Method for producing liquid crystal material, method for evaluating liquid crystal material, measuring device for liquid crystal material, and liquid crystal material

Abstract

This disclosure pertains to a method for manufacturing a liquid crystal material, comprising: step (I), preparing a liquid crystal material; and step (II), measuring the liquid crystal material using a differential delay measuring mechanism for measuring the differential delay value of the liquid crystal material; the differential delay measuring mechanism comprises a coaxial tube including a linear inner conductor and an outer conductor having a gap for inserting the inner conductor, and a mechanism for calculating the differential delay value of the liquid crystal material; the differential delay value of the liquid crystal material is the difference between a propagation delay time t0 and a propagation delay time tv, wherein the propagation delay time t0 is measured by allowing an electromagnetic wave with a continuously varying frequency to propagate in the liquid crystal material filling the gap between the inner conductor and the outer conductor while a reference voltage V0 is applied between the inner conductor and the outer conductor, and the propagation delay time tv is measured by allowing the electromagnetic wave to propagate in the liquid crystal material while an execution voltage V greater than the reference voltage V0 is applied between the inner conductor and the outer conductor.

Description

Technical Field

[0001] This disclosure relates to a method for manufacturing a liquid crystal composition, a method and apparatus for measuring delta delay, and a liquid crystal material. Background Technology

[0002] Liquid crystal materials are not only used in displays such as televisions, monitors, mobile phones, smartphones, and tablets, but also, with the development of autonomous driving technology, in applications such as antennas for transmitting and receiving microwave radio waves between mobile vehicles and communication satellites. Antennas using liquid crystal materials, like displays, activate the liquid crystal by applying an external electric field, thus allowing for free adjustment of the direction of radio wave transmission and reception.

[0003] Therefore, in both display and antenna applications, the change in the molecular arrangement of liquid crystals caused by the application of an electric field is induced by dielectric torque based on the anisotropy of the liquid crystal's dielectric constant. Thus, the anisotropy of the liquid crystal's dielectric constant (Δε = ε∥ - ε⊥) becomes an important physical quantity. Generally, the anisotropy of the dielectric constant (Δε) is defined as the difference between the dielectric constant (ε∥) in the direction parallel to the long axis of the liquid crystal molecules and the dielectric constant (ε⊥) in the direction perpendicular to the long axis of the liquid crystal molecules, and is calculated based on the dielectric constant (complex dielectric constant) of the liquid crystal material.

[0004] Liquid crystals require frequencies ranging from several Hz to several kHz to operate. Therefore, the dielectric anisotropy (Δε) is generally determined by measuring the dielectric constant at 1 kHz. On the other hand, liquid crystal materials used in antenna applications require precise measurement of the magnitude of the dielectric anisotropy at 1 kHz and the dielectric anisotropy in the microwave band in which they are applied.

[0005] Various methods exist for determining the dielectric constant (complex dielectric constant) of dielectrics in microwave bands, such as liquid crystal materials used in antenna applications. Examples include: (1) the cavity resonator method, which calculates the dielectric constant (complex dielectric constant) based on the change in resonant frequency and Q value when the dielectric is inserted into a resonator; (2) the coaxial tube method, which fills a coaxial tube with dielectric and calculates the dielectric constant (complex dielectric constant) based on the amplitude and phase difference of the reflected wave; and (3) the lumped parameter capacitance method, which fills a sample between two electrodes and measures the electrostatic capacitance between the electrodes. Among these, the coaxial tube method (2) is commonly used for determining the dielectric constant (complex dielectric constant) of liquid crystal materials, which exhibit high fluidity, because it can be easily used to measure liquid materials.

[0006] However, it is known that the determination of dielectric constant (complex dielectric constant) by the coaxial tube method requires the use of multiple coaxial tubes of different lengths to measure one test sample separately (Patent Document 1).

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2006-220646 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] In particular, due to the unique dielectric anisotropy of liquid crystal materials (Δε=ε∥-ε⊥), multiple measurements can be forced based on whether or not a voltage is applied, resulting in either a state where the liquid crystal molecules in the sample are not oriented in a specific direction or a state where the liquid crystal molecules in the sample are oriented in a specific direction. Therefore, the current situation is that when using the coaxial tube method to measure the dielectric constant (complex dielectric constant) of liquid crystal materials, there is a problem of accumulated measurement errors (errors due to electromagnetic wave reflection or electromagnetic wave intensity loss) caused by the desorption of the coaxial tube, as well as a decrease in measurement reproducibility.

