (7), the formula (8), or the formula (9). Liquid crystal complex.
  • 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 fluoren-2,7-diyl, where At least one hydrogen is fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl with 1 to 5 carbon atoms, alkoxy with 1 to 5 carbon atoms, alkoxycarbonyl
  • Z 8 , Z 10 , Z 12 , Z 13 and Z 17 are single-bonded, -O-, -COO-, -OCO-, or-.
  • Cyano alkyl with 1 to 20 carbons, alkenyl with 2 to 20 carbons, alkoxy with 1 to 20 carbons, or alkoxycarbonyl with 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 from 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.
  • Item 17. The liquid crystal complex according to any one of Items 1 to 16, wherein the additive A is at least one compound selected from the optically active compounds represented by the formulas (10-1) to (10-7). ..
  • Z is 1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, tetrahydropyran-3,5-diyl, pyrimidine-2, It is 5-diyl, pyridine-2,5-diyl, or bicyclo [2.2.2] octane-1,4-diyl, even if at least one hydrogen in these rings is replaced by fluorine or chlorine.
  • rings R, ring S, ring V, and ring W are 5,6,7,8-tetrahydronaphthalene-1,2-diyl or naphthalene-1,2-diyl;
  • Z 18 to Z 25 are It is a single bond or an alkylene with 1 to 20 carbon atoms, in which at least one -CH 2- may be replaced with -O-, -CO-, -COO-, or -OCO-, at least.
  • X 3 to X 8 are hydrogen or fluorine;
  • p, q, r, s, t, u, v, and w are 1, 2, or 3.
  • Item 18 The liquid crystal composite according to any one of Items 1 to 17, wherein the ratio of the additive A is in the range of 0.03% to 25% based on the liquid crystal composition.
  • Item 19 The liquid crystal composite according to any one of Items 1 to 18, wherein the liquid crystal composition has a spiral pitch of 10 ⁇ m or less.
  • Item 20 The liquid crystal composite according to any one of Items 1 to 19, wherein the liquid crystal composition contains a dichroic dye as an additive B.
  • Additive B is at least one dichroic dye selected from benzothiadiazoles, diketopyrrolopyrroles, azo compounds, and anthraquinones.
  • the liquid crystal complex according to.
  • Item 22 The liquid crystal composite according to Item 20 or 21, wherein the ratio of the additive B is in the range of 0.01% to 25% based on the liquid crystal composition.
  • Item 23 Item 2. The item 1 to 22, wherein the proportion of the polymer is in the range of 3% to 40% and the proportion of the liquid crystal composition is in the range of 97% to 60% based on the liquid crystal composite. Liquid crystal complex.
  • Item 24 Item 2. The item 1 to 22, wherein the proportion of the polymer is in the range of 10% to 70% and the proportion of the liquid crystal composition is in the range of 90% to 30% based on the liquid crystal composite. Liquid crystal complex.
  • Item 25 A liquid crystal dimming element in which the dimming layer is the liquid crystal composite according to any one of Items 1 to 24, the dimming layer is sandwiched between a pair of transparent substrates, and the transparent substrate has a transparent electrode.
  • Item 26 The liquid crystal light control element according to Item 25, wherein the transparent substrate is a glass plate or an acrylic plate.
  • Item 27 The liquid crystal light control element according to Item 25, wherein the transparent substrate is a plastic film.
  • Item 28 Weather resistance test conducted under the conditions of the liquid crystal composite according to any one of Items 1 to 24, illuminance (180 W / m 2 ), irradiation time (100 hours), and tank temperature (35 ° C.).
  • Item 2. The liquid crystal dimming element according to any one of Items 25 to 27, wherein the haze change rate before and after is 20% or less.
  • Item 29 A dimming window using the liquid crystal dimming element according to any one of items 25 to 28.
  • Item 30 A smart window using the liquid crystal dimming element according to any one of Items 25 to 28.
  • Item 31 Use of the liquid crystal composite according to any one of items 1 to 24 for a liquid crystal dimming element.
  • Item 32 Use of the liquid crystal composite according to any one of items 1 to 24 for a liquid crystal dimming element in which the transparent substrate is a plastic film.
  • Item 33 Use of the liquid crystal composite according to any one of items 1 to 24 for a dimming window.
  • Item 34 Use of the liquid crystal complex according to any one of items 1 to 24 for a smart window.
  • the present invention also includes the following items.
  • the present invention also includes the following items.
  • the liquid crystal composition contains the compound (1-1), the compound (1-2), the compound (1-3), the compound (1-9), and the compound (1-13) according to Item 2 as the component A. ), Compound (1-16), Compound (1-21), Compound (1-22), Compound (1-23), Compound (1-24), Compound (1-27), Compound (1-28) , Compound (1-36), compound (1-41), and compound (1-42), the above-mentioned liquid crystal complex containing at least one compound.
  • the present invention also includes the following items.
  • the liquid crystal composition contains the compound (2-1), the compound (2-2), the compound (2-3), the compound (2-4), and the compound (2-6) according to Item 5 as the component B. ), Compound (2-9), Compound (2-10), Compound (2-12), Compound (2-13), Compound (2-14), Compound (2-16), Compound (2-17) , Compound (2-19), and the above liquid crystal complex containing at least one compound selected from compound (2-21).
  • the present invention also includes the following items.
  • the liquid crystal composition contains the compound (3-1), the compound (3-5), the compound (3-6), the compound (3-7), and the compound (3-8) according to Item 8 as the component C. ), Compound (3-12), compound (3-14), compound (3-19), and the above liquid crystal complex containing at least one compound selected from compound (3-34).
  • the present invention also includes the following items.
  • H The above liquid crystal composite in which the proportion of the polymer is in the range of 5% to 10% and the proportion of the liquid crystal composition is in the range of 95% to 90% based on the liquid crystal composite.
  • the present invention also includes the following items.
  • K The above liquid crystal composite in which the proportion of the polymer is in the range of 30% to 40% and the proportion of the liquid crystal composition is in the range of 70% to 60% based on the liquid crystal composite.
  • the present invention also includes the following items.
  • the present invention relates to a liquid crystal composite containing a polymer and a liquid crystal composition having a chiral nematic phase, and a liquid crystal dimming device having this composite.
  • An optically active compound chiral agent
  • the chiral nematic liquid crystal composition is prepared in this way.
  • the liquid crystal composite is composed of a chiral nematic liquid crystal composition and a polymer. It seems that the types of compounds suitable as constituents of the liquid crystal complex have not been reported in the literature. We have found that certain liquid crystal complexes exhibit focal conic state, planar state, homeotropic state, etc. depending on the conditions, and are suitable for dimming devices.
