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

Abstract

The present invention addresses the problem of providing: 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.　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).

Description

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

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

[0002] Liquid crystals, which are widely used in displays, are attracting attention as a new application for LCD antennas that transmit and receive radio waves between mobile vehicles such as automobiles and communication satellites. Traditionally, satellite communications have used parabolic antennas, but when used in mobile vehicles such as automobiles, the antennas must be constantly pointed toward the satellite, necessitating large moving parts. However, LCD antennas can change the direction of radio waves by moving the liquid crystals inside the panel, eliminating the need to move the antenna itself and allowing for flat antenna shapes. Furthermore, to achieve high-capacity, high-speed global communications, low-earth-orbit (LOW-EO) satellite constellations with numerous low-earth-orbit (LOW-EO) satellites are being studied. LCD antennas, which can easily change the direction of radio waves to track LEO satellites that appear constantly moving from the ground, are useful. Autonomous driving, such as in automobiles, generally requires the downloading of large amounts of high-precision 3D map information. However, by incorporating LCD antennas into automobiles, large amounts of data can be downloaded from communication satellites without any mechanical moving parts. The frequency band used in satellite communications is approximately 13 GHz, significantly different from the frequencies used in conventional LCD display applications. Therefore, the physical properties required for liquid crystals vary significantly. For example, a Δn of approximately 0.4 is required for liquid crystals used in antennas, with an operating temperature range of, for example, -20 to 120°C. Furthermore, infrared laser image recognition and ranging devices using liquid crystals are also attracting attention as sensors for autonomous driving of vehicles such as automobiles. Liquid crystals for this application are required to have a Δn of, for example, 0.3 to 0.6, with an operating temperature range of, for example, 10 to 100°C. Furthermore, it is known that many liquid crystal compounds that constitute liquid crystal compositions exhibiting a high Δn of 0.2 or greater have low compatibility. Therefore, it is also important to select liquid crystal compounds with high compatibility. In contrast, technology for liquid crystals used in antennas is described, for example, in Patent Document 1. Furthermore, Non-Patent Document 1 proposes the use of liquid crystal materials as components of high-frequency devices.

[0003] Japanese Patent Application Laid-Open No. 2016-37607

[0004] Dolfi, Electronics Letters, (UK), 1993, Vol. 29, No. 10, pp. 926-928

[0005] Liquid crystal compositions with large Δn often use compounds with extended π conjugation, so the T ｎｉ The liquid crystal composition has a tendency to have a high T value, and when dissolving such a liquid crystal composition, it is necessary to heat the composition to a high temperature, which may cause deterioration of the liquid crystal composition due to heat. There is also a concern about storage stability, and the liquid crystal composition is likely to solidify even at room temperature. ｎｉ does not become too high, i.e., Δn and T ｎｉ The present invention aims to provide 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.

[0006] As a result of intensive investigations, the present inventors have found that the above-mentioned problems can be solved 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 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, a -C≡C- linking group between the ring structures, and an isothiocyanate group (-NCS), and one or more compounds represented by general formula (iii) having a -C≡C- linking group between the ring structures and an isothiocyanate group (-NCS), and thus have completed the present invention.

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

[0008] (In 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, and one or more —CH ２ Each - may be independently substituted with -O-, and one or more -CH ２-CH ２ - may each independently be substituted with -CH=CH- and / or -CF=CF-, one or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom, but oxygen atoms are not directly bonded to each other, and Y ｉ１ and Y ｉｉ１ each independently represents a hydrogen atom or a halogen atom; and

[0009] (In general formula (iii), R ｉｉｉ１ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and one or more —CH ２ Each - may be independently substituted with -O-, and one or more -CH ２ -CH ２ - may each independently be substituted with -CH=CH- and / or -CF=CF-, one or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom, but oxygen atoms are not directly bonded to each other, ｉｉｉ１ is represented by the following general formula (A ｉｉｉ１ -1) to (A ｉｉｉ１ -5)

[0010] (General formula (A ｉｉｉ１ -1) to (A ｉｉｉ１ -5) Middle, White point is R ｉｉｉ１ 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, in which one or more hydrogen atoms may each independently be substituted with a halogen atom; S ｉｉｉ１ When there are a plurality of groups, they may be the same or different. ｉｉｉ１represents a hydrogen atom or a halogen atom.), wherein the total content of the compounds represented by general formulas (i) and (ii) in 100% by mass of the liquid crystal composition is 25% by mass or more, and the total content of the compounds represented by general formula (iii) in 100% by mass of the liquid crystal composition is 20% by mass or more.