[0012] To address this issue, this disclosure introduces a new physical quantity (nsec) called "differential delay" to replace the dielectric constant calculated as one of the electrical properties in previous measurement methods. It confirms that when the electrical properties of liquid crystal materials are specified by this "differential delay", liquid crystal materials with homogeneous electrical properties can be obtained.

[0013] Therefore, the purpose of this disclosure is to provide a liquid crystal material with homogeneous electrical properties and a method for manufacturing the same, as well as a method and apparatus for measuring the liquid crystal material with homogeneous electrical properties.

[0014] Methods for solving problems

[0015] The inventors have conducted intensive research on the above-mentioned issues and have found that when the electrical properties of liquid crystal materials are specifically defined using a physical quantity (differential delay (unit (nsec)), liquid crystal materials with homogeneous electrical properties can be manufactured or evaluated compared to dielectric constants, thus completing the present invention.

[0016] The present invention, which solves the above-mentioned problems, is structured as follows.

[0017] [1] This disclosure is a method for manufacturing a liquid crystal material, characterized by comprising the following steps:

[0018] Process (I), preparation of liquid crystal material; and

[0019] In step (II), the liquid crystal material is measured using a differential delay measuring mechanism that measures the differential delay value of the liquid crystal material described above.

[0020] The aforementioned differential delay measurement mechanism includes a coaxial tube comprising an inner conductor in the shape of a line and an outer conductor having a gap for inserting the inner conductor, and includes a mechanism for calculating the differential delay value of the liquid crystal material; the differential delay value of the liquid crystal material is the difference between the transmission delay time t0 and the transmission delay time tv, the transmission delay time t0 is measured by allowing an electromagnetic wave with a continuously changing frequency to propagate in the liquid crystal material filling the gap between the inner conductor and the outer conductor while a reference voltage V0 is applied between the inner conductor and the outer conductor, and the transmission delay time tv is measured by allowing the electromagnetic wave to propagate in the liquid crystal material while an execution voltage V greater than the reference voltage V0 is applied between the inner conductor and the outer conductor.

[0021] [2] In this embodiment, the electromagnetic wave is preferably a continuous frequency variation in the range of 0.1 to 26.5 GHz.

[0022] [3] In this embodiment, the transmission delay time t0 is preferably measured by propagating an electromagnetic wave with a continuously changing frequency in the liquid crystal material under a state of no bias voltage between the inner conductor and the outer conductor.

[0023] [4] In this embodiment, the liquid crystal material is preferably a liquid crystal compound containing isothiocyanate groups (-NCS).

[0024] [5] This disclosure is a method for measuring differential delay, which is the method for measuring differential delay as follows: using a coaxial tube having an inner conductor in the shape of a line and an outer conductor having a gap for inserting the inner conductor, the change in the propagation delay time of an electromagnetic wave in a liquid crystal material filling the gap is measured.

[0025] The above method for measuring differential delay includes the following steps:

[0026] The process of preparing the above-mentioned liquid crystal materials;

[0027] The process of filling the liquid crystal material between the inner conductor and the outer conductor; and

[0028] The process of calculating the differential retardation value of the above liquid crystal material,

[0029] The differential delay value of the liquid crystal material is the difference between the propagation delay time t0 and the propagation delay time tv. The propagation delay time t0 is measured by allowing an electromagnetic wave with a continuously changing frequency to propagate in the liquid crystal material while a reference voltage V0 is applied between the internal conductor and the external conductor. The propagation delay time tv is measured by allowing the electromagnetic wave to propagate in the liquid crystal material while an execution voltage V greater than the reference voltage V0 is applied between the internal conductor and the external conductor.

[0030] [6] This disclosure is a device for measuring differential delay value, characterized in that it has:

[0031] A coaxial tube having a linear inner conductor, an outer conductor through which the inner conductor is inserted, and a gap between the inner conductor and the outer conductor that can be filled with liquid crystal material.