  • the present invention will be described in the following order. First, the liquid crystal complex will be described. Secondly, the liquid crystal composition will be described. Third, the main properties of the liquid crystal compound and the main effect of this compound on the liquid crystal composition and the device will be described. Fourth, the combinations and preferable ratios of the liquid crystal compounds will be described. Fifth, a preferred form of the liquid crystal compound will be described. Sixth, preferred liquid crystal compounds are shown. Seventh, preferable forms of the polymerizable compound and an example thereof will be described. Eighth, preferred forms of optically active compounds and examples thereof will be described. Ninth, a method for synthesizing a component compound will be described. Tenth, additives that may be added to the polymerizable composition will be described. Finally, the liquid crystal dimming element will be described.
  • the precursor of the liquid crystal complex is a polymerizable composition.
  • the liquid crystal composite is produced by the polymerization of the polymerizable composition.
  • the polymerizable composition is a mixture of the polymerizable compound and the liquid crystal composition.
  • An optically active compound is added to the liquid crystal composition as an additive A.
  • the polymerizable composition is placed in the device and polymerized.
  • the polymer produced by the polymerization is phase-separated to give a liquid crystal composite.
  • Devices having a liquid crystal composite are classified into a polymer support orientation type, a polymer network type, and a polymer dispersion type according to the proportion of the polymer.
  • PSA element When the proportion of polymer is small, a polymer-sustained alignment element is generated. This is abbreviated as PSA element.
  • the monomer was added so as to be 0.5 wt% with respect to the liquid crystal material" (paragraph 0105).
  • the PSA device a small amount of the polymerizable compound is added to the liquid crystal material (liquid crystal composition).
  • the polymer adjusts the pretilt angle of the liquid crystal molecules. By optimizing the pretilt angle, the liquid crystal molecules are stabilized and the response time of the device is shortened.
  • the liquid crystal composition is dispersed like droplets in the polymer. Each droplet is microencapsulated and not contiguous.
  • the liquid crystal molecules are in a random state because they are arranged along the inner wall of the capsule. Since the refractive index of the polymer and the refractive index of the liquid crystal molecules are different, the incident light is scattered. The element is opaque. When a voltage is applied to the device, the refractive index of the liquid crystal molecules changes. When this refractive index becomes the same as the refractive index of the polymer, the incident light passes through the device and the device becomes transparent.
  • the proportion of polymer is medium, polymer network type devices are generated.
  • the polymer has a three-dimensional network structure, and the liquid crystal composition is surrounded by this network but continuous.
  • the liquid crystal molecules are in a random state and the device is opaque.
  • the liquid crystal molecules are arranged in the electric field direction, so that the device becomes transparent.
  • the proportion of the liquid crystal composition based on the liquid crystal composite is preferably large in order to efficiently scatter light.
  • the proportion of the polymer is preferably small from the viewpoint of low drive voltage.
  • Response times are short when droplets and meshes are small. Therefore, the proportion of the polymer is preferably large from the viewpoint of short response time.
  • the preferred proportion of the polymer is in the range of about 3% to about 40% based on the liquid crystal composite in order to scatter the incident light.
  • a more preferred ratio is in the range of about 4% to about 20% based on the liquid crystal complex.
  • a particularly preferred proportion is in the range of about 5% to about 10% based on the liquid crystal complex. Since the total of the polymer and the liquid crystal composition is 100%, the ratio of the liquid crystal composition can be easily calculated.
  • the proportion of the polymer based on the liquid crystal composite is the same as the proportion of the polymerizable compound based on the polymerizable composition.
  • the preferred proportion of the polymer is in the range of about 10% to about 70% based on the liquid crystal composite in order to increase the adhesiveness between the light control layer (liquid crystal composite) and the substrate.
  • a more preferred ratio is in the range of about 20% to about 60% based on the liquid crystal complex.
  • a particularly preferred ratio is in the range of about 30% to about 40% based on the liquid crystal complex.
  • a polymer network type element or a polymer dispersion type element is generated.
  • the polymer network type and the polymer dispersed type seem to coexist. Unlike the PSA element, these elements do not require a polarizing plate.
  • alignment films are used as needed.
  • 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. Devices manufactured by these methods may have display defects such as flow marks and dripping marks. A flow mark is a mark of the polymerizable composition flowing through the device. The dropping marks are marks on which the polymerizable composition is dropped. It is preferable that such display defects are suppressed. The polymerizable compound is then polymerized by heat or light. Ultraviolet irradiation is preferable for the polymerization. The polymer is phase-separated from the polymerizable composition by polymerization. As a result, a dimming layer (liquid crystal composite) is formed between the substrates.
  • a dimming layer liquid crystal composite
  • This composition contains a plurality of liquid crystal compounds.
  • This composition may contain additives. Additives include optically active compounds, antioxidants, UV 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 liquid crystal compounds.
  • the composition A may further contain other liquid crystal compounds, additives and the like in addition to the liquid crystal compound 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 is substantially composed of only a liquid crystal compound selected from compound (1), compound (2), and compound (3). "Substantially" means that composition B may contain additives but does not contain other liquid crystal compounds.
  • the composition B has a smaller number of components than the composition A.
  • the composition B is preferable to the composition A from the viewpoint of reducing the cost.
  • Composition A is preferable to composition B from the viewpoint that the properties can be further adjusted by mixing other liquid crystal compounds.
  • Compound (1) increases the dielectric anisotropy.
  • Compound (2) raises the upper limit temperature or lowers the lower limit temperature.
  • Compound (3) increases the dielectric constant of the liquid crystal molecule in the minor axis direction.
  • a preferred combination is component A + component B, component A + component C, or component A + component B + component C.
  • a more preferable combination is component A + component B, or component A + component B + component C.
  • a specific one or two compounds selected from the component A may be combined with the component B (or component C). The same applies to component B and component C.
  • the preferable ratio of the component A is about 5% or more in order to increase the dielectric anisotropy, and about 90% or less in order to lower the lower limit temperature. More preferred proportions range from about 10% to about 85%. A particularly preferred ratio is in the range of about 20% to about 80%.
  • the preferable ratio of the component B is about 5% or more for raising the upper limit temperature or lowering the lower limit temperature, and about 90% or less for raising the dielectric anisotropy. More preferred proportions range from about 10% to about 85%. A particularly preferred ratio is in the range of about 20% to about 80%.
  • the preferable ratio of the component C is about 3% or more in order to increase the dielectric constant of the liquid crystal molecule in the minor axis direction, and about 25% or less in order to lower the lower limit temperature. More preferred proportions range from about 5% to about 20%. A particularly preferred ratio is in the range of about 5% to about 15%.
  • R 1 is an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, or an alkenyl having 2 to 12 carbon atoms.
  • Preferred R 1 is an alkyl having 1 to 12 carbon atoms for increased stability against light and heat.
  • R 2 and R 3 are alkyls with 1 to 12 carbons, alkoxys with 1 to 12 carbons, alkenyl with 2 to 12 carbons, or 2 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine. It is alkenyl.
