Liquid crystal compositions, as well as liquid crystal display elements, sensors, liquid crystal lenses, optical communication equipment, and antennas using the same.

Abstract

To provide a liquid crystal composition which has a high Δn value but has a Tni which is not excessively high, that is, has an excellent balance between Δn and Tni, and exhibits good storage properties at room temperature; and a liquid crystal display element, a sensor, a liquid crystal lens, an optical communication device and an antenna which are obtained using the liquid crystal composition.SOLUTION: Specifically, provided is a liquid crystal composition which contains: one or more compounds selected from the group consisting of compounds represented by general formulae (i) and (ii); and one or more compounds represented by general formula (iii). The liquid crystal composition contains prescribed quantities of the compound(s) represented by general formulae (i) and (ii) and the compound(s) represented by general formula (iii).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to liquid crystal compositions and to liquid crystal display elements, sensors, liquid crystal lenses, optical communication equipment, and antennas using the same. [Background technology]

[0002] As a new application for liquid crystal displays (LCDs), which are widely used in displays, antennas using LCDs to transmit and receive radio waves between mobile vehicles such as automobiles and communication satellites are attracting attention. Conventionally, satellite communications have used parabolic antennas, but when used in mobile vehicles such as automobiles, the parabolic antenna must be constantly pointed towards the satellite, requiring a large movable part. However, with LCD antennas, the direction of radio wave transmission and reception can be changed by the movement of the LCD inside the panel, so there is no need to move the antenna itself, and the shape of the antenna can be made flat. Furthermore, in order to realize global high-capacity and high-speed communication, studies are underway on low-Earth orbit satellite constellations using many low-Earth orbit satellites. To track low-Earth orbit satellites, which appear to be constantly moving from the ground, LCD antennas that can easily change the direction of radio wave transmission and reception are useful. Generally, autonomous driving systems for vehicles require the download of large amounts of high-precision 3D map data. However, with an antenna using liquid crystal (LCD), by integrating the antenna into the vehicle, large amounts of data can be downloaded from communication satellites without any mechanically moving parts. The frequency band used for satellite communication is approximately 13 GHz, which is significantly different from the frequencies used for conventional LCD displays. Therefore, the required physical properties of the LCD are also significantly different; for example, the required Δn for LCD used in antennas is around 0.4, and the operating temperature range is, for example, -20 to 120°C. Furthermore, infrared laser image recognition and distance measuring devices using liquid crystals are attracting attention as sensors for autonomous driving of mobile vehicles such as automobiles. The required Δn for liquid crystals in this application 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 crystalline compounds constituting liquid crystal compositions exhibiting a high Δn of 0.2 or higher have low compatibility. Therefore, selecting liquid crystalline compounds with high compatibility is also important. In contrast, an example of liquid crystal technology for antennas is Patent Document 1. Furthermore, 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] Japanese Patent Publication No. 2016-37607 [Non-patent literature]

[0004] [Non-Patent Document 1] Dolfi, "Electronics Letters," (UK), 1993, Vol. 29, No. 10, pp. 926-928. [Overview of the project] [Problems that the invention aims to solve]

[0005] Liquid crystal compositions with a large Δn often utilize compounds with extended π-conjugation, thus affecting the T of the liquid crystal composition. ni The liquid crystal composition tends to be high, and since it is necessary to heat it to a high temperature when dissolving such a liquid crystal composition, there is a risk that the liquid crystal composition will degrade due to heat. There are also concerns about storage stability, as the liquid crystal composition tends to solidify even at room temperature. This invention has a large Δn, but T ni The ratio of Δn to T should not become too high, that is, Δn and T ni The objective is to provide a liquid crystal composition with excellent balance and good storage properties at room temperature, as well as liquid crystal display elements, sensors, liquid crystal lenses, optical communication equipment, and antennas using the same. [Means for solving the problem]

[0006] As a result of diligent research, the present inventors have found that the above problems can be solved by providing a liquid crystal composition containing one or more compounds selected from the group consisting of compounds represented by general formulas (i) and (ii), which have three benzene ring structures and -C≡C- and an isothiocyanate group (-NCS) as linking groups between the ring structures, and one or more compounds represented by general formula (iii), which have -C≡C- and an isothiocyanate group (-NCS) as linking groups between the ring structures, and by setting the content of the compounds represented by general formulas (i) and (ii) and the compound represented by general formula (iii) to predetermined amounts, thereby completing the present invention. An example of the configuration of the present invention that solves the above problems is as follows.

[0007] Section 1. The following general formulas (i) and (ii)

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

[0009] [Chemical formula] (In general formula (iii), R iii1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and one or more -CH2- in the alkyl group may each be independently substituted with -O-; one or more -CH2-CH2- in the alkyl group may each be independently substituted with -CH=CH- and / or -CF=CF-; one or more hydrogen atoms in the alkyl group may each be independently substituted with a halogen atom, provided that oxygen atoms are not directly bonded to each other; A iii1 represents the following general formula (A iii1 -1) to (A iii1 -5)

[0010] [Chemical formula] (In general formulas (A iii1 -1) to (A iii1 -5), the white dot represents a bond to R<A iii1 and the black dot represents a bond to -C≡C-; the black dot represents a bond to -C≡C-; 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, and one or more hydrogen atoms in the alkyl group or alkoxy group may each be independently substituted with a halogen atom; S iii1 when there are a plurality of S, they may be the same or different. ) represents a group selected from the group consisting of the 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 above general formulas (i) and (ii) in 100% by mass of the liquid crystal composition is 25% by mass or more. A liquid crystal composition in which the total content of the compound represented by the general formula (iii) in 100% by mass of the liquid crystal composition is 20% by mass or more.

[0011] Section 2. Furthermore, the following general formulas (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 of these 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 be independently substituted with -O- groups. One or more -CH2-CH2- groups in the alkyl group may be independently substituted with -CH=CH- and / or -CF=CF-. One or more hydrogen atoms in the alkyl group may be independently substituted with halogen atoms, Oxygen atoms do not directly bond with each other. A o1 , A o2 , A o3 , A o4 and A o5 Each of these independently gives 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 the cyclohexane ring structure, indicating bonds to -CH=CH- or -C≡C-. The black dots represent -C≡C- or bonds to a benzene ring structure. S o1 / 2 / 3 / 4 / 5 This represents one of the following: 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 be independently substituted with halogen atoms. S o1 / 2 / 3 / 4 / 5 If there are multiple instances, they may be identical or different. This represents a group selected from the group consisting of groups represented by , Y o1 , Y o2 , Y o3 , Y o4 and Y o5 Each of these independently represents either a hydrogen atom or a halogen atom. The liquid crystal composition according to item 1, comprising one or more compounds selected from the group consisting of compounds represented by .