[0032] An electrical signal transceiver unit receives an electrical signal of an electromagnetic wave input to the coaxial tube and receives an output signal of an electromagnetic wave output in response to the electrical signal; and

[0033] The parsing and processing unit performs parsing and processing on the electrical signals transmitted and received by the electrical signal transceiver unit and the output signals.

[0034] The aforementioned analysis processing unit calculates the differential delay value of the liquid crystal material, which is the difference between the propagation delay time t0 and the propagation delay time tv. The propagation delay time t0 is measured by allowing an electromagnetic wave with a continuously changing frequency to propagate in the liquid crystal material while a reference voltage V0 is applied between the internal conductor and the external conductor. The propagation delay time tv is measured by allowing the electromagnetic wave to propagate in the liquid crystal material while an execution voltage V greater than the reference voltage V0 is applied between the internal conductor and the external conductor.

[0035] [7] This disclosure is a liquid crystal material having a differential delay value of 0.01 or higher.

[0036] The effects of the invention

[0037] According to the present invention, a liquid crystal material having homogeneous electrical properties and a method for manufacturing the same, as well as a method and apparatus for measuring the liquid crystal material having homogeneous electrical properties, are provided. Attached Figure Description

[0038] [ Figure 1 ] Figure 1 This is a schematic diagram illustrating an example of the configuration of the differential delay measurement system in this embodiment.

[0039] [ Figure 2 ] Figure 2 It means Figure 1A schematic diagram of a cross-sectional view along direction II. Detailed Implementation

[0040] Hereinafter, embodiments of the present invention (hereinafter referred to as "this embodiment") will be described in detail, but this disclosure is not limited to the following description and can be implemented in various modifications within the scope of its spirit.

[0041] [Manufacturing Method of Liquid Crystal Materials]

[0042] The method for manufacturing liquid crystal material according to this embodiment includes the following steps: step (I), preparing liquid crystal material; and step (II), measuring the liquid crystal material using a differential delay measuring mechanism that measures the differential delay value of the liquid crystal material. The differential delay measuring mechanism includes a coaxial tube comprising an inner conductor in the shape of a wire and an outer conductor having a gap for inserting the inner conductor, and a mechanism for calculating the differential delay value of the liquid crystal material. The differential delay value of the liquid crystal material is the difference between a propagation delay time t0 and a propagation delay time tv. The propagation delay time t0 is measured by allowing an electromagnetic wave with a continuously varying frequency to propagate through the liquid crystal material filling the gap between the inner and outer conductors while a reference voltage V0 is applied between the inner and outer conductors. The propagation delay time tv is measured by allowing the electromagnetic wave to propagate through the liquid crystal material while an execution voltage V greater than the reference voltage V0 is applied between the inner and outer conductors.

[0043] Therefore, a liquid crystal material with homogeneous electrical properties and a method for manufacturing the same can be provided.

[0044] The following is a description of each process.

[0045] (Process (I))

[0046] The method for manufacturing liquid crystal materials in this embodiment includes a step (I) for preparing liquid crystal materials.

[0047] In this embodiment, the liquid crystal material can be any material exhibiting fluidity and liquid crystal properties, or a liquid (e.g., a solution, suspension) exhibiting liquid crystal properties. Therefore, the liquid crystal material can be a material exhibiting liquid crystal properties and fluidity as a monomer of a compound, or it can be a material that exhibits liquid crystal properties and fluidity as a whole in a composition formed by mixing with other compounds.

[0048] The term "exhibiting liquid crystal properties" as used in this specification refers to having rigid regions called mesocrysts and exhibiting orientation. Furthermore, there are no particular limitations on the type of liquid crystal properties exhibited; examples include nematic phases, smectic A phases, (chiral) smectic C phases, cholesteric phases, or diskoid phases, with nematic phases being preferred.

[0049] In addition, the phrase "exhibiting liquid crystal properties" as used in this specification refers to the state at room temperature (25°C).