  • Preferred R 2 or R 3 is an alkenyl having 2 to 12 carbon atoms to raise or lower the upper and lower temperature limits, and an alkyl having 1 to 12 carbon atoms to increase stability to light and heat.
  • R 4 and R 5 are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or alkenyloxy having 2 to 12 carbon atoms.
  • Preferred R 4 or R 5 is an alkyl having 1 to 12 carbon atoms to increase the stability against light and heat, and an alkoxy having 1 to 12 carbon atoms to increase the dielectric constant of the liquid crystal molecule in the minor axis direction. ..
  • Preferred alkyls are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. More preferred alkyls are methyl, ethyl, propyl, butyl, or pentyl to reduce viscosity.
  • Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. More preferred alkoxys for reducing viscosity are methoxy or ethoxy.
  • Preferred alkenyls are 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 preferred alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl to reduce the viscosity.
  • Trans is preferable in alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl for the purpose of lowering the viscosity.
  • Sith is preferred for alkenyl such as 2-butenyl, 2-pentenyl, 2-hexenyl.
  • Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. More preferred alkenyloxy to reduce viscosity are allyloxy or 3-butenyloxy.
  • alkyl in which at least one hydrogen is replaced with fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl. , Or 8-fluorooctyl. More preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl to increase the dielectric anisotropy.
  • alkenyl in which at least one hydrogen is replaced with fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro. -4-pentenyl, or 6,6-difluoro-5-hexenyl. More preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl to reduce 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.
  • Preferred ring A is 1,4-phenylene or 2-fluoro-1,4-phenylene to increase the optical anisotropy.
  • the configuration for 1,4-cyclohexylene is preferably trans over cis in order to raise the upper temperature limit. Tetrahydropyran-2,5-diyl is Or And preferably Is.
  • Rings B and 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-Zile.
  • Preferred ring B or ring C is 1,4-cyclohexylene to raise the upper limit temperature or lower the lower limit temperature, and 1,4-phenylene to lower the lower limit temperature.
  • Rings D and F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen replaced with fluorine or chlorine 1 , 4-Phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine, chromane-2,6-diyl, or at least one hydrogen is fluorine or chlorine. Chroman-2,6-jiyl replaced by.
  • Preferred ring D or ring F is 1,4-cyclohexylene to lower the lower limit temperature or to raise the upper limit temperature, and 1,4-phenylene to lower the lower limit 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.
  • the preferred ring E is 2,3-difluoro-1,4-phenylene to reduce the viscosity and 4,6-difluorodibenzothiophene-3,7-diyl to increase the dielectric constant of the liquid crystal molecule in the minor axis direction. Is.
  • Z 1 is a single bond, ethylene, vinylene, ethynylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy.
  • Preferred Z 1 is a single bond to raise the upper temperature limit and difluoromethyleneoxy to raise 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 for increased stability to light and heat.
  • Z 3 and Z 4 are single bonds, ethylene, vinylene, methyleneoxy, or carbonyloxy.
  • Preferred Z 3 or Z 4 is a single bond to reduce the viscosity, ethylene to lower the lower limit temperature, and methyleneoxy to increase the permittivity of the liquid crystal molecule in the minor axis direction.
  • a particularly preferred Z 3 or Z 4 is a single bond.
  • Divalent groups such as methyleneoxy are asymmetrical. In methyleneoxy, -CH 2 O- is preferable to -OCH 2- . In carbonyloxy, -COO- is preferred over -OCO-. In difluoromethyleneoxy, -CF 2 O- is preferred over -OCF 2- .
  • A is 1, 2, 3, or 4.
  • Preferred a is 2 for lowering the lower limit temperature and 3 for increasing the dielectric anisotropy.
  • b is 1, 2, or 3.
  • Preferred b is 1 to lower the lower limit temperature and 2 or 3 to raise the upper limit temperature.
  • c is 0, 1, 2, or 3, d is 0 or 1, and the sum of c and d is 3 or less.
  • the preferred c is 1 for lowering the lower limit temperature and 2 or 3 for raising the upper limit temperature.
  • Preferred d is 0 to lower the viscosity and 1 to lower the lower limit temperature.
  • X 1 and X 2 are hydrogen or fluorine.
  • Preferred X 1 or X 2 is hydrogen to raise the upper temperature limit and fluorine to raise the dielectric anisotropy.
  • Y 1 is fluorine, chlorine, cyano, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, and an alkoxy having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine.
  • at least one hydrogen is an alkenyloxy having 2 to 12 carbon atoms in which fluorine or chlorine is replaced.
  • Preferred Y 1 is fluorine to reduce the viscosity and cyano to increase the dielectric anisotropy.
  • a preferred example of an alkyl in which at least one hydrogen has been replaced with fluorine or chlorine is trifluoromethyl.
  • a preferred example of an alkoxy in which at least one hydrogen has been replaced with 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 compounds (1) are compounds (1-1) to compounds (1-47) according to Item 2.
  • at least one of the components A 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- 33), compound (1-34), compound (1-41), or compound (1-42) is preferred.
  • At least two of the components A are compound (1-1) and compound (1-2), compound (1-1) and compound (1-9), compound (1-2) and compound (1-9), compound.
  • the preferable compound (2) is the compound (2-1) to the compound (2-23) according to Item 5.
  • at least one of the components B 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).
  • At least two of component B are compound (2-2) and compound (2-9), compound (2-2) and compound (2-10), compound (2-2) and compound (2-12), compound. It is preferably a combination of (2-9) and compound (2-10), compound (2-9) and compound (2-12), or compound (2-10) and compound (2-12).
  • Preferred compounds (3) are compounds (3-1) to compounds (3-35) according to Item 8.
  • at least one of the components C is compound (3-1), compound (3-3), compound (3-6), compound (3-8), compound (3-10), compound (3). -14) or compound (3-34) is preferred.
  • At least two of the components C 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 ( 3-10), or a combination of compound (3-6) and compound (3-14) is preferred.
  • a polymer is derived from the polymerizable compound by polymerization.
  • the precursor of the polymer is a polymerizable compound.
  • the polymerizable compound may be a single compound or a mixture of a plurality of compounds.
  • Preferred polymerizable compounds are compound (4), compound (5), or compound (6).
  • Preferred polymerizable compounds are compound (7), compound (8), or compound (9).
  • the polymerizable compound may be a mixture of compounds selected from compound (4) to compound (9). This mixture may contain a polymerizable compound different from compound (4) to compound (9).
  • Such a mixture contains compound (4), compound (5), or compound (6) as a main component.
  • Such a mixture contains compound (7), compound (8), or compound (9) as a main component.
  • Z 5 is an alkylene having 1 to 20 carbon atoms, in which at least one hydrogen may be replaced with an alkyl, fluorine, chlorine, or P 3 having 1 to 5 carbon atoms.