[0014] Section 3. The compounds represented by the general formulas (i) and (ii) above are the following structural formulas (i-5), (i-6), (ii-5), (ii-6), and (ii-7).

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

[0016] Item 4. Δn at 25℃ and 589nm is 0.40 or greater, and / or the upper limit temperature of the liquid crystal phase (T ni A liquid crystal composition according to any one of items 1 to 3, wherein the temperature is 170°C or lower.

[0017] Item 5. A liquid crystal display element using a liquid crystal composition described in any one of items 1 to 4.

[0018] Item 6. A liquid crystal display element as described in Item 5, driven by an active-matrix or passive-matrix method.

[0019] Item 7. A liquid crystal display element that reversibly switches the dielectric constant by reversibly changing the orientation direction of the liquid crystal molecules of the liquid crystal composition described in any one of items 1 to 4.

[0020] Item 8. A sensor using a liquid crystal composition described in any one of items 1 to 4.

[0021] Item 9. A liquid crystal lens using a liquid crystal composition described in any one of items 1 to 4.

[0022] Item 10. Optical communication equipment using a liquid crystal composition described in any one of items 1 to 4.

[0023] Item 11. An antenna using a liquid crystal composition as described in any one of items 1 to 4.

[0024] Item 12. An antenna as described in Item 11, A first circuit board equipped with multiple slots, A second substrate, which is opposite the first substrate and has a power supply section, A first dielectric layer is provided between the first substrate and the second substrate, Multiple patch electrodes arranged corresponding to the multiple slots, A third substrate on which the aforementioned patch electrodes are provided, The device comprises a liquid crystal layer provided between the first substrate and the third substrate, An antenna in which the liquid crystal layer contains the liquid crystal composition described in any one of items 1 to 4. [Effects 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- and an isothiocyanate group (-NCS) as linking groups between the ring structures, and one or more compounds represented by general formula (iii) having -C≡C- and an isothiocyanate group (-NCS) as linking groups between the ring structures, by setting the content of the compounds represented by general formulas (i) and (ii) and the compound represented by general formula (iii) in predetermined amounts, Δn and T ni This invention provides a liquid crystal composition with excellent balance and storage stability at room temperature, and this liquid crystal composition is useful for liquid crystal display elements, sensors, liquid crystal lenses, optical communication equipment, and antennas. [Modes for carrying out the invention]

[0026] (Compounds represented by general formulas (i) and (ii)) The liquid crystal composition according to the present invention contains 25% by mass or more of one or more compounds selected from the group consisting of compounds represented by the following general formulas (i) and (ii), which have three benzene ring structures and -C≡C- and an isothiocyanate group (-NCS) as linking groups between the ring structures, in a concentration of 25% by mass or more per 100% by mass of the liquid crystal composition.

[0027] [ka]

[0028] In general formulas (i) and (ii), R i1 and R ii1 This 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 a linear alkyl group is preferred. The number of carbon atoms in an alkyl group having 1 to 20 carbon atoms is preferably 2 to 10, and more preferably 2 to 6. One or more -CH2- groups in the alkyl group may be independently substituted with -O- groups. Furthermore, one or more -CH2-CH2- groups in the alkyl group may be independently substituted with -CH=CH- and / or -CF=CF-. Furthermore, one or more hydrogen atoms in the alkyl group may be independently substituted with halogen atoms. Examples of halogen atoms include fluorine, chlorine, and bromine. However, if the alkyl group is substituted with a predetermined group, oxygen atoms will not directly bond to each other. For example, R i1 and R ii1 This can represent an alkoxy group having 1 to 19 carbon atoms by substituting one -CH2- in the alkyl group with -O-. The alkoxy group is a linear, branched, or cyclic alkoxy group, and a linear alkoxy group is preferred. The number of carbon atoms in the alkoxy group is preferably 2 to 10, and more preferably 2 to 6. Also, R i1 and R ii1 This can represent an alkenyl group having 2 to 20 carbon atoms by substituting one or more -CH2-CH2- groups in the alkyl group with -CH=CH- groups. The alkenyl group is a linear, branched, or cyclic alkenyl group, and a linear alkenyl group is preferred. The number of carbon atoms in the alkenyl group is preferably 2 to 10, and more preferably 2 to 6. Also, R i1 and R ii1 This can represent an alkenyloxy group having 2 to 19 carbon atoms, by having one -CH2- in the alkyl group replaced with -O-, and one or more -CH2-CH2- units replaced with -CH=CH-. The alkenyloxy group is a linear, branched, or cyclic alkenyloxy group, and a linear alkenyloxy group is preferred. The number of carbon atoms in the alkenyloxy group is preferably 2 to 10, and more preferably 2 to 6. Also, R i1 and R ii1 This 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 is linear, branched, or cyclic, and is preferably linear. The number of carbon atoms in the alkyl halogen is preferably 2 to 10, and more preferably 2 to 6. Also, R i1 and R ii1 This can represent a halogenated alkoxy group having 1 to 19 carbon atoms, by substituting one -CH2- in the alkyl group with -O-, and substituting one or more hydrogen atoms in the alkyl group with halogen atoms. The halogenated alkoxy group is a linear, branched, or cyclic halogenated alkoxy group, and a linear halogenated alkoxy group is preferred. The number of carbon atoms in the halogenated alkoxy group is preferably 2 to 10, and more preferably 2 to 6. R i1 and R ii1 Specific examples of alkyl groups with 1 to 20 carbon atoms in the formula (including substituted ones) include the formula (R i1 / ii1 -1)~(R i1 / ii1 Examples of bases represented by -31) include the ones shown.