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

[0012] (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, and one or more —CH ２ Each - may be independently substituted with -O-, and one or more -CH ２ -CH ２ - may each independently be substituted with -CH=CH- and / or -CF=CF-, one or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom, but oxygen atoms are not directly bonded to each other, 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) to (A ｏ１／２／３／４／５ -5)

[0013] (Formula (A ｏ１／２／３／４／５ -1) to (A ｏ１／２／３／４／５ In -5), the white dots represent bonds to a cyclohexane ring structure, -CH=CH- or -C≡C-, the black dots represent bonds to a -C≡C- or benzene ring structure, and S ｏ１／２／３／４／５represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, in which one or more hydrogen atoms may each independently be substituted with a halogen atom; S ｏ１／２／３／４／５ When there are a plurality of groups, they may be the same or different. ｏ１ , Y ｏ２ , Y ｏ３ , Y ｏ４ and Y ｏ５ and each independently represents a hydrogen atom or a halogen atom.

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

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

[0016] Item 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 4. The liquid crystal composition according to any one of items 1 to 3, wherein the liquid crystal temperature 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 dielectric constant is reversibly switched by reversibly changing the alignment direction of liquid crystal molecules of the liquid crystal composition according to any one of items 1 to 4.

[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, comprising: 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 provided with the patch electrodes; and a liquid crystal layer provided between the first substrate and the third substrate, wherein the liquid crystal layer contains the liquid crystal composition according to any one of items 1 to 4.

[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, -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 setting the contents of the compounds represented by general formulas (i) and (ii) and the compound represented by general formula (iii) to predetermined amounts, Δn and T ｎｉ The present invention can provide a liquid crystal composition having an excellent balance of properties and 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.

[0026] (Compounds Represented by General Formulae (i) and (ii)) The liquid crystal composition according to the present invention contains one or more compounds selected from the group consisting of compounds represented by the following general formulae (i) and (ii), each having three benzene ring structures, a —C≡C— linking group between the ring structures, and an isothiocyanate group (—NCS), in an amount of 25% by mass or more relative to 100% by mass of the liquid crystal composition:

[0027]

[0028] In general formulas (i) and (ii), Rｉ１ 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 number of carbon atoms in the alkyl group having 1 to 20 carbon atoms is preferably 2 to 10, and more preferably 2 to 6. One or more -CH ２ Each - may be independently substituted with -O-. In addition, one or more -CH ２ -CH ２ Each - 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 a halogen atom. Examples of halogen atoms 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 represents one —CH ２ By substituting - with -O-, an alkoxy group having 1 to 19 carbon atoms can be represented. 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. In addition, R ｉ１ and R ｉｉ１ represents one or more —CH ２ -CH ２ By substituting - with -CH=CH-, it can represent an alkenyl group having 2 to 20 carbon atoms. The alkenyl group is a linear, branched or cyclic alkenyl group, and is preferably a linear alkenyl group. The number of carbon atoms in the alkenyl group is preferably 2 to 10, and more preferably 2 to 6. In addition, R ｉ１ and R ｉｉ１ represents one —CH ２ - is replaced by -O- and one or more -CH２ -CH ２ By replacing - with -CH=CH-, an alkenyloxy group having 2 to 19 carbon atoms can be represented. 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. In addition, R ｉ１ and R ｉｉ１ can represent a halogenated alkyl group having 1 to 20 carbon atoms, with one or more hydrogen atoms in the alkyl group being substituted with halogen atoms. The halogenated alkyl group may be linear, branched, or cyclic, and is preferably a linear halogenated alkyl group. The number of carbon atoms in the halogenated alkyl group is preferably 2 to 10, and more preferably 2 to 6. In addition, R ｉ１ and R ｉｉ１ represents one —CH ２ The halogenated alkoxy group may be a linear, branched, or cyclic halogenated alkoxy group, preferably a linear halogenated alkoxy group. The halogenated alkoxy group preferably has 2 to 10 carbon atoms, more preferably 2 to 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) to (R ｉ１／ｉｉ１ -31).

[0029]

[0030] Formula (R ｉ１／ｉｉ１ -1) to (R ｉ１／ｉｉ１ In the formula (31), the black dots represent bonds to the benzene ring structure. ｉ１ and R ｉｉ１From the viewpoint of Δn and compatibility with other liquid crystal compounds, a linear alkyl group having 2 to 6 carbon atoms is preferred as R ｉ１ and R ｉｉ１ From the viewpoint 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 halogen atoms 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]

[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]

[0036] The number of types of compounds represented by general formula (i) or structural formulas (i-1) to (i-6) used in the liquid crystal composition is one 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 compounds represented by general formula (i) or structural formulae (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 compounds represented by general formula (i) or structural formulae (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 number of types of 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% 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 compounds represented by general formula (ii) or structural formulae (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 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 the total content is less than 25% by mass, it may be difficult to ensure a large Δn of the liquid crystal composition.