  • At least one -CH 2- may be replaced with -O-, -CO-, -COO-, -OCO-, -NH-, or -N (R 6 )-and at least one -CH.
  • the number of carbon atoms is 5 to 35, and at least one hydrogen may be replaced with R 6 or P 3 .
  • R 6 is an alkyl having 1 to 12 carbon atoms, in which at least one -CH 2- can be replaced with -O-, -CO-, -COO-, or -OCO-. Good.
  • divalent groups produced by removing two hydrogens from a carbocyclic or heterocyclic saturated aliphatic compound are 1,4-cyclohexylene, decahydronaphthalene-2,6-diyl, tetrahydropyran-2. , 5-Diyl, 1,3-dioxane-2,5-Diyl, etc.
  • divalent groups produced by removing two hydrogens from a carbocyclic or heterocyclic unsaturated aliphatic compound include 1,4-cyclohexenylene, dihydropyran-2,5-diyl and the like.
  • divalent groups produced 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 an alkylene having 1 to 20 carbon atoms, in which at least one hydrogen may be replaced with an alkyl having 1 to 5 carbon atoms, and at least one -CH 2- is -O. May be replaced with-at least one -CH 2- is replaced with a divalent group produced by removing two hydrogens from a carbocyclic saturated aliphatic compound or a carbocyclic aromatic compound. Often, these divalent groups have 5 to 35 carbon atoms.
  • a more preferred Z 5 is an alkylene having 1 to 20 carbon atoms, in which at least one hydrogen may be replaced by an alkyl having 1 to 5 carbon atoms, where at least one -CH 2- It may be replaced with O-.
  • Preferred Z 5 contains a ring structure such as 1,4-cyclohexylene or 1,4-phenylene in order to increase compatibility with the liquid crystal composition.
  • Preferred Z 5 contains a alkylene-like chain structure for easy formation of the network structure.
  • P 1 , P 2 , and P 3 are polymerizable groups.
  • Preferred polymerizable groups are formulas (P-1) to (P-6). In these equations, the wavy lines indicate the coupling positions. More preferable 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 hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen replaced with fluorine or chlorine. It is an alkyl having 1 to 5 carbon atoms.
  • Preferred M 1 , M 2 , or M 3 is hydrogen or methyl to increase reactivity. The more preferred M 1 is hydrogen or methyl, and the more preferred M 2 or M 3 is hydrogen.
  • the polymer surrounding the droplets becomes hard due to cross-linking, or the network of the polymer becomes dense.
  • Compound (4) gives the corresponding polymer by polymerization. If 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 lowers the drive voltage. In order to improve this effect, 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 to increase reactivity.
  • Preferred Z 6 is an alkylene having 21 to 60 carbon atoms for low voltage drive, in which at least one hydrogen may be replaced with an alkyl having 1 to 20 carbon atoms and at least one-.
  • CH 2- may be replaced by -O-, -COO-, or -OCO-.
  • a more preferred Z 6 is an alkylene in which at least one hydrogen is replaced by an alkyl for low voltage drive. It is preferable to avoid steric hindrance when the two hydrogens of the alkylene are replaced by alkyl.
  • the two alkyls are sufficiently separated, or one of the alkyls is an alkyl having 1 to 5 carbon atoms. The same is true when at least three hydrogens are replaced by alkyl.
  • R 8 and R 10 are alkyls having 1 to 5 carbon atoms
  • R 9 and R 11 are alkyls having 5 to 20 carbon atoms, in which at least one ⁇ CH 2- may be replaced by -O-, -CO-, -COO-, or -OCO-
  • Z 8 is an alkylene with 10 to 30 carbon atoms and at least one -CH in this alkylene.
  • 2- may be replaced by -O-, -CO-, -COO-, or -OCO-.
  • R 8 and R 10 are ethyls
  • R 9 and R 11 are -CH 2 OCOC 9 H 19 , -CH 2.
  • Compound (5) is diacrylate or dimethacrylate. Since Z 6 of the formula (5) is alkylene or the like, the polymer tends to form a network structure. When the molecular chain of Z 6 is short, the cross-linked sites of the polymer are close to each other, so that the network becomes smaller. 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 the Z 6 is branched, the degree of freedom is further improved, so that the drive 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 to increase reactivity.
  • Z 7 is a single bond or an alkylene with 1 to 5 carbon atoms, in which at least one hydrogen may be replaced with fluorine or chlorine, and at least one -CH 2- is -O-,-. It may be replaced by CO-, -COO-, or -OCO-.
  • Preferred Z 7 is alkylene of 5 a single bond or 1 carbon atoms, in the alkylene, at least one of -CH 2 -, -O -, - CO -, - COO-, or replaced by -OCO- You may.
  • R 7 is an alkyl having 1 to 40 carbon atoms, in which at least one hydrogen may be replaced with fluorine or chlorine, and at least one -CH 2- is -O-, -CO-, It may be replaced with -COO- or -OCO-, and at least one -CH 2- is a carbocyclic saturated aliphatic compound, a heterocyclic saturated aliphatic compound, or a carbocyclic unsaturated aliphatic compound. They may be replaced by compounds, heterocyclic unsaturated aliphatic compounds, carbocyclic aromatic compounds, or divalent groups generated by removing two hydrogens from heterocyclic aromatic compounds.
  • the number of carbon atoms is 5 to 35, and at least one hydrogen may be replaced with an alkyl having 1 to 12 carbon atoms, in which at least one -CH 2- is -O-. , -CO-, -COO-, or -OCO- may be replaced.
  • Preferred R 7 is an alkyl having 5 to 30 carbon atoms. A more preferred R 7 is a branched alkyl having 5 to 30 carbon atoms.
  • R 12 is an alkyl having 5 to 20 carbon atoms, in which at least one -CH 2- is -O-, -CO-, May be replaced with -COO-, or -OCO-, where R 13 and R 14 are alkyls with 3 to 10 carbon atoms, in which at least one -CH 2- is -O-,-. It may be replaced by CO-, -COO-, or -OCO-.
  • Compound (6) is acrylate or methacrylate.
  • R 7 of the formula (6) has a cyclic structure, the affinity with the liquid crystal composition is improved.
  • R 7 is alkylene, the polymer tends to form a network structure. In this polymer, the alkylene increases 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 with 1 to 5 carbons, alkoxy with 1 to 5 carbons, alkoxycarbonyl with 2 to 5 carbons.
  • the 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. More preferred rings are 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 single bonds, -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 are single bonds or —O—.
  • Preferred Z 9 , Z 11 , Z 14 or Z 16 are single bonds, -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 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, or 2 to 20 carbon atoms. 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 and the sum of k and m is from 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.
  • M 7 is hydrogen or methyl and e is an integer from 1 to 20.