[0029] [ka]

[0030] Formula (R i1 / ii1 -1)~(R i1 / ii1 -31) In this example, the black dots represent bonds to the benzene ring structure. Note, R i1 and R ii1 From the viewpoint of Δn and compatibility with other liquid crystal compounds, linear alkyl groups having 2 to 6 carbon atoms are preferred. Also, R i1and R ii1 From the viewpoint of liquid crystalline properties and viscosity, linear alkenyl groups having 2 to 6 carbon atoms are preferred.

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

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

[0033] [ka]

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

[0035] [ka]

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

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

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

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

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

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

[0042] Compounds represented by general formulas (i) and (ii) (including sub-concepts) can be synthesized using known synthetic methods, some of which are given below as examples. (Method 1) Preparation of the compound represented by the following general formula (s-5)

[0043] [ka]

[0044] In the formula, R i1 and Y i1 R in the above general formula (i) is i1 and Y i1 It expresses the same meaning. First, by reacting the compound represented by general formula (s-1) with 1-bromo-4-iodobenzene, the compound represented by general formula (s-2) can be obtained. One example of a reaction method is the 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), and tetrakis(triphenylphosphine)palladium(O). Examples of bases include potassium carbonate, sodium carbonate, and potassium phosphate. Next, by reacting the compound represented by general formula (s-2) with the compound represented by general formula (s-3), a compound represented by general formula (s-4) can be obtained. Examples of reaction methods include the 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), and tetrakis(triphenylphosphine)palladium(O). When using palladium(II) acetate as a metal catalyst, ligands such as triphenylphosphine and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl may be added. A specific example of a copper catalyst is copper(I) iodide. Specific examples of bases include triethylamine. Furthermore, by reacting the compound represented by general formula (s-4) with NCS-forming agents such as thiophosgene, carbon disulfide, 1,1-thiocarbonyldiimidazole, and 1,1'-thiocarbonyldi-2(1H)pyridone, the target compound represented by general formula (s-5) can be obtained. (Method 2) Preparation of the compound represented by the following general formula (s-10)

[0045] [ka]

[0046] In the formula, R ii1 and Y ii1 R in the general formula (ii) is ii1 and Y ii1 It expresses the same meaning. First, the compound represented by general formula (s-6) is reacted with trimethylsilylacetylene, and then reacted with potassium carbonate in an alcohol solvent to obtain the compound represented by general formula (s-7). Reactions with trimethylsilylacetylene include the Sonogashira coupling reaction using a palladium catalyst, a copper catalyst, and a base. The above are examples of palladium catalysts and bases. Next, a compound represented by general formula (s-7) can be reacted with a compound represented by general formula (s-8) to obtain a compound represented by general formula (s-9). Examples of reaction methods include the Sonogashira coupling reaction using a palladium catalyst, a copper catalyst, and a base. The above are examples of palladium catalysts, copper catalysts, and bases. Furthermore, by reacting the compound represented by general formula (s-9) with NCS-forming agents such as thiophosgene, carbon disulfide, 1,1-thiocarbonyldiimidazole, and 1,1'-thiocarbonyldi-2(1H)pyridone, the target compound represented by general formula (s-10) can be obtained.

[0047] (Compounds represented by general formula (iii)) The liquid crystal composition according to the present invention contains 20% by mass or more of one or more compounds represented by general formula (iii), which have -C≡C- and an isothiocyanate group (-NCS) as linking groups between ring structures, in a concentration of 20% by mass or more of the liquid crystal composition.

[0048] [ka]

[0049] In general formula (iii), R iii1 This represents an alkyl group with 1 to 20 carbon atoms. The alkyl group is linear, branched, or cyclic, and is preferably linear. The number of carbon atoms in the alkyl group is preferably 2 to 10, and more preferably 2 to 6. One or more -CH2- groups in the alkyl group may be independently substituted with -O- groups. Furthermore, 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 be independently substituted with halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. However, if the alkyl group is substituted with a predetermined group, oxygen atoms will not directly bond to each other. For example, R iii1 This can represent an alkoxy group having 1 to 19 carbon atoms by substituting one -CH2- in the alkyl group with -O-. The alkoxy group is a linear, branched, or cyclic alkoxy group, and a linear alkoxy group is preferred. The number of carbon atoms in the alkoxy group is preferably 2 to 10, and more preferably 2 to 6. Also, R iii1 This can represent an alkenyl group having 2 to 20 carbon atoms by substituting one or more -CH2-CH2- groups in the alkyl group with -CH=CH- groups. The alkenyl group is a linear, branched, or cyclic alkenyl group, and a linear alkenyl group is preferred. The number of carbon atoms in the alkenyl group is preferably 2 to 10, and more preferably 2 to 6. Also, R iii1This can represent an alkenyloxy group having 2 to 19 carbon atoms, by having one -CH2- in the alkyl group replaced with -O-, and one or more -CH2-CH2- units replaced with -CH=CH-. The alkenyloxy group is a linear, branched, or cyclic alkenyloxy group, and a linear alkenyloxy group is preferred. The number of carbon atoms in the alkenyloxy group is preferably 2 to 10, and more preferably 2 to 6. Also, R iii1 This 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 is linear, branched, or cyclic, and is preferably linear. The number of carbon atoms in the alkyl halogen is preferably 2 to 10, and more preferably 2 to 6. Also, R iii1 This can represent a halogenated alkoxy group having 1 to 19 carbon atoms, by substituting one -CH2- in the alkyl group with -O-, and substituting one or more hydrogen atoms in the alkyl group with halogen atoms. The halogenated alkoxy group is a linear, branched, or cyclic halogenated alkoxy group, and a linear halogenated alkoxy group is preferred. The number of carbon atoms in the halogenated alkoxy group is preferably 2 to 10, and more preferably 2 to 6. R iii1 Specific examples of alkyl groups with 1 to 20 carbon atoms in the formula (including substituted ones) include the formula (R iii1 -1)~(R iii1 Examples of bases represented by -30) include the ones shown.

[0050] [ka]

[0051] Formula (Riii1 -1) to (R iii1 -30), the black dots represent the bonds to A iii1 represents the bond to. R iii1 In terms of solubility, a linear alkyl group having 1 to 8 carbon atoms or a linear alkenyl group having 2 to 6 carbon atoms is preferable.