[0042] The compounds represented by general formulas (i) and (ii) (including sub-concepts) can be synthesized using 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]

[0044] In the formula, R ｉ１ and Y ｉ１ represents R in the general formula (i). ｉ１ and Y ｉ１and has the same meaning as above. First, a compound represented by general formula (s-1) can be reacted with 1-bromo-4-iodobenzene to obtain a compound represented by general formula (s-2). Examples of the reaction method include the Suzuki coupling reaction using a palladium catalyst and a base. Specific examples of the palladium catalyst 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(0). Examples of the base include potassium carbonate, sodium carbonate, and potassium phosphate. Next, a compound represented by general formula (s-2) can be reacted with a compound represented by general formula (s-3) to obtain a compound represented by general formula (s-4). Examples of the reaction method 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(0). 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. Specific examples of copper catalysts include copper(I) iodide. Specific examples of bases include triethylamine. Furthermore, the compound represented by the general formula (s-4) can be reacted with an NCS agent such as thiophosgene, disulfuric acid, 1,1-thiocarbonyldiimidazole, or 1,1'-thiocarbonyl-di-2(1H)pyridone to obtain the target compound represented by the general formula (s-5). (Production Method 2) Production of a compound represented by the following general formula (s-10):

[0045]

[0046] In the formula, R ｉｉ１ and Y ｉｉ１ represents R in the general formula (ii). ｉｉ１ and Y ｉｉ１ has the same meaning as above. First, a compound represented by general formula (s-6) is reacted with trimethylsilylacetylene, and then the compound represented by general formula (s-7) can be obtained by reacting the compound with potassium carbonate in an alcohol solvent. The reaction with trimethylsilylacetylene can be carried out by 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, a 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). An example of the reaction method is the Sonogashira coupling reaction using a palladium catalyst, a copper catalyst, and a base. Specific examples of the palladium catalyst, the copper catalyst, and the base include those mentioned above. Furthermore, the compound represented by general formula (s-9) can be reacted with an NCS agent such as thiophosgene, disulfuric acid, 1,1-thiocarbonyldiimidazole, or 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— as a linking group between ring structures and an isothiocyanate group (—NCS) in an amount of 20% by mass or more relative to 100% by mass of the liquid crystal composition.

[0048]

[0049] In general formula (iii), R ｉｉｉ１ represents an alkyl group having 1 to 20 carbon atoms. The alkyl group may be linear, branched, or cyclic, and is preferably a linear alkyl group. The number of carbon atoms in the alkyl group is preferably 2 to 10, and more preferably 2 to 6. One or more —CH ２Each - may be independently substituted with -O-. In addition, one or more -CH ２ -CH ２ - 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 halogen atoms 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 represents one —CH ２ By substituting - with -O-, an alkoxy group having 1 to 19 carbon atoms can be represented. 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. In addition, R ｉｉｉ１ represents one or more —CH ２ -CH ２ By substituting - with -CH=CH-, it can represent an alkenyl group having 2 to 20 carbon atoms. The alkenyl group is a linear, branched or cyclic alkenyl group, and is preferably a linear alkenyl group. The number of carbon atoms in the alkenyl group is preferably 2 to 10, and more preferably 2 to 6. In addition, R ｉｉｉ１ represents one —CH ２ - is replaced by -O- and one or more -CH ２ -CH ２ By replacing - with -CH=CH-, an alkenyloxy group having 2 to 19 carbon atoms can be represented. 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. In addition, R ｉｉｉ１can represent a halogenated alkyl group having 1 to 20 carbon atoms, with one or more hydrogen atoms in the alkyl group being substituted with halogen atoms. The halogenated alkyl group may be linear, branched, or cyclic, and is preferably a linear halogenated alkyl group. The number of carbon atoms in the halogenated alkyl group is preferably 2 to 10, and more preferably 2 to 6. In addition, R ｉｉｉ１ represents one —CH ２ The halogenated alkoxy group may be a linear, branched, or cyclic halogenated alkoxy group, preferably a linear halogenated alkoxy group. The halogenated alkoxy group preferably has 2 to 10 carbon atoms, more preferably 2 to 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) to (R ｉｉｉ１ -30).

[0050]

[0051] Formula (R ｉｉｉ１ -1) to (R ｉｉｉ１ -30) In the middle, black dots are A ｉｉｉ１ Represents a bond to R. ｉｉｉ１ From the viewpoint of solubility, the alkyl group is preferably a linear alkyl group having 1 to 8 carbon atoms or a linear alkenyl group having 2 to 6 carbon atoms.

[0052] In general formula (ii), A ｉｉｉ１ is represented by the following general formula (A ｉｉｉ１ -1) to (A ｉｉｉ１ -5).