  • M 8 and M 9 are hydrogen or methyl, and g and i are integers from 1 to 20.
  • 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 oriented in the same direction together with the liquid crystal compound by the action of the alignment film. This orientation is maintained after polymerization. Such a liquid crystal composite has high transparency.
  • compound (7), compound (8), and a polymerizable compound different from compound (9) may be used in combination.
  • the optically active compound is also used in a TN mode liquid crystal display device.
  • the two substrates have an alignment film.
  • the substrate is placed by rotating the rubbing direction by 90 degrees.
  • the optically active compound is added so that the arrangement of the liquid crystal molecules is twisted by 90 degrees between the substrates.
  • the spiral pitch is much larger than 10 ⁇ m.
  • the spiral pitch of the liquid crystal light control element is 10 ⁇ m or less.
  • the spiral pitch is reduced by increasing the amount of optically active compound. Therefore, the optically active compound preferably has high compatibility with the composition.
  • Preferred optically active compounds are compounds (10-1) to compounds (10-7).
  • the structure of these compounds is similar to that of liquid crystal compounds. These compounds are preferred from the standpoint of large compatibility and small helical pitch.
  • Compound (10-4) and compound (10-5) have axial chirality.
  • Compound (10-6) has an asymmetric carbon.
  • Ring N, Ring P, Ring Q, Ring T, Ring U, Ring X, Ring Y, and Ring Z are 1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl. , Tetrahydropyran-2,5-diyl, tetrahydropyran-3,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, or bicyclo [2.2.2] octane-1,4- It is a dioxane, in which at least one hydrogen may be replaced with fluorine or chlorine.
  • Preferred ring N, ring P, ring Q, ring T, ring U, ring X, ring Y, or ring Z is 1,4-cyclohexylene or 1,4-phenylene.
  • Rings R, S, V, and W are 5,6,7,8-tetrahydronaphthalene-1,2-diyl or naphthalene-1,2-diyl.
  • the preferred ring R, ring S, ring V, or ring W is 5,6,7,8-tetrahydronaphthalene-1,2-diyl.
  • Preferred Z 18 to Z 25 are single bonds, alkylenes having 1 to 20 carbon atoms, or 1 to 20 carbon atoms in which at least one -CH 2- has been replaced with -O-, -COO-, or -OCO-. It is alkylene. More preferred Z 18 to Z 25 are single bonds, -OCH 2- , -COO-, or -OCO-.
  • X 3 to X 8 are hydrogen or fluorine. Preferred X 3 to X 8 are fluorine to increase HTP (helical twisting power).
  • P, q, r, s, t, u, v, and w are 1, 2, or 3.
  • Preferred p, q, r, s, t, u, v, or w is 2 or 3.
  • the preferred proportion of the optically active compound is in the range of about 0.03% to about 25%, based on the liquid crystal composition. A more preferred ratio is in the range of about 0.03% to about 20%. A particularly preferred ratio is in the range of about 0.03% to about 15%.
  • the preferred spiral pitch in the liquid crystal composition is 10 ⁇ m or less. A more preferable spiral pitch is 5 ⁇ m or less. A particularly preferable spiral pitch is 3 ⁇ m or less.
  • additives that may be added to the polymerizable composition will be described.
  • additives include antioxidants, UV absorbers, quenchers, dyes, defoamers, polymerization initiators, polymerization inhibitors, polar compounds and the like.
  • Additives may be added to the liquid crystal composition or the polymerizable compound instead of the polymerizable composition.
  • the compound (11-1) In order to prevent a decrease in resistivity due to heating in the atmosphere, or to maintain a large voltage retention not only at room temperature but also at a temperature close to the upper limit temperature after using the device for a long time, the compound (11-1) ) To an antioxidant such as compound (11-3) may be added to the composition.
  • An ultraviolet absorber may be added to the composition in order to prevent deterioration due to ultraviolet rays.
  • a compound having low volatility is effective in maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after the device has been used for a long time.
  • the preferable ratio of the antioxidant is about 50 ppm or more in order to obtain the effect, and is about 600 ppm or less so as not to lower the upper limit temperature or raise the lower limit temperature.
  • a more preferred ratio is in the range of about 100 ppm to about 300 ppm.
  • UV absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like.
  • Light stabilizers such as amines with steric hindrance are also preferred.
  • Preferred examples of light stabilizers are compounds (12-1) to compounds (12-16).
  • the preferable ratio of these absorbents and stabilizers is about 50 ppm or more in order to obtain the effect, and about 10,000 ppm or less so as not to lower the upper limit temperature or raise the lower limit temperature. A more preferred ratio is in the range of about 100 ppm to about 10000 ppm.
  • the quencher is a compound that prevents the decomposition of the liquid crystal compound by receiving the light energy absorbed by the liquid crystal compound and converting it into heat energy.
  • Preferred examples of the quencher are compounds (13-1) to compounds (13-7) and the like.
  • the preferable ratio of these quenchers is about 50 ppm or more in order to obtain the effect, and about 20000 ppm or less in order not to raise the lower limit temperature. A more preferred ratio is in the range of about 100 ppm to about 10000 ppm.
  • a dichroic dye is added to the composition to accommodate elements in GH (guest host) mode.
  • Liquid crystal dimming elements are sometimes used to partition rooms.
  • a dye is added to the polymerizable composition for the purpose of absorbing specific light. Multiple dyes may be added.
  • Liquid crystal dimming elements are sometimes used to block sunlight.
  • a black (or darkish) dichroic dye is added to the liquid crystal composition. Black color is prepared by mixing cyan, magenta, and yellow dichroic pigments.
  • Japanese Patent Laying-Open No. 2006-193742, Example 42 describes a black dichroic dye. This dye is prepared by mixing three azo compounds with anthraquinones.
  • bicolor dyes examples include benzothiadiazoles, diketopyrrolopyrroles, azo compounds, azomethine compounds, methine compounds, anthraquinones. , Merocyanines, naphthoquinones, tetrazines, pyrromethenes, and reylenes such as perylenes and terrylenes.
  • Such a dichroic dye has at least some of the following characteristics. a) The dye molecule is linear. b) In the central part of the molecule, there is a skeleton peculiar to dichroic dyes such as benzothiadiazole ring and diketopyrrolopyrrole ring. c) The benzene ring and thiophene ring that form the molecule together with the unique skeleton are located on the same plane. d) The side chain is alkyl or alkoxy. e) It has a conjugated double bond in the center.
  • Preferred dichroic dyes are benzothiadiazoles, diketopyrrolopyrroles, azo compounds, anthraquinones, and lilenes.
  • Particularly preferred dichroic dyes are benzothiadiazoles, diketopyrrolopyrroles, azo compounds, and lilenes.
  • the skeletons of these four types of pigments are shown below.
  • benzothiadiazoles mean a dichroic dye having a benzothiadiazole ring.
