Liquid crystal composition, and liquid crystal display element, sensor, liquid crystal lens, optical communication device, and antenna using the same

Abstract

The present invention has a large Δn but T ni not become too high, i.e., Δn and T ni The present invention provides a liquid crystal composition having an excellent balance of the above properties and good storage stability at room temperature, as well as a liquid crystal display element, a sensor, a liquid crystal lens, an optical communication device, and an antenna using the same. Specifically, the liquid crystal composition contains one or more compounds selected from the group consisting of compounds represented by general formulas (i) and (ii) and one or more compounds represented by general formula (iii), and contains the compounds represented by general formulas (i) and (ii) and the compound represented by general formula (iii) in predetermined amounts.

Description

[Technical field]

[0001] The present invention relates to a liquid crystal composition, and a liquid crystal display device, a sensor, a liquid crystal lens, an optical communication device and an antenna using the same. [Background technology]

[0002] Liquid crystals are widely used in displays, but as a new application, liquid crystal antennas that transmit and receive radio waves between a mobile object such as a car and a communication satellite are attracting attention. Conventionally, satellite communication uses parabolic antennas, but when used in a mobile object such as a car, the parabolic antenna must be pointed toward the satellite at any time, which requires a large movable part. However, liquid crystal antennas can change the direction of radio waves by moving the liquid crystal inside the panel, so there is no need to move the antenna itself and the shape of the antenna can be made flat. In addition, in order to realize global high-capacity and high-speed communication, low-orbit satellite constellations using a large number of low-orbit satellites are being studied. Liquid crystal antennas, which can easily change the direction of radio waves, are useful for tracking low-orbit satellites that appear to be constantly moving from the ground. Generally, for autonomous driving of automobiles, downloading of large amounts of high-precision 3D map information is necessary. However, if an antenna using liquid crystal is incorporated into an automobile, downloading of large amounts of data from a communication satellite becomes possible without any mechanical moving parts. The frequency band used in satellite communication is about 13 GHz, which is significantly different from the frequencies used for liquid crystal displays up to now. Therefore, the required physical properties of the liquid crystal are also significantly different, and the Δn required for the liquid crystal for the antenna is, for example, about 0.4, and the operating temperature range is, for example, -20 to 120°C. Infrared laser image recognition and distance measuring devices using liquid crystals are also attracting attention as sensors for automatic driving of moving objects such as automobiles. The Δn required for liquid crystals for this purpose is, for example, 0.3 to 0.6, and the operating temperature range is, for example, 10 to 100°C. Furthermore, it is known that many liquid crystal compounds constituting a liquid crystal composition exhibiting a high Δn of 0.2 or more have low compatibility, and therefore it is important to select a liquid crystal compound having high compatibility. On the other hand, as a technique for liquid crystal for antennas, for example, Patent Document 1 can be mentioned. Moreover, Non-Patent Document 1 proposes the use of liquid crystal materials as components of high-frequency devices. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2016-37607 A [Non-patent literature]

[0004] [Non-Patent Document 1] Dolfi, Electronics Letters, (UK), 1993, Vol. 29, No. 10, pp. 926-928 Summary of the Invention [Problem to be solved by the invention]

[0005] Liquid crystal compositions with large Δn often use compounds with extended π conjugation, so the T ni In order to dissolve such a liquid crystal composition, it is necessary to heat the liquid crystal composition to a high temperature, which may cause deterioration of the liquid crystal composition by heating. In addition, there is a concern about storage stability, and the liquid crystal composition is likely to solidify even at room temperature. The present invention has a large Δn but T ni not become too high, i.e., Δn and T ni The present invention provides a liquid crystal composition having an excellent balance of the above properties and good storage stability at room temperature, as well as a liquid crystal display element, a sensor, a liquid crystal lens, an optical communication device, and an antenna each using the same. [Means for solving the problem]

[0006] As a result of intensive investigations, the present inventors have found that in a liquid crystal composition containing one or more compounds selected from the group consisting of compounds represented by general formulas (i) and (ii) having three benzene ring structures and -C≡C- as a linking group between the ring structures and an isothiocyanate group (-NCS), and one or more compounds represented by general formula (iii) having -C≡C- as a linking group between the ring structures and an isothiocyanate group (-NCS), by adjusting the contents of the compounds represented by general formulas (i) and (ii) and the compounds represented by general formula (iii) to predetermined amounts, the above-mentioned problems can be solved, and the present invention has been completed. An example of the configuration of the present invention that solves the above problem is as follows.

[0007] Item 1. A compound represented by the following general formulas (i) and (ii)

[0008] [ka] (In the general formulas (i) and (ii), R i1 and R ii1 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, One or more -CH2- groups in the alkyl group may each be independently replaced by -O-; One or more -CH2-CH2- in the alkyl group may each independently be replaced by -CH=CH- and / or -CF=CF-; One or more hydrogen atoms in the alkyl group may be independently substituted with a halogen atom. Oxygen atoms do not bond directly to each other, Y i1 and Y ii1 each independently represents a hydrogen atom or a halogen atom. and one or more compounds selected from the group consisting of compounds represented by The following general formula (iii)

[0009] [ka] (In general formula (iii), R iii1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, One or more -CH2- groups in the alkyl group may each be independently replaced by -O-; One or more -CH2-CH2- in the alkyl group may each independently be replaced by -CH=CH- and / or -CF=CF-; One or more hydrogen atoms in the alkyl group may be independently substituted with a halogen atom. Oxygen atoms do not bond directly to each other, A iii1 is represented by the following general formula (A iii1 -1)~(A iii1 -5)

[0010] [ka] (General formula (A iii1 -1)~(A iii1 -5) Medium, The white dot is R iii1 represents a bond to The black dots represent bonds to -C≡C-. S iii1 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, one or more hydrogen atoms in the alkyl or alkoxy group may each be independently substituted with a halogen atom; S iii1 If there are multiple, they may be the same or different.) represents a group selected from the group consisting of groups represented by Y iii1 represents a hydrogen atom or a halogen atom. A liquid crystal composition containing one or more compounds represented by the total content of the compounds represented by the general formulas (i) and (ii) in 100% by mass of the liquid crystal composition is 25% by mass or more, A liquid crystal composition, wherein the total content of the compounds represented by the general formula (iii) is 20% by mass or more based on 100% by mass of the liquid crystal composition.

[0011] Item 2. Furthermore, the following general formulae (o-1) to (o-5)

[0012] [ka] (In general formulas (o-1) to (o-5), R o1 , R o2 , R o3 , R o4 and R o5 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, One or more -CH2- groups in the alkyl group may each be independently replaced by -O-; One or more -CH2-CH2- in the alkyl group may each independently be replaced by -CH=CH- and / or -CF=CF-; One or more hydrogen atoms in the alkyl group may be independently substituted with a halogen atom. Oxygen atoms do not bond directly to each other, A o1 , A o2 , A o3 , A o4 and A o5 are each independently represented by the following general formula (A o1 / 2 / 3 / 4 / 5 -1)~(A o1 / 2 / 3 / 4 / 5 -5)

[0013] [ka] (Formula (A o1 / 2 / 3 / 4 / 5 -1)~(A o1 / 2 / 3 / 4 / 5 -5) Medium, The white dots represent bonds to the cyclohexane ring structure, -CH=CH- or -C≡C-. The black dots represent bonds to the -C≡C- or benzene ring structure. S o1 / 2 / 3 / 4 / 5 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, one or more hydrogen atoms in the alkyl or alkoxy group may each be independently substituted with a halogen atom; S o1 / 2 / 3 / 4 / 5 If there are multiple, they may be the same or different.) represents a group selected from the group consisting of groups represented by Y o1 , Y o2 , Y o3 , Y o4 and Y o5 each independently represents a hydrogen atom or a halogen atom. 2. The liquid crystal composition according to item 1, comprising one or more compounds selected from the group consisting of compounds represented by the following formula:

[0014] Item 3. Compounds represented by the general formulae (i) and (ii) include compounds represented by the following structural formulae (i-5), (i-6), (ii-5), (ii-6) and (ii-7):

[0015] [ka] 3. The liquid crystal composition according to item 1 or 2, comprising one or more compounds selected from the group consisting of compounds represented by the following formula:

[0016] 4.25°C, Δn at 589 nm is 0.40 or more, and / or the upper limit temperature of the liquid crystal phase (T ni 4. The liquid crystal composition according to any one of items 1 to 3, wherein the temperature difference (Tc) is 170° C. or lower.

[0017] Item 5. A liquid crystal display device using the liquid crystal composition according to any one of items 1 to 4.

[0018] Item 6. The liquid crystal display element according to item 5, which is driven by an active matrix method or a passive matrix method.

[0019] Item 7. A liquid crystal display device in which the orientation direction of liquid crystal molecules of the liquid crystal composition according to any one of items 1 to 4 is reversibly changed to reversibly switch the dielectric constant.

[0020] Item 8. A sensor using the liquid crystal composition according to any one of items 1 to 4.