[0053]

[0054] General formula (A ｉｉｉ１ -1) to (A ｉｉｉ１ -5) Middle, white point is R ｉｉｉ１The black dot represents a bond to —C≡C—.

[0055] General formula (A ｉｉｉ１ -1) to (A ｉｉｉ１ -5) Medium, 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. Examples of halogen atoms 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 halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. S ｉｉｉ１ Specific examples of the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms include those represented by the formula (S ｉｉｉ１ -1) to (S ｉｉｉ１ -16) and the like.

[0056]

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

[0058] More specifically, the general formula (A ｉｉｉ１ -2) is represented by the following formula (A ｉｉｉ１ -2-1) to (A ｉｉｉ１ It is preferable that the group represents any one of the following:

[0059]

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

[0061] More specifically, the general formula (A ｉｉｉ１ -3) is represented by the following formula (A ｉｉｉ１ -3-1) to (A ｉｉｉ１ It is preferable that the group represents any one of the following:

[0062]

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

[0064] More specifically, the general formula (A ｉｉｉ１ -4) is represented by the following formula (A ｉｉｉ１ -4-1) to (A ｉｉｉ１ -4-4) is preferably represented.

[0065]

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

[0067] More specifically, the general formula (A ｉｉｉ１ -5) is represented by the following formula (A ｉｉｉ１ -5-1) to (A ｉｉｉ１ -5-4) is preferred.

[0068]

[0069] General formula (A ｉｉｉ１ -5-1) to (A ｉｉｉ１ -5-4) In the middle, the white point 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 halogen atoms 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]

[0073] In general formula (iii-1), R ｉｉｉ１ represents R in the above general formula (iii). ｉｉｉ１ 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 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]

[0075] The number of types of 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 is one 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 compounds represented by general formula (iii), general formula (iii-1), or structural formulae (iii-1.1) to (iii-1.8) in 100% by mass of the liquid crystal composition is preferably 1% by mass or more, more preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by 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 formulae (iii-1.1) to (iii-1.8) in 100% by mass of the liquid crystal composition is preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.

[0078] The total content of the compounds (including sub-concepts) represented by general formula (iii) 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 the T ｎｉ may become too high.

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

[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 formulae (o-1) to (o-5).

[0081]

[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 is a linear, branched, or cyclic alkyl group, and is preferably a linear alkyl group. The number of carbon atoms in the alkyl group is preferably 2 to 10, and more preferably 2 to 6. One or more —CH ２ Each - may be independently substituted with -O-. In addition, one or more -CH ２ -CH ２ - 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 halogen atoms 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 represents one —CH ２ By substituting - with -O-, an alkoxy group having 1 to 19 carbon atoms can be represented. 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. In addition, R ｏ１ , R ｏ２ , R ｏ３ , R ｏ４ and R ｏ５ represents one or more —CH ２ -CH ２ By substituting - with -CH=CH-, it can represent an alkenyl group having 2 to 20 carbon atoms. The alkenyl group is a linear, branched or cyclic alkenyl group, and is preferably a linear alkenyl group. The number of carbon atoms in the alkenyl group is preferably 2 to 10, and more preferably 2 to 6. In addition, R ｏ１ , R ｏ２ , R ｏ３ , R ｏ４ and R ｏ５ represents one —CH ２ - is replaced by -O- and one or more -CH ２ -CH ２ By replacing - with -CH=CH-, an alkenyloxy group having 2 to 19 carbon atoms can be represented. 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. In addition, R ｏ１ , R ｏ２ , R ｏ３ , R ｏ４ and R ｏ５can represent a halogenated alkyl group having 1 to 20 carbon atoms, with one or more hydrogen atoms in the alkyl group being substituted with halogen atoms. The halogenated alkyl group may be linear, branched, or cyclic, and is preferably a linear halogenated alkyl group. The number of carbon atoms in the halogenated alkyl group is preferably 2 to 10, and more preferably 2 to 6. In addition, R ｏ１ , R ｏ２ , R ｏ３ , R ｏ４ and R ｏ５ represents one —CH ２ The halogenated alkoxy group may be a linear, branched, or cyclic halogenated alkoxy group, preferably a linear halogenated alkoxy group. The halogenated alkoxy group preferably has 2 to 10 carbon atoms, more preferably 2 to 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 (R ｏ１／２／３／４／５ -1) to (R ｏ１／２／３／４／５ -31).

[0083]

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

[0085] In general formulas (o-1) to (o-5), Aｏ１ , 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) to (A ｏ１／２／３／４／５ -5).

[0086]

[0087] General formula (A ｏ１／２／３／４／５ -1) to (A ｏ１／２／３／４／５ In -5), 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) to (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 halogen atoms 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 halogen atoms 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) to (S ｏ１／２／３／４／５ -16) and the like.