  • 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., Ltd. 1366, NKX-3538, NKX-3540, NKX-3622, NKX-3739, NKX-3742, NKX-3737, NKX-4010, and NKX-4033; S-428, SI-426, SI- of Mitsui Chemicals Fine Co., Ltd. 486, M-412, and M-483.
  • the preferred proportion of the dichroic dye is in the range of about 0.01% to about 25%, based on the liquid crystal composition. A more preferred ratio is in the range of about 0.02% to about 20%. A particularly preferred ratio is in the range of about 0.03% to about 15%.
  • a defoaming agent such as dimethyl silicone oil or methyl phenyl silicone oil is added to the composition.
  • the preferable ratio of the defoaming agent is about 1 ppm or more in order to obtain the effect, and about 1000 ppm or less in order to prevent display defects. A more preferred ratio is in the range of about 1 ppm to about 500 ppm.
  • Ultraviolet irradiation is preferable for the polymerization of the polymerizable compound.
  • Examples of ultraviolet irradiation lamps are metal halide lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, 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.
  • the preferred wavelength is 330 nm or higher.
  • a more preferable wavelength is 350 nm or more, for example, 365 nm.
  • the reaction may be carried out near room temperature or may be carried out by heating.
  • Polymerization may be carried out in the presence of a polymerization initiator such as a photopolymerization initiator.
  • a polymerization initiator such as a photopolymerization initiator.
  • suitable conditions for polymerization and suitable types and amounts of initiators are known to those of skill in the art and are described in the literature.
  • the photopolymerization initiators Irgacure651®, Irgacure184® (registered trademark; BASF), or Darocur1173® are suitable for radical polymerization.
  • a polymerization inhibitor When storing the 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.
  • polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine and the like.
  • a polar compound is an organic compound having polarity.
  • Compounds having an ionic bond are not included here. Atoms such as oxygen, sulfur, and nitrogen are more electrically negative and tend to have partial negative charges. Carbon and hydrogen tend to be neutral or have a partially positive charge. Polarity arises from the uneven distribution of partial charges between different atoms in a compound.
  • polar compounds have at least one of the substructures such as -OH, -COOH, -SH, -NH 2 ,>NH,> N-.
  • the polar group has a non-covalent interaction with the surface of a glass substrate, a metal oxide film, or the like.
  • the polar compound is adsorbed on the surface of the substrate by the action of the polar group and controls the orientation of the liquid crystal molecules.
  • Polar compounds may control not only liquid crystal molecules but also polymerizable compounds. Such effects are expected for polar compounds.
  • the nematic composition is a mixture of rod-shaped liquid crystal compounds.
  • the chiral nematic composition is prepared by adding an optically active compound (chiral agent) to the nematic composition.
  • the liquid crystal molecule is given a right-handed twist or a left-handed twist by the action of the optically active compound, and becomes a focal conic state.
  • the liquid crystal molecules are arranged in layers, and the directions of the liquid crystal molecules in each layer are twisted in a spiral shape.
  • the axis of twist in this spiral structure is called the helical axis.
  • the length of one cycle in the spiral structure is called the spiral pitch.
  • the focal conic state is an aggregate of such small regions, and the direction of the helical axis is random.
  • FIG. 1 shows a dimming element in normal mode.
  • the dimming layer liquid crystal composite
  • the triangle liquid crystal molecule
  • the curve shows the network of the polymer.
  • the vertical bar liquid crystal molecule
  • a polymerizable composition is prepared by mixing a polymerizable compound with the composition in a focal conic state.
  • This composition is placed in a display device.
  • This device has an ITO electrode.
  • This device is not oriented.
  • a polymerization reaction is carried out by irradiating this element with ultraviolet rays while applying a voltage to produce an element having a liquid crystal composite.
  • the device is opaque because the light is scattered.
  • the liquid crystal molecules shift from the focal conic state to the homeotropic state. Since light is transmitted, the element is transparent. By removing the voltage, the homeotropic state returns to the focal conic state.
  • FIG. 2 shows a dimming element in reverse mode.
  • This device differs from the device of FIG. 1 in that it has a homogeneous alignment film.
  • the liquid crystal molecule is in a planar state due to the action of the alignment film.
  • the element is transparent.
  • the liquid crystal molecules shift to the focal conic state.
  • the device becomes opaque due to light scattering.
  • the focal conic state returns to the planer state.
  • the device may change over time due to long-term use.
  • the haze rate may change compared to the initial stage.
  • the change in the haze rate is preferably small.
  • the haze change rate is preferably 20% or less.
  • a more preferable haze change rate is 10% or less.
  • a particularly preferable haze change rate is 5% or less.
  • the haze change rate is an important factor in the long life of the liquid crystal light control element.
  • the weather resistance of this device it is preferable that the haze change rate before and after that is small.
  • flicker may occur on the display screen. It is presumed that this flicker is related to image burn-in and is caused by a difference between the potential of the positive frame and the potential of the negative frame when the element is driven by alternating current.
  • the flicker rate (%) can be expressed by (
  • the flicker rate of the device is preferably in the range of 0% to 1%.
  • the brightness may partially decrease.
  • An example of such a display defect is a line afterimage. This is a phenomenon in which the brightness between the electrodes is reduced in a streak shape by repeatedly applying different voltages to two adjacent electrodes. It is presumed that this phenomenon is caused by the accumulation of ionic impurities contained in the liquid crystal composition near the electrodes.
  • Such a dimming element has a dimming layer (liquid crystal composite) sandwiched between a pair of transparent substrates having transparent electrodes.
  • a substrate is a material that is not easily deformed, such as a glass plate, a quartz plate, and an acrylic plate.
  • a flexible transparent plastic film such as an acrylic film, a polycarbonate film.
  • one of the substrates may be an opaque material such as silicon resin.
  • This substrate may have a transparent electrode on it. Examples of transparent electrodes are tin-doped indium oxide (ITO) and conductive polymers. This substrate may have an alignment film on the transparent electrode.
  • a thin film such as polyimide or polyvinyl alcohol is suitable for the alignment film.
  • the polyimide alignment film can be obtained by applying a polyimide resin composition on a transparent substrate, heat-curing it at a temperature of about 180 ° C. or higher, and rubbing it with a cotton cloth or rayon cloth, if necessary.
  • the pair of substrates face each other so that the transparent electrode layer is on the inside.
  • Spacers may be inserted 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 dimming layer is from about 2 ⁇ m to about 50 ⁇ m, more preferably from about 5 ⁇ m to about 20 ⁇ m.
  • a general-purpose sealant can be used to bond the pair of substrates together.
  • An example of a sealant is an epoxy thermosetting composition.
  • a light absorption layer, a diffuse reflector, or the like can be arranged on the back surface of the element, if necessary.
  • Functions such as specular reflection, diffuse reflection, retroreflective reflection, and hologram reflection can also be added.