[0050] In this embodiment, when the liquid crystal material is a compound monomer, it can be synthesized according to a known synthesis method, thereby preparing the liquid crystal material. Furthermore, when the liquid crystal material is a liquid crystal composition containing two or more compounds, a general manufacturing method for liquid crystal compositions can be used as the method for preparing the liquid crystal composition. Specifically, the following methods can be used: all compounds that are components of the liquid crystal composition are added to a mixing container, dissolved by heat conduction through the walls of the mixing container from an external high-temperature medium, and mixed under reduced pressure or in an inactive gas environment by means of a stirring blade or the rotation of the container itself. Alternatively, the following methods can be used: a method of defoaming by rotating and revolving the container containing the liquid crystal compounds, while obtaining the liquid crystal composition without heating (planetary stirring); or a method of adding the liquid crystal compounds to a mixing container and heating them by microwave irradiation, etc. Furthermore, all compounds that are components of the liquid crystal composition can be synthesized according to known methods, or commercially available compounds can be purchased. Furthermore, in the preparation of liquid crystal compositions, for example, any known polymerizable (liquid crystal) compounds or orientation aids, other antioxidants, and other additives can be mixed together with various liquid crystal compounds.

[0051] When the liquid crystal material disclosed herein is a liquid crystal composition, the liquid crystal composition may be manufactured, for example, by mixing a compound represented by the following general formula (i), a compound represented by the following general formula (ii), any of the above-mentioned components as needed, and the following additives.

[0052] Examples of additives include: stabilizers, pigment compounds, and polymerizing compounds.

[0053] 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.

[0054] 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 0.5% by mass, and preferably 0.03 to 0.1% by mass.

[0055] In this embodiment, the liquid crystal material is preferably a compound having an isothiocyanate group (-NCS).

[0056] Since isothiocyanate groups have greater electronic polarization in an electric field than fluorine or cyano groups, when using monomers of compounds with isothiocyanate groups (-NCS) or liquid crystal compositions containing such compounds as liquid crystal materials, there is a tendency for the differential retardation value to increase.

[0057] In this embodiment, the liquid crystal material is preferably composed of one or more compounds selected from the group consisting of compounds represented by the following general formulas (i) to (ii).

[0058] The following general formula (i):

[0059] [Chemistry 1]

[0060]

[0061] (in general formula (i),

[0062] R i1 Indicates an alkyl group having 1 to 20 hydrogen atoms or carbon atoms.

[0063] One or more -CH2- atoms in the alkyl group can be independently replaced by -O-, -S-, -CO- and / or -CS-.

[0064] One or more -CH2-CH2- in the alkyl group can be independently replaced by -CO-O-, -O-CO-, -CO-S-, -S-CO-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- and / or -C≡C-.

[0065] One or more -CH2-CH2-CH2- in this alkyl group can be independently replaced by -O-CO-O-.

[0066] One or more of the -CH2-CH2-CH2- in this alkyl group can be independently replaced by -CH=CH-CO-O-, -CH=CH-O-CO-, -CO-O-CH=CH-, or -O-CO-CH=CH-.

[0067] One or more hydrogen atoms in the alkyl group can be independently replaced by halogen atoms.

[0068] Oxygen atoms do not bond directly with each other.

[0069] A i1 and A i2 Each can independently represent either a hydrocarbon ring with 3 to 16 carbon atoms or a heterocycle with 3 to 16 carbon atoms.

[0070] The above A i1 and A i2One or more hydrogen atoms in the form can be independently substituted by the S group. i1 replace,

[0071] Substituent S i1 It represents any one of the following: fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfanyl, nitro, cyano, isocyanate, amino, hydroxyl, mercapto, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyanate, or alkyl group having 1 to 20 carbon atoms.

[0072] One or more -CH2- atoms in the alkyl group can be independently replaced by -O-, -S- and / or -CO-.

[0073] One or more -CH2-CH2- in the alkyl group can be independently replaced by -CH=CH-, -CF=CF-, -C≡C-, -CO-O-, -O-CO-, -CO-S-, -S-CO-, -CO-NH- and / or -NH-CO-.

[0074] One or more -CH2-CH2-CH2- in this alkyl group can be independently replaced by -O-CO-O-.

[0075] One or more of the -CH2-CH2-CH2- in the alkyl group can be independently replaced by -CH=CH-CO-O-, -CH=CH-O-CO-, -CO-O-CH=CH- and / or -O-CO-CH=CH-.

[0076] One or more hydrogen atoms in the alkyl group can be independently replaced by halogen atoms.

[0077] Oxygen atoms do not bond directly with each other.

[0078] In the presence of multiple substituents S i1 In such cases, they can be the same or different.

[0079] L i1 and L i2 Each of the following can independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluoromethylthioalkyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or any alkyl group having 1 to 20 carbon atoms.