[0089]

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

[0091] More specifically, the general formula (A ｏ１／２／３／４／５ -2) is represented by the following formula (A ｏ１／２／３／４／５ -2-1) to (A ｏ１／２／３／４／５ It is preferable that the group represents any one of the following:

[0092]

[0093] General formula (A ｏ１／２／３／４／５ -2-1) to (A ｏ１／２／３／４／５ In the formula (2-4), 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.

[0094] More specifically, the general formula (A ｏ１／２／３／４／５ -3) is represented by the following formula (A ｏ１／２／３／４／５ -3-1) to (A ｏ１／２／３／４／５ It is preferable that the group represents any one of the following:

[0095]

[0096] General formula (A ｏ１／２／３／４／５ -3-1) to (A ｏ１／２／３／４／５ In the formula (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 represented by the following formula (A ｏ１／２／３／４／５ -4-1) to (A ｏ１／２／３／４／５ -4-4) is preferably represented.

[0098]

[0099] General formula (A ｏ１／２／３／４／５ -4-1) to (A ｏ１／２／３／４／５ In the formula (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 represented by the following formula (A ｏ１／２／３／４／５-5-1) to (A ｏ１／２／３／４／５ -5-4) is preferred.

[0101]

[0102] General formula (A ｏ１／２／３／４／５ -5-1) to (A ｏ１／２／３／４／５ In the formula (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 halogen atoms 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]

[0106] In general formula (o-1-1), R ｏ１ represents R in the above general formula (o-1). ｏ１ 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]

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

[0109]

[0110] In general formula (o-2-1), Rｏ２ represents R in the general formula (o-2). ｏ２ 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]

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

[0113]

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

[0115]

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

[0117]

[0118] In general formula (o-4-1), R ｏ４ represents R in the above general formula (o-4). ｏ４ 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]

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

[0121]

[0122] In general formula (o-5-1), R ｏ５ represents R in the above general formula (o-5). ｏ５Specific examples of the compound represented by general formula (o-5-1) include compounds represented by the following structural formulas (o-5-1.1) to (o-5-1.7).

[0123]

[0124] The number of types of compounds represented by general formula (o-1), general formula (o-1-1), or structural formulae (o-1-1.1) to (o-1-1.7) used in the liquid crystal composition is one or two 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 formulae (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 number of types of compounds represented by general formula (o-2), general formula (o-2-1), or structural formulae (o-2-1.1) to (o-2-1.7) used in the liquid crystal composition is one or more, preferably 1 to 10, preferably 1 to 5, and preferably 1 to 3.

[0127] The total content of the compounds represented by general formula (o-2), general formula (o-2-1), or structural formulae (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 number of types of compounds represented by general formula (o-3), general formula (o-3-1), or structural formulae (o-3-1.1) to (o-3-1.7) used in the liquid crystal composition is one or two or more, preferably 1 to 10, preferably 1 to 5, and preferably 1 to 3.

[0129] The total content of the compounds represented by general formula (o-3), general formula (o-3-1), or structural formulae (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 formulae (o-4-1.1) to (o-4-1.7) used in the liquid crystal composition is one or two 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 formulae (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 formulae (o-5-1.1) to (o-5-1.7) used in the liquid crystal composition is one or two 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 formulae (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 general formulae (o-1) to (o-5) (including sub-concepts) can be synthesized 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 compounds represented by the above-mentioned general formula (i) and the compounds represented by the general formula (ii), the compound represented by the general formula (iii), and, if necessary, the above-mentioned other compounds and additives.

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

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

[0138]

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

[0140]