[0021] Item 9. A liquid crystal lens using the liquid crystal composition according to any one of items 1 to 4.

[0022] Item 10. An optical communication device using the liquid crystal composition according to any one of items 1 to 4.

[0023] Item 11. An antenna using the liquid crystal composition according to any one of items 1 to 4.

[0024] Item 12. The antenna according to item 11, a first substrate having a plurality of slots; a second substrate facing the first substrate and provided with a power supply unit; a first dielectric layer provided between the first substrate and the second substrate; A plurality of patch electrodes arranged corresponding to the plurality of slots; a third substrate on which the patch electrode is provided; a liquid crystal layer provided between the first substrate and the third substrate; Item 5. An antenna, wherein the liquid crystal layer contains the liquid crystal composition according to any one of items 1 to 4. Effect of the Invention

[0025] According to the present invention, in a liquid crystal composition containing one or more compounds selected from the group consisting of compounds represented by general formulas (i) and (ii) having three benzene ring structures and -C≡C- as a linking group between the ring structures and an isothiocyanate group (-NCS), and one or more compounds represented by general formula (iii) having -C≡C- as a linking group between the ring structures and an isothiocyanate group (-NCS), the contents of the compounds represented by general formulas (i) and (ii) and the compound represented by general formula (iii) are set to predetermined amounts, whereby Δn and T ni The present invention can provide a liquid crystal composition having an excellent balance of the above properties and excellent storage stability at room temperature, and the liquid crystal composition is useful for liquid crystal display elements, sensors, liquid crystal lenses, optical communication devices and antennas. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] (Compounds represented by general formulas (i) and (ii)) The liquid crystal composition of the present invention contains at least one compound selected from the group consisting of compounds represented by the following general formulas (i) and (ii) having three benzene ring structures and a -C≡C- group and an isothiocyanate group (-NCS) as a linking group between the ring structures, in an amount of at least 25 mass % based on 100 mass % of the liquid crystal composition.

[0027] [ka]

[0028] In the general formulas (i) and (ii), R i1 and R ii1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms is a linear, branched or cyclic alkyl group, and is preferably a linear alkyl group. The alkyl group having 1 to 20 carbon atoms preferably has 2 to 10 carbon atoms, and more preferably has 2 to 6 carbon atoms. One or more -CH2- groups in the alkyl group may each independently be replaced by -O-. In addition, one or more -CH2-CH2- groups in the alkyl group may each independently be substituted with -CH=CH- and / or -CF=CF-. Furthermore, one or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. However, when the alkyl group is substituted with a specific group, the oxygen atoms are not directly bonded to each other. For example, R i1 and R ii1 can represent an alkoxy group having 1 to 19 carbon atoms by replacing one -CH2- in the alkyl group with -O-. The alkoxy group is a linear, branched or cyclic alkoxy group, and is preferably a linear alkoxy group. The alkoxy group preferably has 2-10, and more preferably 2-6, carbon atoms. Also, R i1 and R ii1 can represent an alkenyl group having 2 to 20 carbon atoms by replacing one or more -CH2-CH2- in the alkyl group with -CH=CH-. The alkenyl group is a linear, branched or cyclic alkenyl group, and is preferably a linear alkenyl group. The alkenyl group preferably has 2-10, and more preferably 2-6, carbon atoms. Also, R i1 and R ii1 can represent an alkenyloxy group having 2 to 19 carbon atoms by replacing one -CH2- with -O- and one or more -CH2-CH2- with -CH=CH- in the alkyl group. The alkenyloxy group is a linear, branched or cyclic alkenyloxy group, and is preferably a linear alkenyloxy group. The alkenyloxy group preferably has 2-10, and more preferably 2-6, carbon atoms. Also, R i1 and R ii1 can represent a halogenated alkyl group having 1 to 20 carbon atoms by substituting one or more hydrogen atoms in the alkyl group with halogen atoms. The halogenated alkyl group may be linear, branched or cyclic, and is preferably a linear halogenated alkyl group. The halogenated alkyl group preferably has 2-10 carbon atoms, and more preferably has 2-6 carbon atoms. Also, R i1 and R ii1 can represent a halogenated alkoxy group having 1 to 19 carbon atoms, in which one -CH2- in the alkyl group is replaced with -O-, and one or more hydrogen atoms in the alkyl group are replaced with halogen atoms. The halogenated alkoxy group may be a linear, branched or cyclic halogenated alkoxy group, and is preferably a linear halogenated alkoxy group. The halogenated alkoxy group preferably has 2-10 carbon atoms, and more preferably has 2-6 carbon atoms. R i1 and R ii1 Specific examples of the alkyl group having 1 to 20 carbon atoms (including substituted alkyl groups) in the formula (R i1 / ii1 -1)~(R i1 / ii1 -31) and the like.

[0029] [ka]

[0030] Formula (R i1 / ii1 -1)~(R i1 / ii1 -31), the black dots represent bonds to the benzene ring structure. In addition, R i1 and R ii1 As the alkyl group, from the viewpoints of Δn and compatibility with other liquid crystal compounds, a linear alkyl group having 2 to 6 carbon atoms is preferable. Also, R i1and R ii1 From the viewpoints of liquid crystallinity and viscosity, a linear alkenyl group having 2 to 6 carbon atoms is preferred.

[0031] In the general formulas (i) and (ii), Y i1 and Y ii1 each independently represents a hydrogen atom or a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. From the viewpoint of dielectric anisotropy (Δε) and compatibility, Y i1 and Y ii1 is preferably a fluorine atom.

[0032] Examples of the compound represented by general formula (i) include compounds represented by the following structural formulas (i-1) to (i-6), and from the viewpoints of solubility and low viscosity, the compounds represented by structural formulas (i-5) and (i-6) are preferred.

[0033] [ka]

[0034] Examples of the compound represented by general formula (ii) include compounds represented by the following structural formulas (ii-1) to (ii-7), and from the viewpoints of solubility and low viscosity, the compounds represented by structural formulas (ii-5) and (ii-6) are preferred.

[0035] [ka]

[0036] The compounds represented by general formula (i) or structural formulas (i-1) to (i-6) used in the liquid crystal composition are one or more kinds, preferably 1 to 10 kinds, preferably 1 to 5 kinds, and preferably 1 to 3 kinds.

[0037] The lower limit of the total content of the compounds represented by general formula (i) or structural formulas (i-1) to (i-6) in 100 mass% of the liquid crystal composition is preferably 1 mass% or more, preferably 5 mass% or more, preferably 10 mass% or more, preferably 15 mass% or more, preferably 20 mass% or more, preferably 25 mass% or more, preferably 30 mass% or more, and preferably 35 mass% or more.

[0038] The upper limit of the total content of the compounds represented by general formula (i) or structural formulas (i-1) to (i-6) in 100 mass% of the liquid crystal composition is preferably 50 mass% or less, preferably 45 mass% or less, preferably 40 mass% or less, preferably 35 mass% or less, preferably 30 mass% or less, preferably 25 mass% or less, preferably 20 mass% or less, and preferably 15 mass% or less.

[0039] The number of types of the compounds represented by general formula (ii) or structural formulas (ii-1) to (ii-7) used in the liquid crystal composition is one or more, preferably 1 to 10, preferably 1 to 5, and preferably 1 to 3. The lower limit of the total content of the compounds represented by general formula (ii) or structural formulas (ii-1) to (ii-7) in 100 mass% of the liquid crystal composition is preferably 1 mass% or more, preferably 5 mass% or more, preferably 10 mass% or more, preferably 15 mass% or more, preferably 20 mass% or more, preferably 25 mass% or more, preferably 30 mass% or more, and preferably 35 mass% or more.

[0040] The upper limit of the total content of the compounds represented by general formula (ii) or structural formulas (ii-1) to (ii-7) in 100 mass% of the liquid crystal composition is preferably 50 mass% or less, preferably 45 mass% or less, preferably 40 mass% or less, preferably 35 mass% or less, preferably 30 mass% or less, preferably 25 mass% or less, preferably 20 mass% or less, and preferably 15 mass% or less.

[0041] The total content of the compounds (including sub-concepts) represented by general formulas (i) and (ii) in 100% by mass of the liquid crystal composition is 25% by mass or more, preferably 25 to 50% by mass, and more preferably 30 to 45% by mass. If it is less than 25% by mass, it may not be possible to ensure a large Δn value for the liquid crystal composition.