[0080] One or more -CH2- atoms in the alkyl group can be independently replaced by -O-, -S-, -CO- and / or -CS-.

[0081] One or more -CH2-CH2- in the alkyl group can be independently replaced by -CH=CH-, -CF=CF-, -C≡C-, -CO-O-, -O-CO-, -CO-S-, -S-CO-, -CO-NH- and / or -NH-CO-.

[0082] One or more -CH2-CH2-CH2- in this alkyl group can be independently replaced by -O-CO-O-.

[0083] One or more of the -CH2-CH2-CH2- in the alkyl group can be independently replaced by -CH=CH-CO-O-, -CH=CH-O-CO-, -CO-O-CH=CH- and / or -O-CO-CH=CH-.

[0084] One or more hydrogen atoms in the alkyl group can be independently replaced by halogen atoms.

[0085] Oxygen atoms do not bond directly with each other.

[0086] Z i1 and Z i2 Each can independently represent a single bond or any of the alkylene groups having 1 to 20 carbon atoms.

[0087] One or more -CH2- atoms in the alkylene group can be independently replaced by -O-, -CF2- and / or -CO-.

[0088] One or more -CH2-CH2- in the alkylene group can be independently replaced by -CH2-CH(CH3)-, -CH(CH3)-CH2-, -CH=CH-, -CF=CF-, -CH=C(CH3)-, -C(CH3)=CH-, -CH=N-, -N=CH-, -N=N-, -C≡C-, -CO-O-, and / or -O-CO-.

[0089] One or more -CH2-CH2-CH2-CH2- in this alkylene group can be independently replaced by -CH=NN=CH-.

[0090] Oxygen atoms do not bond directly with each other.

[0091] m i1 Represents integers from 0 to 1.

[0092] n i1 Represents integers from 0 to 3.

[0093] In A i2 or Z i2When multiple cases exist, they can be the same or different.

[0094] The following general formula (ii):

[0095] [Chemistry 2]

[0096]

[0097] (in general formula (ii),

[0098] R ii1 Each alkyl group, having 1 to 20 carbon atoms, is independently represented.

[0099] One or more -CH2- atoms in the alkyl group can be independently replaced by -O-, -S-, -CO- and / or -CS-.

[0100] One or more -CH2-CH2- in the alkyl group can be independently replaced by -CH=CH-, -CO-O-, -O-CO-, -CO-S-, -S-CO-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- and / or -C≡C-.

[0101] One or more -CH2-CH2-CH2- in this alkyl group can be independently replaced by -O-CO-O-.

[0102] One or more hydrogen atoms in the alkyl group can be independently replaced by halogen atoms.

[0103] Oxygen atoms do not bond directly with each other.

[0104] A ii1 and A ii2 Each of the following groups (a), (b), (c), and (d) can be represented independently:

[0105] (a) 1,4-cyclohexylene (one -CH2- or two or more non-adjacent -CH2- groups may be replaced with -O- and / or -S-).

[0106] (b) 1,4-Phenylidene (one -CH= or two or more non-adjacent -CH= groups may be substituted with -N=)

[0107] (c) Naphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl (one -CH= or two or more non-adjacent -CH= in naphthalene-2,6-diyl may be replaced by -N=),

[0108] (d) Thiophene-2,5-diyl, benzothiophene-2,5-diyl, benzothiophene-2,6-diyl, dibenzothiophene-3,7-diyl, dibenzothiophene-2,6-diyl, thieno[3,2-b]thiophene-2,5-diyl (one -CH= or two or more non-adjacent -CH= in this group may be replaced with -N=);

[0109] The above A ii1 and A ii2 One or more hydrogen atoms can be independently substituented by the S group. ii1 replace,

[0110] Substituent S ii1 The term represents any one of the following: halogen atom, pentafluoromethylthioalkyl, nitro, cyano, isocyano, amino, hydroxyl, mercapto, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyano, or alkyl group having 1 to 20 carbon atoms.

[0111] One or more -CH2- atoms in the alkyl group can be independently replaced by -O-, -S-, -CO- and / or -CS-.

[0112] One or more -CH2-CH2- in the alkyl group can be independently replaced by -CO-O-, -O-CO-, -CO-S-, -S-CO-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- and / or -C≡C-.