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

[0053]

Chemical formula

[0054] [[ID=3C]] In general formula (A iii1 -1) to (A iii1 -5), the white dots represent the bonds to R iii1 and the black dots represent the bonds to -C≡C-.

[0055] In general formula (A<00000c94>-1) to (A iii1 -5), 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 be independently substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. [[ID=5C]]S iii1Specific examples of alkyl groups with 1 to 6 carbon atoms and alkoxy groups with 1 to 6 carbon atoms in the formula (S iii1 -1)~(S iii1 Examples of bases represented by -16) include the ones shown.

[0056] [ka]

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

[0058] More specifically, the general formula (A iii1 -2) is given by the following formula (A iii1 -2-1)~(A iii1 It is preferable to represent one of the following (-2-4):

[0059] [ka]

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

[0061] More specifically, the general formula (A iii1 -3) is given by the following formula (A iii1 -3-1)~(A iii1 It is preferable to represent one of the following (-3-4):

[0062] [ka]

[0063] General formula (A iii1 -3-1)~(Aiii1 -3-4) Among them, the white dots are R iii1 The black dot represents a bond to -C≡C-, and the black dot represents a bond to -C≡C-.

[0064] More specifically, the general formula (A iii1 -4) is given by the following formula (A iii1 -4-1)~(A iii1 It is preferable to represent one of the following: -4-4)

[0065] [ka]

[0066] General formula (A iii1 -4-1)~(A iii1 -4-4) White dots are R iii1 The black dot represents a bond to -C≡C-, and the black dot represents a bond to -C≡C-.

[0067] More specifically, the general formula (A iii1 -5) is given by the following formula (A iii1 -5-1)~(A iii1 It is preferable to represent one of the following (-5-4):

[0068] [ka]

[0069] General formula (A iii1 -5-1)~(A iii1 -5-4) Among them, the white dots are R iii1 The black dot represents a bond to -C≡C-, and 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 halogen atoms include fluorine, chlorine, and bromine. From the viewpoint of dielectric anisotropy (Δε) and compatibility, Y iii1 A fluorine atom is preferred.

[0071] As for the compound represented by general formula (iii), it is preferable that it be the 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 R in the above general formula (iii) is iii1 It expresses the same meaning. Specific examples of compounds represented by general formula (iii-1) include those represented by structural formulas (iii-1.1) to (iii-1.7) below. From the viewpoint of Δn, compounds represented by structural formulas (iii-1.5) and (iii-1.6) are preferred, and from the viewpoint of solubility and low viscosity, compounds represented by structural formulas (iii-1.1) and (iii-i-8) are preferred.

[0074] [ka]

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

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

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

[0078] The total content of the compound represented by general formula (iii) (including its sub-concept) in 100% by mass of the liquid crystal composition is 20% by mass or more, preferably 20 to 55% by mass, preferably 25 to 55% by mass, and preferably 35 to 50% by mass. If the content is less than 20% by mass, the content of other compounds will increase, ni Sometimes the price can become too high.

[0079] Compounds represented by general formula (iii) (including sub-concepts) can be synthesized using known synthetic methods.

[0080] (Other compounds) The liquid crystal composition according to the present invention comprises Δn and / or Δε r From this perspective, the compound 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 of these independently represents either a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The alkyl group is linear, branched, or cyclic, and is preferably linear. The number of carbon atoms in the alkyl group is preferably 2 to 10, and more preferably 2 to 6. One or more -CH2- groups in the alkyl group may be independently substituted with -O- groups. Furthermore, 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 be independently substituted with halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. However, if the alkyl group is substituted with a predetermined group, oxygen atoms will not directly bond to each other. For example, R o1 , R o2 , R o3 , R o4 and R o5 This can represent an alkoxy group having 1 to 19 carbon atoms by substituting one -CH2- in the alkyl group with -O-. The alkoxy group is a linear, branched, or cyclic alkoxy group, and a linear alkoxy group is preferred. The number of carbon atoms in the alkoxy group is preferably 2 to 10, and more preferably 2 to 6. Also, R o1 , R o2 , R o3 , R o4 and R o5 This can represent an alkenyl group having 2 to 20 carbon atoms by substituting one or more -CH2-CH2- groups in the alkyl group with -CH=CH- groups. The alkenyl group is a linear, branched, or cyclic alkenyl group, and a linear alkenyl group is preferred. The number of carbon atoms in the alkenyl group is preferably 2 to 10, and more preferably 2 to 6. Also, R o1 , R o2 , R o3 , R o4 and R o5This can represent an alkenyloxy group having 2 to 19 carbon atoms, by having one -CH2- in the alkyl group replaced with -O-, and one or more -CH2-CH2- units replaced with -CH=CH-. The alkenyloxy group is a linear, branched, or cyclic alkenyloxy group, and a linear alkenyloxy group is preferred. The number of carbon atoms in the alkenyloxy group is preferably 2 to 10, and more preferably 2 to 6. Also, R o1 , R o2 , R o3 , R o4 and R o5 This 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 is linear, branched, or cyclic, and is preferably linear. The number of carbon atoms in the alkyl halogen is preferably 2 to 10, and more preferably 2 to 6. Also, R o1 , R o2 , R o3 , R o4 and R o5 This can represent a halogenated alkoxy group having 1 to 19 carbon atoms, by substituting one -CH2- in the alkyl group with -O-, and substituting one or more hydrogen atoms in the alkyl group with halogen atoms. The halogenated alkoxy group is a linear, branched, or cyclic halogenated alkoxy group, and a linear halogenated alkoxy group is preferred. The number of carbon atoms in the halogenated alkoxy group is preferably 2 to 10, and more preferably 2 to 6. R o1 , R o2 , R o3 , R o4 and R o5 Specific examples of alkyl groups with 1 to 20 carbon atoms in the formula (including substituted ones) include the formula (Ro1 / 2 / 3 / 4 / 5 -1)~(R o1 / 2 / 3 / 4 / 5 Examples of bases represented by -31) include the ones shown.

[0083] [ka]

[0084] Formula (R o1 / 2 / 3 / 4 / 5 -1)~(R o1 / 2 / 3 / 4 / 5 -31) In this example, 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, linear alkyl groups having 1 to 6 carbon atoms and linear alkenyl groups having 2 to 6 carbon atoms are preferred.