[0042] The compounds represented by general formulae (i) and (ii) (including sub-concepts) can be synthesized by known synthesis methods, some of which are exemplified below. (Production Method 1) Production of a compound represented by the following general formula (s-5):

[0043] [ka]

[0044] In the formula, R i1 and Y i1 is R in the general formula (i). i1 and Y i1 It has the same meaning as: First, a compound represented by general formula (s-2) can be obtained by reacting a compound represented by general formula (s-1) with 1-bromo-4-iodobenzene. The reaction method includes, for example, Suzuki coupling reaction using a palladium catalyst and a base. Specific examples of palladium catalysts include [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride, palladium(II) acetate, dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphino]palladium(II), dichlorobis(triphenylphosphine)palladium(II), tetrakis(triphenylphosphine)palladium(0), and the like. Examples of the base include potassium carbonate, sodium carbonate, potassium phosphate, and the like. Next, the compound represented by general formula (s-2) is reacted with a compound represented by general formula (s-3) to obtain a compound represented by general formula (s-4). The reaction method includes, for example, Sonogashira coupling reaction using a palladium catalyst, a copper catalyst and a base. Specific examples of palladium catalysts include [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride, palladium(II) acetate, dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphino]palladium(II), dichlorobis(triphenylphosphine)palladium(II), tetrakis(triphenylphosphine)palladium(0), and the like. When palladium(II) acetate is used as the metal catalyst, a ligand such as triphenylphosphine or 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl may be added. A specific example of a copper catalyst is copper(I) iodide. A specific example of the base is triethylamine. Furthermore, the compound represented by general formula (s-4) can be reacted with an NCS reagent such as thiophosgene, disulfuric acid, 1,1-thiocarbonyldiimidazole, and 1,1'-thiocarbonyl-di-2(1H)pyridone to obtain the target compound represented by general formula (s-5). (Production Method 2) Production of a compound represented by the following general formula (s-10)

[0045] [ka]

[0046] In the formula, R ii1 and Y ii1 is R in the general formula (ii) ii1 and Y ii1 It has the same meaning as: First, the compound represented by the general formula (s-6) is reacted with trimethylsilylacetylene, and then reacted with potassium carbonate in an alcohol solvent to obtain the compound represented by the general formula (s-7). Reactions with trimethylsilylacetylene include the Sonogashira coupling reaction using a palladium catalyst, a copper catalyst and a base. Specific examples of the palladium catalyst and the base include those mentioned above. Next, the compound represented by general formula (s-7) is reacted with a compound represented by general formula (s-8) to obtain a compound represented by general formula (s-9). The reaction method includes, for example, Sonogashira coupling reaction using a palladium catalyst, a copper catalyst and a base. Specific examples of the palladium catalyst, copper catalyst and base include those mentioned above. Furthermore, the compound represented by general formula (s-9) can be reacted with an NCS reagent such as thiophosgene, disulfuric acid, 1,1-thiocarbonyldiimidazole, and 1,1'-thiocarbonyl-di-2(1H)pyridone to obtain the target compound represented by general formula (s-10).

[0047] (Compound represented by general formula (iii)) The liquid crystal composition according to the present invention contains one or more compounds represented by general formula (iii) having -C≡C- and an isothiocyanate group (-NCS) as a linking group between ring structures in an amount of 20% by mass or more based on 100% by mass of the liquid crystal composition.

[0048] [ka]

[0049] In general formula (iii), R iii1 represents an alkyl group having 1 to 20 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, and is preferably a linear alkyl group. The alkyl group preferably has 2-10 carbon atoms, and more preferably 2-6 carbon atoms. One or more -CH2- groups in the alkyl group may each independently be replaced by -O-. In addition, one or more -CH2-CH2- groups in the alkyl group may be substituted with -CH=CH- and / or -CF=CF-. Furthermore, one or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. However, when the alkyl group is substituted with a specific group, the oxygen atoms are not directly bonded to each other. For example, R iii1 can represent an alkoxy group having 1 to 19 carbon atoms by replacing one -CH2- in the alkyl group with -O-. The alkoxy group is a linear, branched or cyclic alkoxy group, and is preferably a linear alkoxy group. The alkoxy group preferably has 2-10, and more preferably 2-6, carbon atoms. Also, R iii1 can represent an alkenyl group having 2 to 20 carbon atoms by replacing one or more -CH2-CH2- in the alkyl group with -CH=CH-. The alkenyl group is a linear, branched or cyclic alkenyl group, and is preferably a linear alkenyl group. The alkenyl group preferably has 2-10, and more preferably 2-6, carbon atoms. Also, R iii1can represent an alkenyloxy group having 2 to 19 carbon atoms by replacing one -CH2- with -O- and one or more -CH2-CH2- with -CH=CH- in the alkyl group. The alkenyloxy group is a linear, branched or cyclic alkenyloxy group, and is preferably a linear alkenyloxy group. The alkenyloxy group preferably has 2-10, and more preferably 2-6, carbon atoms. Also, R iii1 can represent a halogenated alkyl group having 1 to 20 carbon atoms by substituting one or more hydrogen atoms in the alkyl group with halogen atoms. The halogenated alkyl group may be linear, branched or cyclic, and is preferably a linear halogenated alkyl group. The halogenated alkyl group preferably has 2-10 carbon atoms, and more preferably has 2-6 carbon atoms. Also, R iii1 can represent a halogenated alkoxy group having 1 to 19 carbon atoms, in which one -CH2- in the alkyl group is replaced with -O-, and one or more hydrogen atoms in the alkyl group are replaced with halogen atoms. The halogenated alkoxy group may be a linear, branched or cyclic halogenated alkoxy group, and is preferably a linear halogenated alkoxy group. The halogenated alkoxy group preferably has 2-10 carbon atoms, and more preferably has 2-6 carbon atoms. R iii1 Specific examples of the alkyl group having 1 to 20 carbon atoms (including substituted alkyl groups) in the formula (R iii1 -1)~(R iii1 -30) groups.

[0050] [ka]

[0051] Formula (Riii1 -1)~(R iii1 -30) Black dots are A iii1 Represents a bond to . R iii1 From the viewpoint of solubility, a linear alkyl group having 1 to 8 carbon atoms and a linear alkenyl group having 2 to 6 carbon atoms are preferred.

[0052] In general formula (ii), A iii1 is represented by the following general formula (A iii1 -1)~(A iii1 -5) represents a group selected from the group consisting of groups represented by the formula (I).

[0053] [ka]

[0054] General formula (A iii1 -1)~(A iii1 -5) Medium, white point is R iii1 The black dot represents a bond to -C≡C-.

[0055] General formula (A iii1 -1)~(A iii1 -5) Medium, S iii1 represents any one of a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group having 1 to 6 carbon atoms is a linear, branched or cyclic alkyl group, and is preferably a linear alkyl group. The alkoxy group having 1 to 6 carbon atoms is a linear, branched or cyclic alkoxy group, and is preferably a linear alkoxy group. One or more hydrogen atoms in the alkyl group or alkoxy group may each independently be substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. S iii1Specific examples of the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms in the formula (S iii1 -1)~(S iii1 -16) groups.

[0056] [ka]

[0057] Formula (S iii1 -1)~(S iii1 -16), the black dots represent bonds to the benzene ring structure. In addition, S iii1 When there are multiple, they may be the same or different.

[0058] More specifically, the general formula (A iii1 -2) is expressed by the following formula (A iii1 -2-1)~(A iii1 -2-4) is preferable.

[0059] [ka]

[0060] General formula (A iii1 -2-1)~(A iii1 -2-4) In the middle, the white dot is R iii1 The black dot represents a bond to -C≡C-.

[0061] More specifically, the general formula (A iii1 -3) is expressed by the following formula (A iii1 -3-1)~(A iii1 -3-4) is preferable.

[0062] [ka]

[0063] General formula (A iii1 -3-1)~(Aiii1 -3-4) In the middle, the white dot is R iii1 The black dot represents a bond to -C≡C-.

[0064] More specifically, the general formula (A iii1 -4) is expressed by the following formula (A iii1 -4-1)~(A iii1 -4-4) is preferable.

[0065] [ka]

[0066] General formula (A iii1 -4-1)~(A iii1 -4-4) In the middle, the white dot is R iii1 The black dot represents a bond to -C≡C-.

[0067] More specifically, the general formula (A iii1 -5) is expressed by the following formula (A iii1 -5-1)~(A iii1 -5-4) is preferable.

[0068] [ka]

[0069] General formula (A iii1 -5-1)~(A iii1 -5-4) In the middle, the white dot is R iii1 The black dot represents a bond to -C≡C-.

[0070] In general formula (iii), Y iii1 represents a hydrogen atom or a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. From the viewpoint of dielectric anisotropy (Δε) and compatibility, Y iii1 is preferably a fluorine atom.

[0071] The compound represented by general formula (iii) is preferably a compound represented by the following general formula (iii-1) from the viewpoint of low viscosity.

[0072] [ka]

[0073] In general formula (iii-1), R iii1 is R in the above general formula (iii). iii1 It has the same meaning as: Specific examples of the compound represented by general formula (iii-1) include compounds represented by the following structural formulas (iii-1.1) to (iii-1.7), and the like. From the viewpoint of Δn, the compounds represented by structural formulas (iii-1.5) and (iii-1.6) are preferred, and from the viewpoints of solubility and low viscosity, the compounds represented by structural formulas (iii-1.1) and (iii-i-8) are preferred.