[0113] One or more -CH2-CH2-CH2- in this alkyl group can be independently replaced by -O-CO-O-.

[0114] One or more of the -CH2-CH2-CH2- in this alkyl group can be independently replaced by -CH=CH-CO-O-, -CH=CH-O-CO-, -CO-O-CH=CH-, or -O-CO-CH=CH-.

[0115] One or more hydrogen atoms in the alkyl group can be independently replaced by halogen atoms.

[0116] Oxygen atoms do not bond directly with each other.

[0117] In the presence of multiple substituents S ii1 In such cases, they can be the same or different.

[0118] Z ii1 It refers to any alkylene group with a single bond and 1 to 20 carbon atoms.

[0119] One or more -CH2- atoms in this alkylene group can be independently replaced by -O- atoms.

[0120] One or more -CH2-CH2- in the alkylene group can be independently replaced by -CH2-CH(CH3)-, -CH(CH3)-CH2-, -CH=CH-, -CF=CF-, -CH=C(CH3)-, -C(CH3)=CH-, -CH=N-, -N=CH-, -N=N-, -C≡C-, -CO-O-, and / or -O-CO-.

[0121] One or more -CH2-CH2-CH2- in this alkyl group can be independently replaced by -O-CO-O-.

[0122] One or more -CH2-CH2-CH2-CH2- in the alkylene group can be independently converted by -C(R) ia )=NN=C(R ib )-replace,

[0123] Oxygen atoms do not bond directly with each other.

[0124] The above R ia and R ib Each of the following can be independently represented: a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms.

[0125] One or more -CH2- atoms in the alkyl group can be independently replaced by -O-, -CO- and / or -S-.

[0126] One or more of the -CH2-CH2- groups in the alkyl group can be substituted with -CH=CH-, -CO-O-, -O-CO-, and / or -C≡C-.

[0127] Oxygen atoms do not bond directly with each other.

[0128] n ii1 Represents integers from 1 to 4.

[0129] In A ii1 and Z ii1 When multiple cases exist, they can be the same or different.

[0130] In addition, the liquid crystal material in this embodiment may be one liquid crystal compound selected from the group consisting of compounds represented by general formulas (i) to (ii), or it may be a liquid crystal composition formed by mixing two or more liquid crystal compounds.

[0131] (Process (II))

[0132] The liquid crystal material manufacturing method of this embodiment includes a step (II) of measuring the liquid crystal material by means of a differential delay measuring mechanism that measures the differential delay value of the liquid crystal material.

[0133] Therefore, step (II) is a step of measuring the differential retardation value of the liquid crystal material prepared in step (I).

[0134] By specifying the differential delay value, liquid crystal materials with less measurement error can be provided, thus providing liquid crystal materials with homogeneous electrical properties and methods for their manufacture.

[0135] In (II) above, at least a portion of the liquid crystal material prepared in step (I) may be extracted and evaluated by a differential delay measurement mechanism that measures the differential delay value.

[0136] The "differential delay value" in this specification, also known as the change in group delay (Δt), refers to the absolute value of the difference between the delay time from when a continuously varying frequency electrical signal (electromagnetic wave) is applied to the liquid crystal at a reference voltage V0 until the generation of flux density and the delay time from when a continuously varying frequency electrical signal (electromagnetic wave) is applied to the liquid crystal at an execution voltage V until the generation of flux density. In other words, it is the absolute value of the difference between the group delay of the measured object at the execution voltage V and the group delay of the measured object at the reference voltage V0. Furthermore, the differential delay value in this embodiment is measured using the so-called FDR method, as described below, calculated based on the S-parameters of a circuit network analyzer, such as a vector network analyzer, consisting of a signal source, a power splitter, a coupler, and at least three receivers (here, a reference receiver (R), a reflection receiver (A), and a transmission receiver (B)). More specifically, the transmission delay time t (= group delay) can be expressed using the phase of S21 and as shown in the following formula (I).

[0137] [Number 1]

[0138]

[0139] (In the above formula (I), ω is the angular frequency, S21 is a parameter representing the input-output characteristics of the measured object with 2 ports, and represents the transmission coefficient from port 1 to port 2).

[0140] In addition, the differential delay value (Δt) calculated by applying a high-frequency electric field to the liquid crystal material filled in the coaxial tube of transmission line length l and using the FDR method can also be expressed by the following formula (II).