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

[0086] [ka]

[0087] General formula (A o1 / 2 / 3 / 4 / 5 -1)~(A o1 / 2 / 3 / 4 / 5 -5) In this diagram, the white dots represent bonds to the cyclohexane ring structure, -CH=CH- or -C≡C-, and the black dots represent bonds to the -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 of these independently represents either a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. The alkyl group having 1 to 6 carbon atoms is a linear, branched, or cyclic alkyl group, and a linear alkyl group is preferred. The alkoxy group having 1 to 6 carbon atoms is a linear, branched, or cyclic alkoxy group, and a linear alkoxy group is preferred. One or more hydrogen atoms in the alkyl or alkoxy group may be independently substituted with halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. S o1 / 2 / 3 / 4 / 5 Specific examples of alkyl groups with 1 to 6 carbon atoms and alkoxy groups with 1 to 6 carbon atoms (including substituted ones) in formula (S o1 / 2 / 3 / 4 / 5 -1)~(S o1 / 2 / 3 / 4 / 5 Examples of bases represented by -16) include the ones shown.

[0089] [ka]

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

[0091] More specifically, the general formula (A o1 / 2 / 3 / 4 / 5 -2) is given by the following formula (A o1 / 2 / 3 / 4 / 5 -2-1)~(A o1 / 2 / 3 / 4 / 5 It is preferable to represent one of the following (-2-4):

[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 the cyclohexane ring structure, -CH=CH- or -C≡C-, while the black dots represent bonds to the -C≡C- or benzene ring structure.

[0094] More specifically, the general formula (A o1 / 2 / 3 / 4 / 5 -3) is given by the following formula (A o1 / 2 / 3 / 4 / 5 -3-1)~(A o1 / 2 / 3 / 4 / 5 It is preferable to represent one of the following (-3-4):

[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 the cyclohexane ring structure, -CH=CH- or -C≡C-, while the black dots represent bonds to the -C≡C- or benzene ring structure.

[0097] More specifically, the general formula (A o1 / 2 / 3 / 4 / 5 -4) is given by the following formula (A o1 / 2 / 3 / 4 / 5 -4-1)~(A o1 / 2 / 3 / 4 / 5 It is preferable to represent one of the following: -4-4)

[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 the cyclohexane ring structure, -CH=CH- or -C≡C-, while the black dots represent bonds to the -C≡C- or benzene ring structure.

[0100] More specifically, the general formula (A o1 / 2 / 3 / 4 / 5 -5) is given by the following formula (A o1 / 2 / 3 / 4 / 5 -5-1)~(A o1 / 2 / 3 / 4 / 5 It is preferable to represent one of the following (-5-4):

[0101] [Chemical]

[0102] General formula (A o1 / 2 / 3 / 4 / 5 -5-1) to (A o1 / 2 / 3 / 4 / 5 -5-4), the white dots represent bonds to a cyclohexane ring structure, -CH=CH- or -C≡C-, and the black dots represent bonds to -C≡C- or a 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 represent 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 viewpoints of dielectric anisotropy (Δε) and compatibility, Y o1 , Y o2 , Y o3 , Y o4 and Y o5 are preferably fluorine atoms.

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

[0105] [Chemical]

[0106] In general formula (o-1-1), R o1 represents the same meaning as R o1 in the above general formula (o-1). 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), etc. [[ID=Y64]]

[0107] [Chemical]

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

[0109] [ka]

[0110] In general formula (o-2-1), R o2 This is R in the above general formula (o-2). o2 It expresses the same meaning. Specific examples of compounds represented by the general formula (O-2-1) include those 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 the compound represented by the following general formula (O-3-1).

[0113] [ka]

[0114] In general formula (o-3-1), R o3 This is R in the above general formula (o-3). o3 It expresses the same meaning. Specific examples of compounds represented by the general formula (O-3-1) include those 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 the compound represented by the following general formula (o-4-1).

[0117] [Chemical formula]

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

[0119] [Chemical formula]

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

[0121] [Chemical formula]

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

[0123] [Chemical formula]

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

[0125] The total content 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) in 100% by mass of the liquid crystal composition is preferably 1 to 60% by mass, preferably 5 to 55% by mass, and preferably 10 to 50% by mass.

[0126] The types of 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 two or more types, preferably 1 to 10 types, preferably 1 to 5 types, and preferably 1 to 3 types.

[0127] The total content of 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, preferably 10 to 40% by mass, and preferably 15 to 35% by mass.

[0128] The types of 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 two or more types, preferably 1 to 10 types, preferably 1 to 5 types, and preferably 1 to 3 types.

[0129] The total content of 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, preferably 1 to 10% by mass, and preferably 3 to 7% by mass.

[0130] The types of compounds used in the liquid crystal composition 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) are one or two or more, preferably 1 to 10, preferably 1 to 5, and preferably 1 to 3.

[0131] The total content 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) in 100% by mass of the liquid crystal composition is preferably 1 to 15% by mass, preferably 1 to 10% by mass, and preferably 3 to 7% by mass.

[0132] The 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 are one or two or more types, preferably 1 to 10 types, preferably 1 to 5 types, and preferably 1 to 3 types.

[0133] The total content 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) in 100% by mass of the liquid crystal composition is preferably 5 to 35% by mass, preferably 10 to 30% by mass, and preferably 15 to 25% by mass.

[0134] Compounds represented by general formulas (o-1) to (o-5) (including sub-concepts) can be synthesized using known synthetic 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 general formula (i) and the compound represented by general formula (ii) described above, a compound represented by general formula (iii), and, if necessary, other compounds and additives described above.

[0136] Examples of additives include stabilizers, dye compounds, polymerizable compounds, azotran compounds, and isothiocyanate compounds (NCS compounds).