[0074] [ka]

[0075] The compounds represented by general formula (iii), general formula (iii-1), or structural formulas (iii-1.1) to (iii-1.8) used in the liquid crystal composition are one or more kinds, preferably 1 to 10 kinds, preferably 1 to 5 kinds, and preferably 1 to 3 kinds.

[0076] The lower limit of the total content of the compounds represented by general formula (iii), general formula (iii-1), or structural formulas (iii-1.1) to (iii-1.8) in 100 mass% of the liquid crystal composition is preferably 1 mass% or more, more preferably 3 mass% or more, more preferably 5 mass% or more, and more preferably 10 mass% or more.

[0077] The upper limit of the total content of the compounds represented by general formula (iii), general formula (iii-1), or structural formulas (iii-1.1) to (iii-1.8) in 100 mass% of the liquid crystal composition is preferably 20 mass% or less, more preferably 15 mass% or less, more preferably 10 mass% or less, and more preferably 5 mass% or less.

[0078] The total content of the compounds represented by general formula (iii) (including subordinate concepts) in 100% by mass of the liquid crystal composition is 20% by mass or more, preferably 20 to 55% by mass, more preferably 25 to 55% by mass, and even more preferably 35 to 50% by mass. If it is less than 20% by mass, the content of other compounds increases, and T ni may become too high.

[0079] The compound represented by the general formula (iii) (including sub-concepts) can be synthesized by using a known synthesis method.

[0080] (Other compounds) The liquid crystal composition according to the present invention has a Δn and / or Δε r From this viewpoint, the composition may contain one or more compounds selected from the group consisting of compounds represented by the following general formulas (o-1) to (o-5).

[0081] [ka]

[0082] In general formulas (o-1) to (o-5), R o1 , R o2 , R o3 , R o4 and R o5 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, and is preferably a linear alkyl group. The alkyl group preferably has 2-10 carbon atoms, and more preferably 2-6 carbon atoms. One or more -CH2- groups in the alkyl group may each independently be replaced by -O-. In addition, one or more -CH2-CH2- groups in the alkyl group may be substituted with -CH=CH- and / or -CF=CF-. Furthermore, one or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. However, when the alkyl group is substituted with a specific group, the oxygen atoms are not directly bonded to each other. For example, R o1 , R o2 , R o3 , R o4 and R o5 can represent an alkoxy group having 1 to 19 carbon atoms by replacing one -CH2- in the alkyl group with -O-. The alkoxy group is a linear, branched or cyclic alkoxy group, and is preferably a linear alkoxy group. The alkoxy group preferably has 2-10, and more preferably 2-6, carbon atoms. Also, R o1 , R o2 , R o3 , R o4 and R o5 can represent an alkenyl group having 2 to 20 carbon atoms by replacing one or more -CH2-CH2- in the alkyl group with -CH=CH-. The alkenyl group is a linear, branched or cyclic alkenyl group, and is preferably a linear alkenyl group. The alkenyl group preferably has 2-10, and more preferably 2-6, carbon atoms. Also, R o1 , R o2 , R o3 , R o4 and R o5can represent an alkenyloxy group having 2 to 19 carbon atoms by replacing one -CH2- with -O- and one or more -CH2-CH2- with -CH=CH- in the alkyl group. The alkenyloxy group is a linear, branched or cyclic alkenyloxy group, and is preferably a linear alkenyloxy group. The alkenyloxy group preferably has 2-10, and more preferably 2-6, carbon atoms. Also, R o1 , R o2 , R o3 , R o4 and R o5 can represent a halogenated alkyl group having 1 to 20 carbon atoms by substituting one or more hydrogen atoms in the alkyl group with halogen atoms. The halogenated alkyl group may be linear, branched or cyclic, and is preferably a linear halogenated alkyl group. The halogenated alkyl group preferably has 2-10 carbon atoms, and more preferably has 2-6 carbon atoms. Also, R o1 , R o2 , R o3 , R o4 and R o5 can represent a halogenated alkoxy group having 1 to 19 carbon atoms, in which one -CH2- in the alkyl group is replaced with -O-, and one or more hydrogen atoms in the alkyl group are replaced with halogen atoms. The halogenated alkoxy group may be a linear, branched or cyclic halogenated alkoxy group, and is preferably a linear halogenated alkoxy group. The halogenated alkoxy group preferably has 2-10 carbon atoms, and more preferably has 2-6 carbon atoms. R o1 , R o2 , R o3 , R o4 and R o5 Specific examples of the alkyl group having 1 to 20 carbon atoms (including substituted alkyl groups) in the formula (Ro1 / 2 / 3 / 4 / 5 -1)~(R o1 / 2 / 3 / 4 / 5 -31) and the like.

[0083] [ka]

[0084] Formula (R o1 / 2 / 3 / 4 / 5 -1)~(R o1 / 2 / 3 / 4 / 5 -31), the black dots represent bonds to the cyclohexane ring structure or the benzene ring structure. R o1 , R o2 , R o3 , R o4 and R o5 From the viewpoint of solubility, a linear alkyl group having 1 to 6 carbon atoms or a linear alkenyl group having 2 to 6 carbon atoms is preferred.

[0085] In general formulas (o-1) to (o-5), A o1 , A o2 , A o3 , A o4 and A o5 are each independently represented by the following general formula (A o1 / 2 / 3 / 4 / 5 -1)~(A o1 / 2 / 3 / 4 / 5 -5) represents a group selected from the group consisting of groups represented by the formula (I).

[0086] [ka]

[0087] General formula (A o1 / 2 / 3 / 4 / 5 -1)~(A o1 / 2 / 3 / 4 / 5 In -5), the white dots represent bonds to a cyclohexane ring structure, -CH=CH- or -C≡C-, and the black dots represent bonds to a -C≡C- or benzene ring structure.

[0088] General formula (A o1 / 2 / 3 / 4 / 5 -1)~(A o1 / 2 / 3 / 4 / 5 -5) Medium, S o1 / 2 / 3 / 4 / 5 each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group having 1 to 6 carbon atoms is a linear, branched or cyclic alkyl group, and is preferably a linear alkyl group. The alkoxy group having 1 to 6 carbon atoms is a linear, branched or cyclic alkoxy group, and is preferably a linear alkoxy group. One or more hydrogen atoms in the alkyl group or alkoxy group may each independently be substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. S o1 / 2 / 3 / 4 / 5 Specific examples of the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms (including substituted groups) in the formula (S o1 / 2 / 3 / 4 / 5 -1)~(S o1 / 2 / 3 / 4 / 5 -16) and the like.

[0089] [ka]

[0090] Formula (S o1 / 2 / 3 / 4 / 5 -1)~(S o1 / 2 / 3 / 4 / 5 -16), the black dots represent bonds to the benzene ring structure. In addition, S o1 / 2 / 3 / 4 / 5 When there are multiple, they may be the same or different.

[0091] More specifically, the general formula (A o1 / 2 / 3 / 4 / 5 -2) is expressed by the following formula (A o1 / 2 / 3 / 4 / 5 -2-1)~(A o1 / 2 / 3 / 4 / 5 -2-4) is preferable.

[0092] [ka]

[0093] General formula (A o1 / 2 / 3 / 4 / 5 -2-1)~(Ao1 / 2 / 3 / 4 / 5 In -2-4), the white dots represent bonds to a cyclohexane ring structure, -CH=CH- or -C≡C-, and the black dots represent bonds to a -C≡C- or benzene ring structure.

[0094] More specifically, the general formula (A o1 / 2 / 3 / 4 / 5 -3) is expressed by the following formula (A o1 / 2 / 3 / 4 / 5 -3-1)~(A o1 / 2 / 3 / 4 / 5 -3-4) is preferable.

[0095] [ka]

[0096] General formula (A o1 / 2 / 3 / 4 / 5 -3-1)~(A o1 / 2 / 3 / 4 / 5 In -3-4), the white dots represent bonds to a cyclohexane ring structure, -CH=CH- or -C≡C-, and the black dots represent bonds to a -C≡C- or benzene ring structure.

[0097] More specifically, the general formula (A o1 / 2 / 3 / 4 / 5 -4) is expressed by the following formula (A o1 / 2 / 3 / 4 / 5 -4-1)~(A o1 / 2 / 3 / 4 / 5 -4-4) is preferable.

[0098] [ka]

[0099] General formula (A o1 / 2 / 3 / 4 / 5 -4-1)~(A o1 / 2 / 3 / 4 / 5 In -4-4), the white dots represent bonds to a cyclohexane ring structure, -CH=CH- or -C≡C-, and the black dots represent bonds to a -C≡C- or benzene ring structure.

[0100] More specifically, the general formula (A o1 / 2 / 3 / 4 / 5 -5) is expressed by the following formula (A o1 / 2 / 3 / 4 / 5 -5-1)~(A o1 / 2 / 3 / 4 / 5 -5-4) is preferable.