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

[0142] The combination of compounds used in the liquid crystal composition may be determined by the solubility, Δn and / or T ｎｉFrom the viewpoint of the above, 1) a combination of a compound represented by general formula (i) (including subordinate concepts) and a compound represented by general formula (iii) (including subordinate 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 subordinate concepts) and a compound represented by general formula (iii) (including subordinate 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 subordinate concepts), a compound represented by general formula (ii) (including subordinate concepts), and a compound represented by general formula (iii) (including subordinate 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 a phase transition from a nematic phase to an isotropic phase. ｎｉ The T is measured by preparing a preparation in which the liquid crystal composition is sandwiched between a slide glass and a cover glass, and observing it under a polarizing microscope while heating it on a hot stage. It can also be measured by differential scanning calorimetry (DSC). The unit is "°C". ｎｉ The higher the T, 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, the liquid crystal may be thermally deteriorated 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 storage stability and high liquid crystal phase temperature (T ｎｉ ) can be appropriately set depending on whether the liquid crystal display element is used indoors, in a car, or the like where the external temperature can be controlled, or whether it is used outdoors, but from the viewpoint of the operating temperature range, it is preferably 170°C or lower, 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 the liquid crystal composition undergoes a phase transition from other phases (glass phase, smectic phase, crystalline phase) to the nematic phase. →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 temperature as it is raised. It can also be measured by differential scanning calorimetry (DSC). The unit is "°C". T →ｎ The lower the temperature, the more the nematic phase can be maintained at a low temperature, and therefore the wider the operating temperature range can be. →ｎ ) is preferably 10°C or lower, more preferably -70 to 0°C, and even more preferably -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 optical sensors, which will be described later. The larger Δn is, the greater the phase modulation power of light of the target wavelength, making it particularly suitable for optical sensors. Δn at 25°C and 589 nm was determined by measuring the extraordinary refractive index (n ｅ ) and ordinary refractive index (n ｏ ) difference (n ｅ -n ｏ ) Δn can also be determined using a retardation measurement device. The relationship Δn = Re / d holds between retardation Re, liquid crystal layer thickness d, and Δn. 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 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.). Measurements are performed at a temperature of 25°C and a wavelength of 589 nm, and are unitless. 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 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] Rotational viscosity (γ １ ) is the viscosity related to the rotation of the liquid crystal molecules. １ The γ can be measured by filling a glass cell with a cell gap of approximately 10 μm with the liquid crystal composition, applying a voltage of 50 V, and using an LCM-2 (manufactured by Toyo Corporation). A horizontally aligned cell is used for a liquid crystal composition with a positive dielectric anisotropy, and a vertically aligned cell is used for a liquid crystal composition with a negative dielectric anisotropy. Measurements are made at a temperature of 25°C, and the unit is mPa·s. １ The smaller the rotational viscosity (γ) of the liquid crystal composition at 25° C. of the liquid crystal composition according to the present invention is, the faster the response speed of the liquid crystal composition becomes, and therefore, it is suitable for any liquid crystal display device. １ From the viewpoint of response speed, the viscosity is preferably 150 to 1200 mPa·s, more preferably 200 to 900 mPa·s, and even more preferably 250 to 700 mPa·s.

[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, making it particularly suitable for antenna applications. Furthermore, in antenna applications, the smaller the dielectric loss tangent in the high frequency region, the smaller the energy loss in the target frequency band, making it suitable. In the liquid crystal composition according to the present invention, the dielectric anisotropy Δε at 10 GHz, which represents the characteristics in the high frequency region, is ｒ and the average value of the dielectric tangent tanδ ｉｓｏ was measured. ｒ =(ε ｒ∥ -ε ｒ⊥ ) and tan δ ｉｓｏ = (2ε ｒ⊥ tan δ ⊥ +ε ｒ∥ tan δ ∥ ) / (2ε ｒ⊥ +ε ｒ∥ ) where "εr" is the dielectric constant, "tanδ" is the dielectric loss 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 tube used here has an inner radius of 0.80 mm, an outer radius of 0.835 mm, and 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.) with a resonance frequency of 10 GHz. This cavity resonator has an outer diameter of 30 mm and a width of 26 mm. A signal is then input, and the output signal is recorded using a network analyzer (manufactured by Keysight Technologies, Inc.). The dielectric constant (ε) at 10 GHz is calculated using the difference between the resonance frequency of a PTFE capillary tube without the liquid crystal composition and the resonance frequency of a PTFE capillary tube containing the liquid crystal composition. ｒ) and loss angle (δ) are determined. The tangent of the obtained δ is the dielectric loss tangent (tan δ). The resonance frequency and other parameters using a PTFE capillary filled with a liquid crystal composition are determined by controlling the orientation of the liquid crystal molecules, as the values ​​of characteristic components perpendicular and parallel to the orientation direction of the liquid crystal molecules. A magnetic field from a permanent magnet or electromagnet is used to align the liquid crystal molecules in the perpendicular direction (perpendicular to the effective length direction) or parallel direction (parallel to the effective length direction) of the PTFE capillary. The magnetic field has, for example, a pole-to-pole distance of 45 mm and a magnetic field strength of 0.23 Tesla near the center. The desired characteristic components are obtained by rotating the PTFE capillary filled with the liquid crystal composition parallel or perpendicular to the magnetic field. Measurements are performed at a temperature of 25°C, and Δε 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. 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 Element, Sensor, Liquid Crystal Lens, Optical Communication Device, and Antenna) Hereinafter, 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.