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

[0138] [ka]

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

[0140] [ka]

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

[0142] Furthermore, the combination of compounds used in the liquid crystal composition includes solubility, Δn and / or T ni From this perspective, 1) A combination of a compound represented by general formula (i) (including its sub-concept) and a compound represented by general formula (iii) (including its sub-concept), 2) Combinations of a compound represented by general formula (i) (including sub-concepts), a compound represented by general formula (iii) (including sub-concepts), and a compound represented by general formula (o-1) (including sub-concepts), 3) Combinations of a compound represented by general formula (i) (including sub-concepts), a compound represented by general formula (iii) (including sub-concepts), and a compound represented by general formula (o-2) (including sub-concepts), 4) Combinations of a compound represented by general formula (i) (including its sub-concept), a compound represented by general formula (iii) (including its sub-concept), and a compound represented by general formula (o-5) (including its sub-concept), 5) Combinations of compounds represented by general formula (ii) (including sub-concepts) and compounds represented by general formula (iii) (including sub-concepts), 6) Combinations of a compound represented by general formula (ii) (including its sub-concept), a compound represented by general formula (iii) (including its sub-concept), and a compound represented by general formula (o-2) (including its sub-concept), 7) Combinations 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) Combinations of a compound represented by general formula (i) (including sub-concepts), a compound represented by general formula (ii) (including sub-concepts), a compound represented by general formula (iii) (including sub-concepts), and a compound represented by general formula (o-1) (including sub-concepts), 9) Combinations of a compound represented by general formula (i) (including sub-concepts), a compound represented by general formula (ii) (including sub-concepts), a compound represented by general formula (iii) (including sub-concepts), and a compound represented by general formula (o-2) (including sub-concepts), 10) Combinations of a compound represented by general formula (i) (including sub-concepts), a compound represented by general formula (ii) (including sub-concepts), a compound represented by general formula (iii) (including sub-concepts), and a compound represented by general formula (o-3) (including sub-concepts), It is preferable.

[0143] <Characteristic values ​​of liquid crystal compositions> Liquid crystal phase upper limit temperature (T ni ) is the temperature at which the liquid crystal composition undergoes a phase transition from the nematic phase to the isotropic phase. T ni This is measured by preparing a slide by sandwiching the liquid crystal composition between a glass slide and a cover slip, and then observing it under a polarizing microscope while heating it on a hot stage. It can also be measured using differential scanning calorimetry (DSC). The unit used is "℃". T ni The higher the temperature, the more the nematic phase can be maintained even at high temperatures, allowing for a wider operating temperature range. However, since it is heated and melted during manufacturing, excessively high temperatures can cause thermal degradation of the liquid crystal and require high-temperature melting equipment, which is undesirable. ni The higher the T value, the poorer the storage stability at low temperatures tends to be. ni Achieving both high storage stability and good storage stability is difficult. The upper limit temperature of the liquid crystal phase of the liquid crystal composition according to the present invention (T ni The temperature can be set appropriately depending on whether the liquid crystal display element is used indoors or in a car where the ambient temperature can be controlled, or outdoors. However, from the viewpoint of the operating temperature range, it is preferably 170°C or lower, preferably 110 to 170°C, and preferably 115 to 165°C.

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

[0145] Δn (refractive index anisotropy) correlates with Δn in the near-infrared region used in optical sensors, which will be discussed later. A larger Δn results in greater phase modulation power for light of the target wavelength, making it particularly suitable for optical sensors. Δn at 25℃ and 589nm is the anomalous refractive index (n) of the liquid crystal composition using an Abbe refractometer. e ) and the refractive index (n o ) difference (n e -n o ) Furthermore, Δn can also be determined from the phase difference measurement device. The relationship Δn = Re / d holds between the phase difference Re, the thickness d of the liquid crystal layer, and Δn. A liquid crystal composition is injected into a glass cell with a polyimide alignment film that has undergone antiparallel rubbing treatment and has a cell gap (d) of approximately 3.0 μm. The in-plane Re is measured using a phase difference film / optical material inspection device RETS-100 (manufactured by Otsuka Electronics Co., Ltd.). The measurement was performed at a temperature of 25°C and a wavelength of 589nm, and there are no units. From the viewpoint of the phase modulation power of light of the wavelength, the Δn of the liquid crystal composition according to the present invention at 25°C and 589nm is preferably 0.40 or more, preferably 0.40 to 0.55, preferably 0.41 to 0.50, and preferably 0.43 to 0.48.

[0146] Rotational viscosity (γ1) is the viscosity related to the rotation of liquid crystal molecules. γ1 can be measured by filling a glass cell with a liquid crystal composition and a cell gap of approximately 10 μm, applying a voltage of 50 V, and using LCM-2 (manufactured by Toyo Technica). For liquid crystal compositions with positive dielectric anisotropy, horizontally aligned cells are used; for liquid crystal compositions with negative dielectric anisotropy, vertically aligned cells are used. Measurements are performed at a temperature of 25°C, and the unit used is mPa·s. Since a smaller γ1 value results in a faster response speed for the liquid crystal composition, this 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, preferably 200 to 900 mPa·s, and preferably 250 to 700 mPa·s, from the viewpoint of response speed.

[0147] Higher dielectric anisotropy in the high-frequency range results in greater phase modulation power for radio waves in the target frequency band, making it particularly suitable for antenna applications. Furthermore, for antenna applications, a smaller dielectric loss tangent in the high-frequency range is preferable because it reduces energy loss in the target frequency band. 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 region. r and the average value of the dielectric loss tangent, tanδ iso We measured it. Δε r =( ε r∥ -ε r⊥ ) and tanδ iso =(2ε r⊥ tanδ ⊥ +ε r∥ tanδ ∥ ) / (2ε r⊥ +ε r∥ ) Here, "εr" is the dielectric constant, "tanδ" is the dielectric loss tangent, the subscript "∥" indicates a component parallel to the orientation direction of the liquid crystal, and "⊥" indicates a component perpendicular to the orientation direction of the liquid crystal.