[0101] [ka]

[0102] General formula (A o1 / 2 / 3 / 4 / 5 -5-1)~(A o1 / 2 / 3 / 4 / 5 In -5-4), the white dots represent bonds to a cyclohexane ring structure, -CH=CH- or -C≡C-, and the black dots represent bonds to a -C≡C- or benzene ring structure.

[0103] In general formulas (o-1) to (o-5), Y o1 , Y o2 , Y o3 , Y o4 and Y o5 each independently represents a hydrogen atom or a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. From the viewpoint of dielectric anisotropy (Δε) and compatibility, Y o1 , Y o2 , Y o3 , Y o4 and Y o5 is preferably a fluorine atom.

[0104] The compound represented by general formula (o-1) is preferably a compound represented by the following general formula (o-1-1).

[0105] [ka]

[0106] In general formula (o-1-1), R o1 R in the above general formula (o-1) o1 It has the same meaning as: Specific examples of the compound represented by general formula (o-1-1) include compounds represented by the following structural formulas (o-1-1.1) to (o-1-1.7).

[0107] [ka]

[0108] The compound represented by general formula (o-2) is preferably a compound represented by the following general formula (o-2-1).

[0109] [ka]

[0110] In general formula (o-2-1), R o2 R in the above general formula (o-2) o2 It has the same meaning as: Specific examples of the compound represented by general formula (o-2-1) include compounds represented by the following structural formulas (o-2-1.1) to (o-2-1.7).

[0111] [ka]

[0112] The compound represented by general formula (o-3) is preferably a compound represented by the following general formula (o-3-1).

[0113] [ka]

[0114] In general formula (o-3-1), R o3 R in the above general formula (o-3) o3 It has the same meaning as: Specific examples of the compound represented by general formula (o-3-1) include the compounds represented by the following structural formulas (o-3-1.1) to (o-3-1.7).

[0115] [ka]

[0116] The compound represented by general formula (o-4) is preferably a compound represented by the following general formula (o-4-1).

[0117] [ka]

[0118] In general formula (o-4-1), R o4 R in the above general formula (o-4) o4 It has the same meaning as: Specific examples of the compound represented by general formula (o-4-1) include compounds represented by the following structural formulas (o-4-1.1) to (o-4-1.7).

[0119] [ka]

[0120] The compound represented by general formula (o-5) is preferably a compound represented by the following general formula (o-5-1).

[0121] [ka]

[0122] In general formula (o-5-1), R o5 R in the above general formula (o-5) o5 It has the same meaning as: Specific examples of the compound represented by general formula (o-5-1) include the compounds represented by the following structural formulas (o-5-1.1) to (o-5-1.7).

[0123] [ka]

[0124] The number of types of compounds represented by general formula (o-1), general formula (o-1-1), or structural formulas (o-1-1.1) to (o-1-1.7) used in the liquid crystal composition is one or more, preferably 1 to 10, preferably 1 to 5, and preferably 1 to 3.

[0125] The total content of the compounds represented by general formula (o-1), general formula (o-1-1), or structural formulas (o-1-1.1) to (o-1-1.7) in 100% by mass of the liquid crystal composition is preferably 1 to 60% by mass, more preferably 5 to 55% by mass, and even more preferably 10 to 50% by mass.

[0126] The compounds represented by general formula (o-2), general formula (o-2-1), or structural formulas (o-2-1.1) to (o-2-1.7) used in the liquid crystal composition are one or more kinds, preferably 1 to 10 kinds, preferably 1 to 5 kinds, and preferably 1 to 3 kinds.

[0127] The total content of the compounds represented by general formula (o-2), general formula (o-2-1), or structural formulas (o-2-1.1) to (o-2-1.7) in 100% by mass of the liquid crystal composition is preferably 5 to 45% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 35% by mass.

[0128] The compounds represented by general formula (o-3), general formula (o-3-1), or structural formulas (o-3-1.1) to (o-3-1.7) used in the liquid crystal composition are one or more kinds, preferably 1 to 10 kinds, preferably 1 to 5 kinds, and preferably 1 to 3 kinds.

[0129] The total content of the compounds represented by general formula (o-3), general formula (o-3-1), or structural formulas (o-3-1.1) to (o-3-1.7) in 100% by mass of the liquid crystal composition is preferably 1 to 15% by mass, more preferably 1 to 10% by mass, and even more preferably 3 to 7% by mass.

[0130] The number of types of compounds represented by general formula (o-4), general formula (o-4-1), or structural formulas (o-4-1.1) to (o-4-1.7) used in the liquid crystal composition is one or more, preferably 1 to 10, preferably 1 to 5, and preferably 1 to 3.

[0131] The total content of the compounds represented by general formula (o-4), general formula (o-4-1), or structural formulas (o-4-1.1) to (o-4-1.7) in 100% by mass of the liquid crystal composition is preferably 1 to 15% by mass, more preferably 1 to 10% by mass, and even more preferably 3 to 7% by mass.

[0132] The number of types of compounds represented by general formula (o-5), general formula (o-5-1), or structural formulas (o-5-1.1) to (o-5-1.7) used in the liquid crystal composition is one or more, preferably 1 to 10, preferably 1 to 5, and preferably 1 to 3.

[0133] The total content of the compounds represented by general formula (o-5), general formula (o-5-1), or structural formulas (o-5-1.1) to (o-5-1.7) in 100% by mass of the liquid crystal composition is preferably 5 to 35% by mass, more preferably 10 to 30% by mass, and even more preferably 15 to 25% by mass.

[0134] The compounds represented by the general formulae (o-1) to (o-5) (including sub-concepts) can be synthesized by using known synthesis methods.

[0135] (Liquid crystal composition) The liquid crystal composition according to the present invention can be produced, for example, by mixing a compound selected from the group consisting of the compound represented by the above-mentioned general formula (i) and the compound represented by the general formula (ii), a compound represented by the general formula (iii), and, if necessary, the above-mentioned other compounds and additives.

[0136] Examples of the additives include a stabilizer, a dye compound, a polymerizable compound, an azotolane compound, and an isothiocyanate compound (NCS compound).

[0137] Examples of the stabilizer include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, hindered phenols, and hindered amines. Examples of the hindered phenols include hindered phenol-based antioxidants represented by the following structural formulas (XX-1) to (XX-3).

[0138] [ka]

[0139] Examples of the hindered amines include hindered amine-based light stabilizers represented by the following structural formulas (YY-1) to (YY-2).

[0140] [ka]

[0141] When a stabilizer is used, the type of stabilizer used in the liquid crystal composition is one or more, preferably 1 to 10 types, preferably 1 to 8 types, preferably 1 to 6 types, preferably 1 to 4 types, and preferably 1 to 2 types. When stabilizers are used, the total content of the stabilizers in 100% by mass of the liquid crystal composition is preferably 0.005 to 1% by mass, more preferably 0.02 to 0.50% by mass, and even more preferably 0.03 to 0.35% by mass.

[0142] In addition, the combination of compounds used in the liquid crystal composition may be determined based on the solubility, Δn and / or T ni From the viewpoint of 1) A combination of a compound represented by general formula (i) (including sub-concepts) and a compound represented by general formula (iii) (including sub-concepts), 2) A combination of a compound represented by general formula (i) (including subordinate concepts), a compound represented by general formula (iii) (including subordinate concepts), and a compound represented by general formula (o-1) (including subordinate concepts), 3) A combination of a compound represented by general formula (i) (including subordinate concepts), a compound represented by general formula (iii) (including subordinate concepts), and a compound represented by general formula (o-2) (including subordinate concepts), 4) A combination of a compound represented by general formula (i) (including subordinate concepts), a compound represented by general formula (iii) (including subordinate concepts), and a compound represented by general formula (o-5) (including subordinate concepts), 5) A combination of a compound represented by general formula (ii) (including sub-concepts) and a compound represented by general formula (iii) (including sub-concepts), 6) A combination of a compound represented by general formula (ii) (including subordinate concepts), a compound represented by general formula (iii) (including subordinate concepts), and a compound represented by general formula (o-2) (including subordinate concepts), 7) A combination of a compound represented by general formula (i) (including sub-concepts), a compound represented by general formula (ii) (including sub-concepts), and a compound represented by general formula (iii) (including sub-concepts), 8) A combination of a compound represented by general formula (i) (including subordinate concepts), a compound represented by general formula (ii) (including subordinate concepts), a compound represented by general formula (iii) (including subordinate concepts), and a compound represented by general formula (o-1) (including subordinate concepts), 9) A combination of a compound represented by general formula (i) (including subordinate concepts), a compound represented by general formula (ii) (including subordinate concepts), a compound represented by general formula (iii) (including subordinate concepts), and a compound represented by general formula (o-2) (including subordinate concepts), 10) A combination of a compound represented by general formula (i) (including subordinate concepts), a compound represented by general formula (ii) (including subordinate concepts), a compound represented by general formula (iii) (including subordinate concepts), and a compound represented by general formula (o-3) (including subordinate concepts), is preferred.