[0151] The liquid crystal display element of 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 of the present invention is preferably a liquid crystal display element that reversibly switches the dielectric constant 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 liquid crystal composition described above. Examples of the sensor include a distance measuring sensor that uses electromagnetic waves, visible light, or infrared light, an infrared sensor that uses temperature changes, 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 voltage or current, a radiation sensor that uses a temperature change associated with the track of a radiation particle, an ultrasonic sensor that uses a change in the alignment of liquid crystal molecules due to mechanical vibration of ultrasound, and an electromagnetic field sensor that uses a change in the wavelength of reflected light due to a change in the alignment of liquid crystal molecules due to a temperature change or an electric field. The distance measuring sensor is preferably for LiDAR (Light Detection and Ranging) that uses a light source. LiDAR is preferably for use in 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, and more preferably a laser. The light used in LiDAR is preferably infrared light, and preferably has a wavelength of 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 used and sensitivity in all weather conditions are important, a 905 nm infrared laser is preferred, and 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, and therefore a sensor with large phase modulation power in the visible light, infrared light, and electromagnetic wave regions and excellent detection sensitivity can be provided.

[0153] The liquid crystal lens according to the present invention is characterized by using the liquid crystal composition described above, and, for example, in one embodiment, has a first transparent electrode layer, a second transparent electrode layer, a liquid crystal layer containing the liquid crystal composition described above and 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, etc.

[0154] The optical communication device according to the present invention is characterized by using the above-mentioned liquid crystal composition, and one example of the optical communication device is a liquid crystal on silicon (LCOS) structure having a liquid crystal layer on a reflective layer (electrode) in which liquid crystals constituting each of a plurality of pixels are arranged two-dimensionally. 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-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 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 provided with the patch electrodes, and a liquid crystal layer provided between the first substrate and the third substrate, wherein the liquid crystal layer contains the above-described liquid crystal composition. By using the liquid crystal composition according to the present invention, an antenna having high reliability against external stimuli such as heat can be provided. Furthermore, an antenna enabling greater phase control for microwave or millimeter wave electromagnetic waves can be provided. The antenna according to the present invention preferably operates in the Ka band frequency, K band frequency, or Ku band frequency used for satellite communications. The antenna according to the present invention is preferably configured to combine a radial line slot array and a patch antenna array. The structure of the antenna according to the present invention can be applied by taking into consideration, for example, the matters described in International Publication No. 2021 / 157189 and the like.

[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 contain each compound at the ratio shown in the table, and the content is expressed in "mass %". The compounds are represented by the following abbreviations. Note that compounds that can take cis and trans forms represent the trans form unless otherwise specified. <Ring structure>

[0157]

[0158] <Terminal structure>

[0159] (Note that n in the table is a natural number. The alkyl group represented by n is a linear alkyl group.)

[0160] <Connection structure>

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

[0162] (hindered phenol antioxidant)

[0163]

[0164] (Hindered amine light stabilizer)

[0165]

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

[0167]

[0168] (Examples 1 to 14 and Comparative Examples 1 and 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), 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, and therefore 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 degassing was carried out by deaerating at 150 to 250 Pa for 10 minutes. 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 (SH-241, manufactured by Espec Corp.) at 25°C for 2 weeks, and the occurrence of crystallization of the liquid crystal composition was visually confirmed every week.

[0169]

[0170]

[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 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 has been confirmed that the balance of Δε ｒ , tanδ ｉｓｏ On the other hand, from Comparative Examples 1 and 2, it was found that the liquid crystal compositions that did not contain 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 temperature was as high as 175°C or higher. In Comparative Example 1, it was confirmed that LC-A crystallized 4 days after preparation. Furthermore, from Examples 2 to 14, it was confirmed that the same effect was 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) is described below. (Synthesis Example 1) Production of the compound represented by formula (I-1)

[0172]

[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 placed in a reaction vessel, and the reaction vessel was heated to 70°C. After completion of the reaction, 10% by mass hydrochloric acid was poured into the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated saline, and the solvent was then distilled off. The residue was then dispersed and washed with hexane, yielding 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 placed in a reaction vessel. Then, while heating at 85°C, a solution prepared by dissolving 13 g of the compound represented by formula (I-1-3) in 25 mL of N,N-dimethylformamide was added dropwise, and the mixture was stirred at 85°C for 3 hours. After completion of the reaction, 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 completion of the reaction, 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 Compound Represented by Formula (I-2)

[0174]

[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 prepared by dissolving 20 g of trimethylsilylacetylene in 50 mL of N,N-dimethylformamide was added dropwise, and the mixture was stirred at 70°C for 2 hours. After completion of the reaction, 10% by mass hydrochloric acid was poured into the reaction solution, and the mixture was extracted with toluene. The organic layer was washed with saturated saline, followed by column chromatography (silica gel, toluene) and solvent distillation. 20 g of potassium carbonate and 200 ml of methanol were then added, and the reaction vessel was heated to 50°C and reacted for 2 hours. The reaction solution was then extracted with toluene, the organic layer was washed with saturated saline, followed by column chromatography (silica gel, toluene), and solvent distillation, yielding 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 prepared by dissolving 14 g of the compound represented by formula (I-2-2) in 25 mL of N,N-dimethylformamide was added dropwise, and the mixture was stirred at 85°C for 3 hours. After completion of the reaction, 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 the mixture was allowed to react 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) Production of the compound represented by formula (I-3)