[0148] Δε r and tanδ iso It can be measured by the following method. First, the liquid crystal composition is introduced into a capillary tube made of polytetrafluoroethylene (PTFE). The capillary tube 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. A capillary tube containing a liquid crystal composition is introduced into the center of a cavity resonator (manufactured by EM Lab Co., Ltd.) with a resonant frequency of 10 GHz. This cavity resonator has an outer diameter of 30 mm and an outer width of 26 mm. Then, a signal is input, and the result of the output signal is recorded using a network analyzer (manufactured by Keysight Technologies, Inc.). Using the difference between the resonance frequency of a PTFE capillary tube without a liquid crystal composition and the resonance frequency of a PTFE capillary tube with a liquid crystal composition, the dielectric constant (ε) at 10 GHz is determined. r ) and the loss angle (δ) are determined. The resulting tangent to δ is the dielectric loss tangent (tanδ). Furthermore, the resonance frequency and other properties of a PTFE capillary tube containing a liquid crystal composition are determined by controlling the orientation of the liquid crystal molecules, and are obtained as the values ​​of characteristic components perpendicular to and parallel to the orientation direction of the liquid crystal molecules. A magnetic field from a permanent magnet or electromagnet is used to align liquid crystal molecules perpendicular to the PTFE capillary (perpendicular to the effective length direction) or parallel to it (parallel to the effective length direction). For example, with a magnetic pole distance of 45 mm, the magnetic field strength near the center is 0.23 Tesla. Desired characteristic components are obtained by rotating a PTFE capillary tube containing a liquid crystal composition parallel or perpendicular to a magnetic field. The measurement was performed at a temperature of 25°C, and Δε r and tanδ iso Neither has units.

[0149] Δε at 25°C for the liquid crystal composition according to the present invention r While a larger value is preferable, from the viewpoint of phase modulation power in the GHz band, it is preferably 0.90 or higher, preferably 0.90 to 1.50, preferably 0.95 to 1.40, and preferably 1.00 to 1.35. The tanδ of the liquid crystal composition according to the present invention at 25°C iso While a smaller value is preferable, 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 equipment, and antennas) The following describes liquid crystal display elements, sensors, liquid crystal lenses, optical communication equipment, and antennas using the liquid crystal composition according to the present invention.

[0151] The liquid crystal display element according to the present invention is characterized by using the above-described liquid crystal composition and is preferably driven by an active matrix or passive matrix method. Furthermore, the liquid crystal display element according to the present invention is preferably a liquid crystal display element that reversibly switches the dielectric constant by reversibly changing the orientation 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 such embodiments include a distance measuring sensor that utilizes electromagnetic waves, visible light or infrared light, an infrared sensor that utilizes temperature changes, a temperature sensor that utilizes changes in reflected light wavelength due to changes in the pitch of cholesteric liquid crystal, a pressure sensor that utilizes changes in reflected light wavelength, an ultraviolet sensor that utilizes changes in reflected light wavelength due to changes in composition, an electrical sensor that utilizes temperature changes due to voltage or current, a radiation sensor that utilizes temperature changes associated with the tracks of radiation particles, an ultrasonic sensor that utilizes changes in liquid crystal molecular arrangement due to mechanical vibrations of ultrasound, and an electromagnetic field sensor that utilizes changes in reflected light wavelength due to temperature changes or changes in liquid crystal molecular arrangement due to electric fields. For the distance measuring sensor, it is preferable to use one designed for LiDAR (Light Detection and Ranging) which uses a light source. LiDAR is preferably used for satellites, aircraft, unmanned aerial vehicles (drones), automobiles, railways, and ships. For automotive applications, it is particularly preferable for autonomous vehicles. The light source is preferably an LED or a laser, and is preferably a laser. The light used in LiDAR is preferably infrared light, and its wavelength is preferably 800 to 2000 nm. In particular, infrared lasers with wavelengths of 905 nm or 1550 nm are preferred. If the cost of the photodetector used and sensitivity in all weather conditions are important, a 905nm infrared laser is preferred, while if safety regarding human vision is important, a 1550nm infrared laser is preferred. Because the liquid crystal composition according to the present invention exhibits a high Δn, it has a large phase modulation capability in the visible light, infrared light, and electromagnetic wave regions, and can provide a sensor with excellent detection sensitivity.

[0153] The liquid crystal lens according to the present invention is characterized by using the above-described liquid crystal composition, and for example, in one embodiment, it comprises a first transparent electrode layer, a second transparent electrode layer, a liquid crystal layer containing the above-described 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 can be 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-described liquid crystal composition, and one example of such a device is an LCOS (Liquid crystal on silicon) having a liquid crystal layer on a reflective layer (electrode) in which liquid crystals constituting each of a plurality of pixels are arranged in a two-dimensional manner. The optical communication device according to the present invention can be used, for example, as a spatial phase modulator.

[0155] The antenna according to the present invention is characterized by using the above-described liquid crystal composition. More specifically, the antenna according to the present invention comprises a first substrate having a plurality of slots, a second substrate facing the first substrate and provided with 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 on which the patch electrodes are provided, 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 has high reliability against external stimuli such as heat. Furthermore, it is possible to provide an antenna that enables greater phase control for microwave or millimeter-wave electromagnetic waves. The antenna according to the present invention preferably operates in the Ka-band, K-band, or Ku-band frequencies used for satellite communications. The antenna according to the present invention preferably has a configuration that combines a radial line slot array and a patch antenna array. The antenna structure according to the present invention can be applied by taking into consideration, for example, matters described in International Publication No. 2021 / 157189, etc. [Examples]

[0156] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way to the following examples. The compositions of the following examples and comparative examples contain each compound in the proportions shown in the table, and the content is indicated in "mass%". Furthermore, the following abbreviations will be used to describe the compounds. Note that compounds that can exist as both cis and trans isomers will be referred to as the trans isomer unless otherwise specified. <Ring structure>

[0157] [ka]

[0158] <Terminal structure>

[0159] [Table 1] (However, n in the table is a natural number. Also, the alkyl group represented by n is a linear alkyl group.)

[0160] <Connection structure>

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

[0162] (Hindered phenol antioxidants)

[0163] [ka]

[0164] (Hindered amine-based light stabilizers)

[0165] [ka]

[0166] (Preparation of liquid crystal composition) LC-A to B and LC-01 to 08, as listed in Table 3, were prepared.