[0143] <Characteristic values ​​of liquid crystal composition> Liquid crystal phase upper limit temperature (T ni ) is the temperature at which the liquid crystal composition undergoes phase transition from a nematic phase to an isotropic phase. T ni The measurement is performed by preparing a preparation in which the liquid crystal composition is sandwiched between a slide glass and a cover glass, and observing the preparation under a polarizing microscope while heating the preparation on a hot stage. It can also be measured by differential scanning calorimetry (DSC). The unit used is "℃". T ni The higher T is, the more the nematic phase can be maintained even at high temperatures, and the wider the operating temperature range can be. However, since the liquid crystal is heated and melted during production, if the temperature is too high, it can deteriorate and high-temperature melting equipment is required, which is not preferable. ni The higher the T, the poorer the storage stability at low temperatures. ni It is difficult to achieve both high and low storage stability. The upper limit temperature of the liquid crystal phase of the liquid crystal composition according to the present invention (T ni ) can be appropriately set depending on whether the liquid crystal display element is used indoors, in a car, or outdoors where the external temperature can be controlled, but from the viewpoint of the driving temperature range, it is preferably 170° C. or less, more preferably 110 to 170° C., and even more preferably 115 to 165° C.

[0144] Liquid crystal phase lower limit temperature (T →n ) is the temperature at which a liquid crystal composition undergoes phase transition from another phase (glass phase, smectic phase, crystalline phase) to the nematic phase. T →n is measured by filling a glass capillary with the liquid crystal composition, immersing it in a refrigerant at -70°C to cause the liquid crystal composition to undergo a phase transition to another phase, and observing the change while increasing the temperature. It can also be measured by differential scanning calorimetry (DSC). The unit used is "℃". T →n The lower the temperature, the more the nematic phase can be maintained even at low temperatures, and therefore the operating temperature range can be made wider. The liquid crystal phase lower limit temperature (T →n ) is preferably 10°C or lower, more preferably from -70 to 0°C, and even more preferably from -40 to -5°C, from the viewpoint of the driving temperature.

[0145] Δn (refractive index anisotropy) correlates with Δn in the near-infrared region used in the optical sensor described below. The larger Δn is, the greater the phase modulation power of light of the target wavelength is, and therefore, it is particularly suitable for optical sensors. The extraordinary refractive index (n e ) and ordinary refractive index (n o ) difference (n e -n o ) is calculated. Also, Δn can be obtained from a phase difference measuring device. The relationship between the retardation Re, the thickness d of the liquid crystal layer, and Δn is Δn=Re / d. A liquid crystal composition is injected into a glass cell with a polyimide alignment film that has been subjected to anti-parallel rubbing treatment and has a cell gap (d) of approximately 3.0 μm, and the in-plane Re is measured using a retardation film / optical material inspection device RETS-100 (manufactured by Otsuka Electronics Co., Ltd.). The measurement is performed at a temperature of 25° C. and at 589 nm, and has no unit. From the viewpoint of the phase modulation power of light of the wavelength, Δn of the liquid crystal composition according to the present invention at 25° C. and at 589 nm is preferably 0.40 or more, more preferably 0.40 to 0.55, more preferably 0.41 to 0.50, and even more preferably 0.43 to 0.48.

[0146] The rotational viscosity (γ1) is the viscosity related to the rotation of liquid crystal molecules. γ1 can be measured by filling the liquid crystal composition into a glass cell having a cell gap of about 10 μm, applying a voltage of 50 V, and using an LCM-2 (manufactured by Toyo Corporation). In the case of a liquid crystal composition having a positive dielectric anisotropy, a horizontally aligned cell is used, whereas in the case of a liquid crystal composition having a negative dielectric anisotropy, a vertically aligned cell is used. The measurement is carried out at 25°C and the unit is mPa·s. The smaller γ1 is, the faster the response speed of the liquid crystal composition becomes, and therefore, it is suitable for any liquid crystal display element. The rotational viscosity (γ1) of the liquid crystal composition according to the present invention at 25° C. is preferably 150 to 1200 mPa·s, more preferably 200 to 900 mPa·s, and even more preferably 250 to 700 mPa·s, from the viewpoint of response speed.

[0147] The higher the dielectric anisotropy in the high frequency region, the greater the phase modulation power for radio waves in the target frequency band, and therefore the material is particularly suitable for use in antennas. In addition, in antenna applications, the smaller the dielectric tangent in the high frequency range, the smaller the energy loss in the target frequency band, which is preferable. In the liquid crystal composition according to the present invention, the dielectric anisotropy Δε at 10 GHz is representative of the characteristics in the high frequency range. r and the average value of the dielectric tangent, tanδ iso was measured. Δε r =(ε r∥ -ε r⊥ ) and tan δ iso =(2ε r⊥ tan δ ⊥ +ε r∥ tan δ ∥ ) / (2ε r⊥ +ε r∥ ). Here, “εr” is the dielectric constant, “tan δ” is the dielectric tangent, the subscript “∥” indicates the component parallel to the alignment direction of the liquid crystal, and “⊥” indicates the component perpendicular to the alignment direction of the liquid crystal.

[0148] Δε r and tan δ iso can be measured by the following method. First, a liquid crystal composition is introduced into a capillary tube made of polytetrafluoroethylene (PTFE). The capillary used here has an inner radius of 0.80 mm and an outer radius of 0.835 mm, with an effective length of 4.0 cm. The capillary tube containing the liquid crystal composition is introduced into the center of a cavity resonator (manufactured by EM Lab Co., Ltd.) having a resonance frequency of 10 GHz. The cavity has an outer diameter of 30 mm and a width of 26 mm. A signal is then input and the resulting output signal is recorded using a network analyzer (Keysight Technologies, Inc.). The dielectric constant (ε r ) and loss angle (δ). The tangent of the obtained δ is the dielectric tangent (tan δ). The resonance frequency and the like using a PTFE capillary tube filled with a liquid crystal composition are determined as values ​​of characteristic components perpendicular and parallel to the alignment direction of the liquid crystal molecules by controlling the alignment of the liquid crystal molecules. The magnetic field of a permanent magnet or electromagnet is used to align the liquid crystal molecules vertically (perpendicular to the effective length) or parallel to the PTFE capillary tube (parallel to the effective length). For example, the magnetic field has a pole-to-pole distance of 45 mm and a magnetic field strength of 0.23 Tesla near the center. The liquid crystal composition is filled in a PTFE capillary tube, which is then rotated parallel or perpendicular to the magnetic field to obtain the desired characteristic components. The measurement was performed at 25°C. r and tan δ iso Neither has a unit.

[0149] Δε at 25° C. of the liquid crystal composition according to the present invention r is preferably larger, but from the viewpoint of phase modulation power in the GHz band, it is preferably 0.90 or more, more preferably 0.90 to 1.50, more preferably 0.95 to 1.40, and even more preferably 1.00 to 1.35. Tan δ of the liquid crystal composition according to the present invention at 25° C. iso is preferably smaller, but from the viewpoint of loss in the GHz band, it is preferably 0.025 or less, preferably 0.001 to 0.025, preferably 0.003 to 0.020, preferably 0.005 to 0.017, preferably 0.007 to 0.015, preferably 0.008 to 0.013, and preferably 0.009 to 0.012.

[0150] (Liquid crystal display elements, sensors, liquid crystal lenses, optical communication devices and antennas) A liquid crystal display element, a sensor, a liquid crystal lens, an optical communication device, and an antenna using the liquid crystal composition according to the present invention will be described below.

[0151] The liquid crystal display element according to the present invention is characterized by using the above-mentioned liquid crystal composition, and is preferably driven by an active matrix system or a passive matrix system. The liquid crystal display element according to the present invention is preferably a liquid crystal display element in which the dielectric constant is reversibly switched by reversibly changing the alignment direction of the liquid crystal molecules of the above-mentioned liquid crystal composition.

[0152] The sensor according to the present invention is characterized by using the above-mentioned liquid crystal composition, and examples of its embodiments include a distance measuring sensor that uses electromagnetic waves, visible light or infrared light, an infrared sensor that uses a change in temperature, a temperature sensor that uses a change in the wavelength of reflected light due to a change in the pitch of a cholesteric liquid crystal, a pressure sensor that uses a change in the wavelength of reflected light, an ultraviolet sensor that uses a change in the wavelength of reflected light due to a change in composition, an electrical sensor that uses a temperature change due to a voltage or current, a radiation sensor that uses a temperature change accompanying the track of a radiation particle, an ultrasonic sensor that uses a change in the arrangement of liquid crystal molecules due to mechanical vibration of ultrasonic waves, and an electromagnetic field sensor that uses a change in the wavelength of reflected light due to a change in temperature or a change in the arrangement of liquid crystal molecules due to an electric field. The distance measurement sensor is preferably for use in LiDAR (Light Detection And Ranging) that uses a light source. As the LiDAR, preferred applications include artificial satellites, aircraft, unmanned aerial vehicles (drones), automobiles, railways, and ships. For automobiles, self-driving automobiles are particularly preferred. The light source is preferably an LED or a laser, preferably a laser. The light used in LiDAR is preferably infrared light, and the wavelength is preferably 800 to 2000 nm. In particular, an infrared laser with a wavelength of 905 nm or 1550 nm is preferred. When the cost of the photodetector to be used and sensitivity in all weather conditions are important, a 905 nm infrared laser is preferred, whereas when safety regarding human vision is important, a 1550 nm infrared laser is preferred. The liquid crystal composition according to the present invention exhibits a high Δn value, and therefore has a large phase modulation power in the visible light, infrared light and electromagnetic wave regions, and can provide a sensor with excellent detection sensitivity.