[0176]

[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 prepared by dissolving 20 g of trimethylsilylacetylene in 50 mL of N,N-dimethylformamide was added dropwise, and the mixture was stirred at 70°C for 2 hours. After completion of the reaction, 10% by mass hydrochloric acid was poured into the reaction solution, and the mixture was extracted with toluene. The organic layer was washed with saturated saline, followed by column chromatography (silica gel, toluene) and solvent distillation. 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 solution was then extracted with toluene, the organic layer was washed with saturated saline, followed by column chromatography (silica gel, toluene), and solvent distillation, yielding 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 a reaction vessel. Then, while heating at 85°C, a solution prepared by dissolving 15 g of the compound represented by formula (I-3-2) in 25 mL of N,N-dimethylformamide was added dropwise, and the mixture was stirred at 85°C for 3 hours. After completion of the reaction, 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-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 mixture was allowed to react 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

[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. A compound represented by the following general formulas (i) and (ii): (In 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, ２ Each - may be independently substituted with -O-, and one or more -CH ２ -CH ２ each - 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 a halogen atom, but oxygen atoms are not directly bonded to each other, and Y ｉ１ and Y ｉｉ１ each independently represents a hydrogen atom or a halogen atom; and (In general formula (iii), R ｉｉｉ１ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, ２ Each - may be independently substituted with -O-, and one or more -CH ２ -CH ２ each - 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 a halogen atom, but the oxygen atoms are not directly bonded to each other, ｉｉｉ１ is represented by the following general formula (A ｉｉｉ１ -1) to (A ｉｉｉ１ -5) (General formula (A ｉｉｉ１ -1) to (A ｉｉｉ１ -5) Middle, white point is R ｉｉｉ１ A black dot represents a bond to -C≡C-, and 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, in which one or more hydrogen atoms may each be independently substituted with a halogen atom; S ｉｉｉ１ When there are a plurality of Y's, they may be the same or different; ｉｉｉ１ represents a hydrogen atom or a halogen atom.) wherein the total content of the compounds represented by general formulas (i) and (ii) in 100% by mass of the liquid crystal composition is 25% by mass or more, and the total content of the compound represented by general formula (iii) in 100% by mass of the liquid crystal composition is 20% by mass or more.

2. Furthermore, the following general formulae (o-1) to (o-5) (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, ２ Each - may be independently substituted with -O-, and one or more -CH ２ -CH ２ each - 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 a halogen atom, but the oxygen atoms are not directly bonded to each other, ｏ１ , A ｏ２ , A ｏ３ , A ｏ４ and A ｏ５ each independently represents the following general formula (A ｏ１／２／３／４／５ -1) to (A ｏ１／２／３／４／５ -5) (Formula (A ｏ１／２／３／４／５ -1) to (A ｏ１／２／３／４／５ In the formula (5), the white dots represent bonds to a cyclohexane ring structure, -CH=CH- or -C≡C-, the black dots represent bonds to a -C≡C- or benzene ring structure, and 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, in which one or more hydrogen atoms may each be independently substituted with a halogen atom; S ｏ１／２／３／４／５ When there are a plurality of Y's, they may be the same or different; ｏ１ , Y ｏ２ , Y ｏ３ , Y ｏ４ and Y ｏ５ and each independently represents a hydrogen atom or a halogen atom.

3. Compounds represented by the general formulas (i) and (ii) include compounds represented by the following structural formulas (i-5), (i-6), (ii-5), (ii-6) and (ii-7):

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 any one of claims 1 to 4.

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

7. A liquid crystal display device in which the dielectric constant is reversibly switched by reversibly changing the alignment direction of the liquid crystal molecules of the liquid crystal composition according to any one of claims 1 to 4.

8. A sensor using the liquid crystal composition according to any one of claims 1 to 4.

9. A liquid crystal lens using the liquid crystal composition according to any one of claims 1 to 4.

10. An optical communication device using the liquid crystal composition according to any one of claims 1 to 4.

11. An antenna using the liquid crystal composition according to any one of claims 1 to 4.

12. An antenna as described in claim 11, comprising: 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 provided with the patch electrodes; and a liquid crystal layer provided between the first substrate and the third substrate, wherein the liquid crystal layer contains the liquid crystal composition as described in any one of claims 1 to 4.

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