[0167] [Table 3]

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

[0169] [Table 4]

[0170] [Table 5]

[0171] From Example 1 and Comparative Examples 1-2, a liquid crystal composition containing one or more compounds selected from the group consisting of compounds represented by the general formulas (i) and (ii) and one or more compounds represented by the general formula (iii) in predetermined amounts is found to have Δn and T ni It has been confirmed to have an excellent balance and good storage properties at room temperature, Δε r , tanδ iso It also showed good values. On the other hand, as shown in Comparative Examples 1 and 2, liquid crystal compositions that do not contain a predetermined amount of one or more compounds selected from the group consisting of compounds represented by the general formulas (i) and (ii) and one or more compounds represented by the general formula (iii) have a Δn of less than 0.40 or T ni The results showed temperatures as high as 175°C or higher. Furthermore, in Comparative Example 1, it was confirmed that LC-A crystallized four days after preparation. Furthermore, as shown in Examples 2 to 14, similar effects were confirmed when various compounds were used or when hindered phenol antioxidants or hindered amine light stabilizers were used in combination. The synthesis of compounds represented by general formulas (i) and (ii) is described below. (Synthesis Example 1) Preparation of the compound represented by formula (I-1)

[0172] [ka]

[0173] Under a nitrogen atmosphere, 17 g of the compound represented by formula (I-1-1), 2.3 g of tetrakis(triphenylphosphine)palladium, 20 g of potassium carbonate, 29 g of 1-bromo-4-iodobenzene, 200 mL of tetrahydrofuran, and 40 mL of water were added to a reaction vessel, and the reaction vessel was heated to 70°C. After the reaction was complete, 10% by mass hydrochloric acid was poured into the reaction mixture and extracted with ethyl acetate. The organic layer was washed with saturated brine, the solvent was removed by distillation, and dispersion washing with hexane was performed to obtain 23 g 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 the reaction vessel. Then, while heating at 85°C, a solution of 13 g of the compound represented by formula (I-1-3) dissolved in 25 mL of N,N-dimethylformamide was added dropwise, and the mixture was stirred at 85°C for 3 hours. After the reaction was complete, saturated aqueous ammonium chloride solution was poured into the reaction mixture and extracted with ethyl acetate. The organic layer was washed with saturated brine, 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 the reaction was carried out at room temperature. After the reaction was complete, the organic layer was washed with saturated brine, 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] Under a nitrogen atmosphere, 21.0 g of the compound represented by formula (I-2-1), 0.8 g of copper(I) iodide, 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 of 20 g of trimethylsilylacetylene dissolved in 50 mL of N,N-dimethylformamide was added dropwise, and the mixture was stirred at 70°C for 2 hours. After the reaction was complete, 10% by mass hydrochloric acid was poured into the reaction mixture and extracted with toluene. The organic layer was washed with saturated brine, and then subjected to column chromatography (silica gel, toluene) and solvent removal. Further, 20 g of potassium carbonate and 200 ml of methanol were added, and the reaction vessel was heated to 50°C and reacted for 2 hours. The reaction mixture was then extracted with toluene, the organic layer was washed with saturated brine, and then subjected to column chromatography (silica gel, toluene) and solvent removal 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 the reaction vessel. Then, while heating at 85°C, a solution of 14 g of the compound represented by formula (I-2-2) dissolved in 25 mL of N,N-dimethylformamide was added dropwise, and the mixture was stirred at 85°C for 3 hours. After the reaction was complete, saturated aqueous ammonium chloride solution was poured into the reaction mixture and extracted with ethyl acetate. The organic layer was washed with saturated brine, 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 the reaction was carried out at room temperature. After the reaction was complete, the organic layer was washed with saturated brine, 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] Under a nitrogen atmosphere, 22.5 g of the compound represented by formula (I-3-1), 0.8 g of copper(I) iodide, 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 of 20 g of trimethylsilylacetylene dissolved in 50 mL of N,N-dimethylformamide was added dropwise, and the mixture was stirred at 70°C for 2 hours. After the reaction was complete, 10% by mass hydrochloric acid was poured into the reaction mixture and extracted with toluene. The organic layer was washed with saturated brine, and then subjected to column chromatography (silica gel, toluene) and solvent removal. Further, 20 g of potassium carbonate and 200 ml of methanol were added, and the reaction vessel was heated to 50°C and reacted for 2 hours. The reaction mixture was then extracted with toluene, the organic layer was washed with saturated brine, and then subjected to column chromatography (silica gel, toluene) and solvent removal to obtain 15 g of the compound represented by formula (I-3-2). Next, under a nitrogen atmosphere, 22.5 g of the compound represented by formula (I-3-3), 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 the reaction vessel. Then, while heating at 85°C, a solution of 15 g of the compound represented by formula (I-3-2) dissolved in 25 mL of N,N-dimethylformamide was added dropwise, and the mixture was stirred at 85°C for 3 hours. After the reaction was complete, saturated aqueous ammonium chloride solution was poured into the reaction mixture and extracted with ethyl acetate. The organic layer was washed with saturated brine, and then recrystallized with toluene to obtain 22 g 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 the reaction was carried out at room temperature. After the reaction was complete, the organic layer was washed with saline solution, 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 elements, sensors, liquid crystal lenses, optical communication equipment, and antennas.

Claims

1. The following general formula (i) or (ii) 【Chemistry 1】 (In general formulas (i) and (ii), R i1 and R iii1 each independently represent an alkenyl group having 2 to 20 carbon atoms or an alkenyloxy group having 2 to 19 carbon atoms. Oxygen atoms do not directly bond with each other. Y i1 and Y iii1 each independently represent a hydrogen atom or a halogen atom. A compound represented by the formula.

2. The compound according to claim 1, wherein Y i1 and Y iii1 represent halogen atoms.

3. Ri1 and Rii1 are given by the following formulas (Ri1 / iii1 -12) to (Ri1 / iii1 -21) and formulas (Ri1 / iii1 -27) to (Ri1 / iii1 -31) 【Chemistry 1】 (In equations (R i1 / iii1 -12) to (R i1 / iii1 -21) and equations (R i1 / iii1 -27) to (R i1 / iii1 -31), The black dots represent bonds to the benzene ring structure. A compound according to claim 1 or 2, selected from the group consisting of groups represented by the following:

4. A liquid crystal composition containing one or more compounds according to claim 1 or 2.

5. The liquid crystal composition according to claim 4, wherein the total content of the compound represented by general formula (i) or general formula (ii) in 100% by mass of the liquid crystal composition is 1% by mass or more.

6. The liquid crystal composition according to claim 4, wherein the Δn of the liquid crystal composition at 25°C and 589 nm is 0.43 or more.

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