[0153] The liquid crystal lens of the present invention is characterized by using the above-mentioned liquid crystal composition, and for example, in one embodiment thereof, has a first transparent electrode layer, a second transparent electrode layer, a liquid crystal layer containing the above-mentioned liquid crystal composition provided between the first transparent electrode layer and the second transparent electrode layer, an insulating layer provided between the second transparent electrode layer and the liquid crystal layer, and a high-resistance layer provided between the insulating layer and the liquid crystal layer. The liquid crystal lens according to the present invention is used, for example, as a 2D / 3D switching lens, a lens for adjusting the focus of a camera, and the like.

[0154] The optical communication device according to the present invention is characterized by using the above-mentioned liquid crystal composition, and one of its embodiments is, for example, LCOS (Liquid crystal on silicon) having a liquid crystal layer in which liquid crystals constituting each of a plurality of pixels are arranged two-dimensionally on a reflective layer (electrode). The optical communication device according to the present invention is used, for example, as a spatial phase modulator.

[0155] The antenna according to the present invention is characterized by using the above-mentioned liquid crystal composition. More specifically, the antenna of the present invention comprises a first substrate having a plurality of slots, a second substrate facing the first substrate and having a power supply section, a first dielectric layer provided between the first substrate and the second substrate, a plurality of patch electrodes arranged corresponding to the plurality of slots, a third substrate having the patch electrodes provided thereon, and a liquid crystal layer provided between the first substrate and the third substrate, wherein the liquid crystal layer contains the above-mentioned liquid crystal composition. By using the liquid crystal composition according to the present invention, it is possible to provide an antenna that is highly reliable against external stimuli such as heat. It is also possible to provide an antenna that allows greater phase control for microwave or millimeter wave electromagnetic waves. Preferably, the antenna according to the invention operates in the Ka or K or Ku band frequencies used for satellite communications. The antenna according to the present invention preferably has a configuration in which a radial line slot array and a patch antenna array are combined. The structure of the antenna according to the present invention can be applied by taking into consideration the matters described in, for example, International Publication No. 2021 / 157189. EXAMPLES

[0156] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples in any way. The compositions of the following Examples and Comparative Examples contained each compound in the proportions shown in the table, and the contents are shown in "mass %". The compounds are described using the following abbreviations. In addition, compounds which can take either cis or trans form will represent the trans form unless otherwise specified. <Ring structure>

[0157] [ka]

[0158] <Terminal structure>

[0159] [Table 1] (Note that n in the table is a natural number. Also, the alkyl group represented by n is a straight-chain alkyl group.)

[0160] <Connection structure>

[0161] [Table 2] (Note that n in the table is a natural number. Also, the alkylene group represented by n is a linear alkylene group.)

[0162] (Hindered phenol antioxidant)

[0163] [ka]

[0164] (Hindered amine light stabilizer)

[0165] [ka]

[0166] (Preparation of Liquid Crystal Composition) LC-A to B and LC-01 to 08 shown in Table 3 were prepared.

[0167] [Table 3]

[0168] (Examples 1 to 14 and Comparative Examples 1 to 2) Liquid crystal compositions were prepared using LC-A to B and LC-01 to 08, hindered phenol antioxidants (XX-1) to (XX-3), and hindered amine light stabilizers (YY-1) to (YY-2), and the physical properties of the compositions were measured and a storage stability test was carried out. The results are shown in Tables 4 and 5. Note that in Comparative Example 1, crystallization occurred at room temperature, so the high frequency characteristics (Δε r and tan δ iso ) was not measured. <Storage test> 0.5 g of the liquid crystal composition was weighed into a 1 mL sample bottle (manufactured by Maruemu Co., Ltd.) and degassed for 10 minutes at 150 to 250 Pa. After that, the bottle was purged with dry nitrogen and the attached lid was put on. This was stored in a temperature-controlled thermostatic chamber (manufactured by Espec Corp., SH-241) at 25°C for two weeks, and the occurrence of crystallization of the liquid crystal composition was visually confirmed every week.

[0169] [Table 4]

[0170] [Table 5]

[0171] From Example 1 and Comparative Examples 1 and 2, it was found that a liquid crystal composition containing a predetermined amount of one or more compounds selected from the group consisting of the compounds represented by the general formulas (i) and (ii) and one or more compounds represented by the general formula (iii) has a low Δn and T ni It was confirmed that the balance of Δε r , tan δ iso also showed good values. On the other hand, from Comparative Examples 1 and 2, the liquid crystal composition not containing a predetermined amount of one or more compounds selected from the group consisting of the compounds represented by the general formulas (i) and (ii) and one or more compounds represented by the general formula (iii) had a small Δn of less than 0.40 or a T ni The results showed that the temperatures were as high as 175°C or higher. In addition, in Comparative Example 1, it was confirmed that LC-A was crystallized 4 days after its preparation. Furthermore, from Examples 2 to 14, it was confirmed that the same effects were obtained when various compounds were used or when a hindered phenol-based antioxidant or a hindered amine-based light stabilizer was used in combination. The synthesis of the compounds represented by general formulas (i) and (ii) will be described below. (Synthesis Example 1) Preparation of the compound represented by formula (I-1)

[0172] [ka]

[0173] Under a nitrogen atmosphere, 17g of the compound represented by formula (I-1-1), 2.3g of tetrakis(triphenylphosphine)palladium, 20g of potassium carbonate, 29g of 1-bromo-4-iodobenzene, 200mL of tetrahydrofuran, and 40mL of water were added to a reaction vessel, and the reaction vessel was heated to 70°C. After the reaction was completed, 10% by mass of hydrochloric acid was poured into the reaction liquid, and the liquid was extracted with ethyl acetate. The organic layer was washed with saturated saline, and then the solvent was distilled off, and the mixture was dispersed and washed with hexane to obtain 23g of the compound represented by formula (I-1-2). Next, under a nitrogen atmosphere, 23.0 g of the compound represented by formula (I-1-2), 0.7 g of copper (I) iodide, 1.25 g of bis(triphenylphosphine)palladium (II) dichloride, 50 mL of triethylamine, and 150 mL of N,N-dimethylformamide were added to a reaction vessel. Then, while heating at 85°C, a solution in which 13 g of the compound represented by formula (I-1-3) was dissolved in 25 mL of N,N-dimethylformamide was dropped, and the mixture was stirred at 85°C for 3 hours. After the reaction was completed, a saturated aqueous ammonium chloride solution was poured into the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated saline, and then recrystallized with toluene to obtain 22 g of the compound represented by formula (I-1-4). Next, 22 g of the compound represented by formula (I-1-4), 100 ml of dichloromethane, and 16 g of 1,1'-thiocarbonyl-di-2(1H)pyridone were added to a reaction vessel and reacted at room temperature. After the reaction was completed, the organic layer was washed with saturated saline, and then purified by column chromatography (silica gel, toluene) and recrystallization (toluene / hexane=2 / 1) to obtain 20.5 g of the compound represented by formula (I-1). MS(EI): m / z=401 (Synthesis Example 2) Preparation of the compound represented by formula (I-2)

[0174] [ka]

[0175] In a nitrogen atmosphere, 21.0 g of the compound represented by formula (I-2-1), 0.8 g of copper iodide (I), 1.4 g of bis(triphenylphosphine)palladium (II) dichloride, 50 mL of triethylamine, and 150 mL of N,N-dimethylformamide were added to a reaction vessel. Then, while heating at 70 ° C, a solution in which 20 g of trimethylsilylacetylene was dissolved in 50 mL of N,N-dimethylformamide was dropped, and the mixture was stirred at 70 ° C for 2 hours. After the reaction was completed, 10% by mass hydrochloric acid was poured into the reaction liquid, and the mixture was extracted with toluene. The organic layer was washed with saturated saline, and then column chromatography (silica gel, toluene) and solvent distillation were performed. Further, 20 g of potassium carbonate were added, and 200 ml of methanol was added, and the reaction vessel was heated to 50 ° C and reacted for 2 hours. Then, the reaction liquid was extracted with toluene, and the organic layer was washed with saturated saline, and then column chromatography (silica gel, toluene) and solvent distillation were performed to obtain 14 g of the compound represented by formula (I-2-2). Next, under a nitrogen atmosphere, 23.0 g of the compound represented by formula (I-2-3), 0.7 g of copper (I) iodide, 1.25 g of bis(triphenylphosphine)palladium (II) dichloride, 50 mL of triethylamine, and 150 mL of N,N-dimethylformamide were added to a reaction vessel. Then, while heating at 85°C, a solution in which 14 g of the compound represented by formula (I-2-2) was dissolved in 25 mL of N,N-dimethylformamide was dropped, and the mixture was stirred at 85°C for 3 hours. After the reaction was completed, a saturated aqueous ammonium chloride solution was poured into the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated saline, and then recrystallized with toluene to obtain 20 g of the compound represented by formula (I-2-4). Next, 20 g of the compound represented by formula (I-2-4), 100 ml of dichloromethane, and 15 g of 1,1'-thiocarbonyl-di-2(1H)pyridone were added to a reaction vessel and reacted at room temperature. After the reaction was completed, the organic layer was washed with saturated saline, and then purified by column chromatography (silica gel, toluene) and recrystallization (toluene / hexane=2 / 1) to obtain 18 g of the compound represented by formula (I-2). MS(EI): m / z=401 (Synthesis Example 3) Preparation of the compound represented by formula (I-3)