  • Such an element has a function as a light control film or a 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 and for partitioning the conference room from the corridor. That is, there are applications such as electronic blinds, dimming windows, and smart windows. Further, 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 present invention is not limited to these examples.
  • the composition (M1), the composition (M2), and the like are described.
  • the mixture of the composition (M1) and the composition (M2) is not described. However, this mixture is also considered to be disclosed. Mixtures of at least two compositions selected from the examples are also considered to be disclosed. It is reasonable to consider that a liquid crystal complex containing a mixture of these and a liquid crystal dimming device having this complex belong to the present invention and have the effect of the present invention.
  • the synthesized compound was identified by a method such as NMR analysis.
  • the properties of the compound, composition and device were measured by the following methods.
  • NMR analysis A DRX-500 manufactured by Bruker Biospin was used for the measurement. 1 In the 1 H-NMR measurement, the sample was dissolved in a deuterated solvent such as CDCl 3, and the measurement was carried out at room temperature under the conditions of 500 MHz and 16 times of integration. Tetramethylsilane was used as an internal standard. 19 In the F-NMR measurement, CFCl 3 was used as an internal standard, and the number of integrations was 24. In the description of the nuclear magnetic resonance spectrum, s is singlet, d is doublet, t is triplet, q is quartet, quin is quintet, sex is sextet, m is multiplet, and br is broad.
  • a GC-14B type gas chromatograph manufactured by Shimadzu Corporation was used for the measurement.
  • the carrier gas is helium (2 mL / min).
  • the sample vaporization chamber was set to 280 ° C. and the detector (FID) was set to 300 ° C.
  • a capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m; fixed liquid phase was dimethylpolysiloxane; non-polar) manufactured by Agilent Technologies Inc. was used for separation of the component compounds.
  • the column was held at 200 ° C. for 2 minutes and then warmed to 280 ° C. at a rate of 5 ° C./min.
  • the sample was prepared in an acetone solution (0.1%), and then 1 ⁇ L thereof was injected into the sample vaporization chamber.
  • the recorder is a C-R5A type Chromatopac manufactured by Shimadzu Corporation or an equivalent product thereof.
  • the resulting gas chromatogram showed the peak retention time and peak area corresponding to the constituent compounds.
  • Chloroform, hexane or the like may be used as the solvent for diluting the sample.
  • the following capillary columns may be used to separate the constituent compounds.
  • HP-1 length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m
  • Rtx-1 length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m
  • BP-1 manufactured by SGE International Pty. Ltd (length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m).
  • a capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 ⁇ m) manufactured by Shimadzu Corporation may be used for the purpose of preventing overlapping of compound peaks.
  • the proportion of the liquid crystal compound contained in the composition may be calculated by the following method.
  • a mixture of liquid crystal compounds is analyzed by gas chromatography (FID).
  • the area ratio of peaks in the gas chromatogram corresponds to the proportion of liquid crystal compounds.
  • the correction coefficient of each liquid crystal compound may be regarded as 1. Therefore, the proportion of the liquid crystal compound can be calculated from the area ratio of the peak.
  • Measurement sample When measuring the characteristics of the composition and the device having this composition, the composition was used as it was as a sample.
  • a sample for measurement was prepared by mixing this compound (15%) with the mother liquid crystal (85%). From the values obtained by the measurement, the characteristic values of the compound were calculated by the extrapolation method.
  • (Extrapolated value) ⁇ (Measured value of sample) ⁇ 0.85 ⁇ (Measured value of mother liquid crystal) ⁇ /0.15.
  • the smectic phase (or crystal) was precipitated at 25 ° C. at this ratio, the ratio of the compound and the mother liquid crystal was changed in the order of 10%: 90%, 5%: 95%, 1%: 99%.
  • the values of upper temperature, optical anisotropy, viscosity, and permittivity anisotropy for the compound were determined by this extrapolation method.
  • Measurement method The characteristics were measured by the following method. Many of these are methods described in the JEITA standard (JEITA ED-2521B) deliberated and enacted by the Japan Electronics and Information Technology Industries Association (JEITA), or a modified method. Met. A thin film transistor (TFT) was not attached to the TN (twisted nematic) element used for the measurement.
  • TFT thin film transistor
  • Upper limit temperature of nematic phase (NI; ° C.): A sample was placed on a hot plate of a melting point measuring device equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature at which a part of the sample changed from the nematic phase to the isotropic liquid was measured.
  • the upper limit temperature of the nematic phase may be abbreviated as "upper limit temperature”.
  • T C Minimum Temperature of a Nematic Phase
  • Viscosity Bulk viscosity; ⁇ ; measured at 20 ° C.; mPa ⁇ s: An E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used for the measurement.
  • Viscosity (rotational viscosity; ⁇ 1; measured at 25 ° C; mPa ⁇ s): The measurement is performed by 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 the two glass substrates of 5 ⁇ m. A stepwise application was applied to this device in 0.5 V increments in the range of 16 V to 19.5 V. After no application for 0.2 seconds, application was repeated under the conditions of only one square wave (rectangular pulse; 0.2 seconds) and no application (2 seconds).
  • the peak current (peak current) and peak time (peak time) of the transient current (transient current) generated by this application were measured.
  • the value of rotational viscosity 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 required for this calculation was obtained by the method described below using the device whose rotational viscosity was measured.
  • Threshold voltage (Vth; measured at 25 ° C.; V): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement.
  • the light source was a halogen lamp.
  • the sample was placed in a normally white mode TN element in which the distance (cell gap) between the two glass substrates was 0.45 / ⁇ n ( ⁇ m) and the twist angle was 80 degrees.
  • the voltage (32 Hz, square wave) applied to this device was gradually increased by 0.02 V from 0 V to 10 V.
  • the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured.
  • a voltage-transmittance curve was created in which the transmittance was 100% when the amount of light was maximum and the transmittance was 0% when the amount of light was minimum.
  • the threshold voltage is expressed as the voltage when the transmittance reaches 90%.
  • VHR Voltage retention rate
  • the TN element 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 placed in this TN element and sealed with an adhesive that cures with ultraviolet rays.
  • This TN element 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 period was determined.
  • Area B was the area when there was no attenuation.
  • the voltage holding ratio is expressed as a percentage of the area A with respect to the area B.
  • 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 for the transmittance to change from 10% to 90%.
  • the response time was expressed as the sum of the rise time and the fall time obtained in this way.
  • Permittivity in the minor axis direction ( ⁇ ; measured at 25 ° C.): The sample was placed in a TN element having a distance (cell gap) between two glass substrates of 9 ⁇ m and a twist angle of 80 degrees. .. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the permittivity ( ⁇ ) of the liquid crystal molecule in the minor axis direction was measured.
  • Pre-tilt angle (degrees): A spectroscopic ellipsometer M-2000U (manufactured by J.A. Woollam Co., Inc.) was used for measuring the pre-tilt angle.
  • Flicker rate (measured at 25 ° C.;%): A multimedia display tester 3298F manufactured by Yokogawa Electric Corporation was used for the measurement.
  • the light source was an LED.
  • the sample was placed in a normally black mode element 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 UV curable adhesive. A voltage was applied to this device, and the voltage at which the amount of light transmitted through the device was maximized was measured. While applying this voltage to the element, the sensor unit 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 brightness of the area with the line afterimage and the brightness of the remaining area (reference area) were measured. The rate at which the brightness decreased due to the line afterimage was calculated, and the magnitude of the line afterimage was expressed by this rate.
  • Luminance measurement An image of the device was taken using an imaging color luminance meter (Radiant Zemax, PM-1433F-0). The brightness of each region of the device was calculated by analyzing this image using software (Prometric 9.1, manufactured by Radiant Imaging). An LED backlight having an average brightness of 3500 cd / m 2 was used as the light source.
  • V255 square wave, 30 Hz
  • 0.5 V square wave, 30 Hz
  • V127 square wave, 0.25 Hz
  • the surface afterimage was calculated from the following formula.
  • (Surface afterimage) (luminance C-luminance D) / brightness D ⁇ 100.
  • the luminance C was the average luminance of 8 cells to which V255 was applied
  • the luminance D was the average luminance of 8 cells to which 0.5 V was applied.
  • the surface afterimage is preferably small.
  • P-FISP the surface afterimage is shown by P-FISP.
  • N-FISP the surface afterimage was shown by N-FISP.
  • Haze rate (%) A haze meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) was used for measuring the haze rate.
  • 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 carried out according to Japanese Industrial Standards (JIS) K5600-7-7, accelerated weather resistance and accelerated light resistance (xenon lamp method). For the measurement, (Super xenon weather meter SX75 type manufactured by Suga Test Instruments Co., Ltd. was used. The measurement conditions were illuminance (UVA; 180 W / m 2 ), irradiation time (100 hours), and black panel temperature (63 ⁇ ). 2 ° C.), the temperature inside the tank (35 ° C.), and the relative humidity inside the tank (40% RH). UVA means ultraviolet A (ultraviolet A).
  • Liquid crystal compounds are represented by symbols based on the definitions in Table 3 below.
  • Table 3 the configuration for 1,4-cyclohexylene is trans.
  • the number in parentheses after the symbolized compound represents the chemical formula to which the compound belongs.
  • the symbol (-) means other liquid crystal compounds.
  • the polymerizable compound was appropriately selected from the following compounds and used.
  • optically active compounds were used in the examples.
  • Example 1 (1) Preparation of Liquid Crystal Dimming Element
  • the composition (M1) had a positive dielectric anisotropy.
  • the optically active compound (10-4-1) was added at a rate of 1.0% based on the composition (M1).
  • the spiral pitch was 1.1 ⁇ m.
  • a polymerizable compound (RM-15) was mixed with this composition to prepare a polymerizable composition.
  • Irgacure 651 photopolymerization initiator; registered trademark; BASF
  • BASF photopolymerization initiator
  • This polymerizable composition was injected into an element in which the distance (cell gap) between the two glass substrates was 10 ⁇ m.
  • the device was not oriented. While applying 30 V (60 Hz) to this device, an ultraviolet ray of 18 mW / cm 2 was irradiated for 56 seconds with a high-pressure mercury lamp to prepare an device having a liquid crystal composite. This device was opaque. When a voltage of 30 V was applied to this device and it was irradiated with light, it became transparent. From this result, it was found that this element is in the normal mode.
  • Example 2 (1) Preparation of Liquid Crystal Dimming Element
  • the composition (M2) had a positive dielectric anisotropy.
  • the optically active compound (10-4-1) was added at a rate of 0.94% based on the composition (M2).
  • the spiral pitch was 1.0 ⁇ m.
  • a polymerizable compound (RM-1) and a polymerizable compound (RM-5) were mixed with this composition to prepare a polymerizable composition.
  • Irgacure 651 photopolymerization initiator; registered trademark; BASF
  • BASF photopolymerization initiator
  • This polymerizable composition was injected into an element in which the distance (cell gap) between the two glass substrates was 10 ⁇ m.
  • the device was not oriented.
  • This device was irradiated with ultraviolet rays of 18 mW / cm 2 for 56 seconds with a high-pressure mercury lamp while applying 30 V (60 Hz) to prepare an device having a liquid crystal composite.
  • This device was opaque. When a voltage of 30 V was applied to this device and it was irradiated with light, it became transparent. From this result, it was found that this element is in the normal mode.
  • Examples 3 to 5 The haze change rate was calculated in the same manner as in Example 2. The results are summarized in Table 4. To Examples 3 to 5, an optically active compound (10-4-1) was added at a rate of 1.0% based on the composition.
  • the liquid crystal dimming element containing the liquid crystal composite of the present invention can be used for a dimming window, a smart window, and the like.

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112882268A (zh) * 2021-01-11 2021-06-01 华南师范大学 一种光反射薄膜及其制备方法和传感器

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07507083A (ja) * 1992-05-18 1995-08-03 ケント ステイト ユニバーシティ 液晶光変調デバイスと物質
WO2018025996A1 (ja) * 2016-08-04 2018-02-08 Jnc株式会社 液晶デバイス用材料および液晶デバイス
WO2018036989A1 (en) * 2016-08-24 2018-03-01 Merck Patent Gmbh Liquid crystalline medium and liquid crystal display
WO2018078968A1 (ja) * 2016-10-27 2018-05-03 Jnc株式会社 調光用液晶組成物および液晶調光素子
WO2019026621A1 (ja) * 2017-08-02 2019-02-07 Jnc株式会社 液晶複合体および液晶調光素子

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07507083A (ja) * 1992-05-18 1995-08-03 ケント ステイト ユニバーシティ 液晶光変調デバイスと物質
WO2018025996A1 (ja) * 2016-08-04 2018-02-08 Jnc株式会社 液晶デバイス用材料および液晶デバイス
WO2018036989A1 (en) * 2016-08-24 2018-03-01 Merck Patent Gmbh Liquid crystalline medium and liquid crystal display
WO2018078968A1 (ja) * 2016-10-27 2018-05-03 Jnc株式会社 調光用液晶組成物および液晶調光素子
WO2019026621A1 (ja) * 2017-08-02 2019-02-07 Jnc株式会社 液晶複合体および液晶調光素子

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112882268A (zh) * 2021-01-11 2021-06-01 华南师范大学 一种光反射薄膜及其制备方法和传感器
CN112882268B (zh) * 2021-01-11 2022-06-21 华南师范大学 一种光反射薄膜及其制备方法和传感器

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