[0176] [ka]

[0177] In a nitrogen atmosphere, 22.5 g of the compound represented by formula (I-3-1), 0.8 g of copper iodide (I), 1.4 g of bis(triphenylphosphine)palladium (II) dichloride, 50 mL of triethylamine, and 150 mL of N,N-dimethylformamide were added to a reaction vessel. Then, while heating at 70 ° C, a solution in which 20 g of trimethylsilylacetylene was dissolved in 50 mL of N,N-dimethylformamide was dropped, and the mixture was stirred at 70 ° C for 2 hours. After the reaction was completed, 10% by mass hydrochloric acid was poured into the reaction liquid, and the mixture was extracted with toluene. The organic layer was washed with saturated saline, and then column chromatography (silica gel, toluene) and solvent distillation were performed. Further, 20 g of potassium carbonate were added, and 200 ml of methanol was added, and the reaction vessel was heated to 50 ° C and reacted for 2 hours. Then, the reaction liquid was extracted with toluene, and the organic layer was washed with saturated saline, and then column chromatography (silica gel, toluene) and solvent distillation were performed to obtain 15 g of the compound represented by formula (I-3-2). Next, under a nitrogen atmosphere, 22.5g of the compound represented by formula (I-3-3), 0.7g of copper (I) iodide, 1.25g of bis(triphenylphosphine)palladium (II) dichloride, 50mL of triethylamine, and 150mL of N,N-dimethylformamide were added to a reaction vessel. Then, while heating at 85°C, a solution in which 15g of the compound represented by formula (I-3-2) was dissolved in 25mL of N,N-dimethylformamide was added dropwise, and the mixture was stirred at 85°C for 3 hours. After the reaction was completed, a saturated aqueous solution of ammonium chloride was poured into the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated saline, and then recrystallized with toluene to obtain 22g of the compound represented by formula (I-3-4). Next, 22 g of the compound represented by formula (I-3-4), 100 ml of dichloromethane, and 16 g of 1,1'-thiocarbonyl-di-2(1H)pyridone were added to a reaction vessel and reacted at room temperature. After the reaction was completed, the organic layer was washed with saline, and then purified by column chromatography (silica gel, toluene) and recrystallization (toluene / hexane=2 / 1) to obtain 19 g of the compound represented by formula (I-3). MS(EI): m / z=415 [Industrial Applicability]

[0178] The liquid crystal composition of the present invention can be used in liquid crystal display devices, sensors, liquid crystal lenses, optical communication devices and antennas.

Claims

1. The following general formulas (i) and (ii) 【Chemistry 1】 (In the general formulas (i) and (ii), R ｉ１ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, One or more -CH 2 - in the alkyl group may each independently be replaced by -O-; One or more -CH 2 -CH 2 - in the alkyl group may each independently be replaced by -CH=CH- and / or -CF=CF-; Oxygen atoms do not bond directly to each other, R ii1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; One or more -CH in the alkyl group ２ Each - may be independently replaced by -O-; One or more -CH in the alkyl group ２ -CH ２ each - may independently be substituted with -CH=CH- and / or -CF=CF-; One or more hydrogen atoms in the alkyl group may be independently substituted with a halogen atom. Oxygen atoms do not bond directly to each other, Y ｉ１ and Y ｉｉ１ each independently represents a hydrogen atom or a halogen atom. and one or more compounds selected from the group consisting of compounds represented by The following general formula (iii): 【Chemistry 2】 (In general formula (iii), R ｉｉｉ１ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, One or more -CH in the alkyl group ２ Each - may be independently replaced by -O-; One or more -CH in the alkyl group ２ -CH ２ each - may independently be substituted with -CH=CH- and / or -CF=CF-; One or more hydrogen atoms in the alkyl group may be independently substituted with a halogen atom. Oxygen atoms do not bond directly to each other, A ｉｉｉ１ is represented by the following general formula (A ｉｉｉ１ -1) to (A ｉｉｉ１ -5) 【Chemistry 3】 (General formula (A ｉｉｉ１ -1)~(A ｉｉｉ１ -5) Middle, The white point is R ｉｉｉ１ represents a bond to The black dot represents a bond to -C≡C-. S ｉｉｉ１ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, one or more hydrogen atoms in the alkyl or alkoxy group may each independently be substituted with a halogen atom; S ｉｉｉ１ When there are multiple, they may be the same or different.) represents a group selected from the group consisting of groups represented by Y ｉｉｉ１ represents a halogen atom.) and one or more compounds represented by the formula: The following general formula (o-1): 【Chemistry 4】 (In general formula (o-1), R o1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; One or more -CH 2 - in the alkyl group may each independently be replaced by -O-; One or more -CH 2 -CH 2 - in the alkyl group may each independently be replaced by -CH=CH- and / or -CF=CF-; One or more hydrogen atoms in the alkyl group may be independently substituted with a halogen atom. Oxygen atoms do not bond directly to each other, A o1 is represented by the following general formula (A o1 / 2 / 3 / 4 / 5 -1) to (A o1 / 2 / 3 / 4 / 5 -5): 【Chemistry 5】 (Formula (A o1 / 2 / 3 / 4 / 5 -1) to (A o1 / 2 / 3 / 4 / 5 -5), The white dots represent bonds to the cyclohexane ring structure. The black dot represents a bond to -C≡C-. S o1 / 2 / 3 / 4 / 5 each represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; one or more hydrogen atoms in the alkyl or alkoxy group may each independently be substituted with a halogen atom; When there are a plurality of S o1 / 2 / 3 / 4 / 5, they may be the same or different. represents a group selected from the group consisting of groups represented by Y o1 represents a hydrogen atom or a halogen atom. A liquid crystal composition containing one or more compounds represented by the formula: the total content of the compounds represented by the general formulas (i) and (ii) in 100% by mass of the liquid crystal composition is 25% by mass or more, A liquid crystal composition, wherein the total content of the compound represented by formula (iii) is 20% by mass or more based on 100% by mass of the liquid crystal composition.

2. The liquid crystal composition according to claim 1, wherein the total content of the compound represented by general formula (o-1) in 100 mass% of the liquid crystal composition is 1 to 60 mass%.

3. As the compounds represented by the general formulae (i) and (ii), compounds represented by the following structural formulae (i-5), (i-6), (ii-5), (ii-6) and (ii-7) 【Chemistry 6】 3. The liquid crystal composition according to claim 1, further comprising one or more compounds selected from the group consisting of compounds represented by the following formula:

4. Δn at 25° C. and 589 nm is 0.40 or more, and / or the upper limit temperature of the liquid crystal phase (T ｎｉ 3. The liquid crystal composition according to claim 1, wherein the liquid crystal temperature is 170° C. or lower.

5. A liquid crystal display device using the liquid crystal composition according to claim 1 or 2.

6. 6. The liquid crystal display element according to claim 5, which is driven by an active matrix method or a passive matrix method.

7. 3. A liquid crystal display device which reversibly switches the dielectric constant by reversibly changing the alignment direction of liquid crystal molecules of the liquid crystal composition according to claim 1 or 2.

8. A sensor using the liquid crystal composition according to claim 1 or 2.

9. A liquid crystal lens using the liquid crystal composition according to claim 1 or 2.

10. 3. An optical communication device using the liquid crystal composition according to claim 1.

11. An antenna using the liquid crystal composition according to claim 1 or 2.

12. 12. The antenna of claim 11, a first substrate having a plurality of slots; a second substrate facing the first substrate and having a power supply unit provided thereon; a first dielectric layer provided between the first substrate and the second substrate; A plurality of patch electrodes arranged corresponding to the plurality of slots; a third substrate on which the patch electrode is provided; a liquid crystal layer provided between the first substrate and the third substrate; 3. An antenna, wherein the liquid crystal layer contains the liquid crystal composition according to claim 1.

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