[0141] [Number 2]

[0142]

[0143] (In the above formula (II), l is the transmission line length, c is the speed of light, ε(v) is the real part of the complex permittivity of the liquid crystal material under the execution voltage, and ε(0) is the real part of the complex permittivity of the liquid crystal material under the reference voltage).

[0144] First, refer to Figure 1 and Figure 2 The overall picture of the differential delay measurement system 100 of this embodiment, which is equipped with a differential delay measurement mechanism for measuring the differential delay value of the measured object (liquid crystal material), will be described below.

[0145] Figure 1 This is a schematic diagram illustrating an example of the configuration of the differential delay measurement system 100 in this embodiment. A coaxial tube 6 filled with liquid crystal material is connected between the signal transmitting terminal L and the signal receiving terminal R of the vector network analyzer 2 via DC block capacitors 3a and b, coaxial components 4a and b, and adapters 5a and b. Furthermore, a DC power supply 7 is electrically connected via coaxial components 4a and b. Additionally, a processing device 1 is connected to the vector network analyzer 2.

[0146] Therefore, the measurement results obtained by the differential delay measurement system 100 are displayed on the display unit of the vector network analyzer 2 and transmitted to the processing device 1 connected to the vector network analyzer 2. As the processing device 1, devices such as plotters and computers (personal computers) can be switched or connected in parallel as needed. Based on the measurement results of the transmission characteristics displayed on the display unit or the processing results obtained by the processing device 1, the transmission characteristics of the liquid crystal material filled in the coaxial tube 6 are calculated.

[0147] When measuring transmission characteristics, the oscillation frequency range of the scanning frequency oscillator of the network analyzer 2 can be set to the blocking frequency when the liquid crystal material containing the object under test is filled in the coaxial tube 6. The differential delay value can be displayed on the display unit of the vector network analyzer 2, or it can be directly read and calculated from the frequency characteristics of the transmission coefficient recorded on the plotter, or the differential value related to the frequency of the transmission coefficient can be obtained by the processing device 1 and calculated based on the frequency at which its maximum value is given.

[0148] Generally, the signal transmitting terminal L and the signal receiving terminal R can use either a coaxial tube connector or a waveguide. Figure 1 The example of a coaxial tube connector is used as an example. Additionally, the network analyzer 2 includes a scan frequency oscillator (not shown), a level detector (not shown), and a correction circuit (not shown).

[0149] exist Figure 1In this example, the coaxial tube 6 is shown in which a linear body, serving as the inner conductor 8, is inserted into the interior of a cylindrical outer conductor. Furthermore, a gap (space) exists between the inner conductor 8 and the inner wall of the cylindrical outer conductor. The object being measured, such as liquid crystal material, fills this gap. Then, using... Figure 2 The state in which the gap of the coaxial tube 6 is filled with liquid crystal material will be explained.

[0150] Figure 2 (a) and (b) both indicate that... Figure 1 The diagram shows a cross-sectional view of the coaxial tube 6 cut along direction II. More specifically, Figure 2 (a) is a schematic diagram showing the orientation of liquid crystal molecules 10 in a state (no bias state) where a reference voltage Vo (e.g., 0V) is applied between the inner conductor 8 and the outer conductor 9 without current flowing through the inner conductor 8 from the DC power supply 7 via coaxial components 4a and b, or with a weak current flowing through it. Figure 2 (b) is a schematic diagram showing the orientation of liquid crystal molecules in a state where current flows through the inner conductor 8 from the DC power supply 7 via the coaxial components 4a and b, and an operating voltage V (e.g., more than 0V) is applied between the inner conductor 8 and the outer conductor 9.

[0151] When the voltage between the inner conductor 8 and the outer conductor 9 is below the reference voltage Vo, such as Figure 2 As shown in (a), the long axis of the liquid crystal molecules 10 is randomly oriented relative to the direction of the electric field E0, therefore the liquid crystal molecules 10 are in a so-called random orientation state. Furthermore, when the voltage between the inner conductor 8 and the outer conductor 9 is greater than or equal to the operating voltage V, as... Figure 2 As shown in (b), the liquid crystal molecules 10 are formed in relation to the electric field E. v An orientation state in which the long axis directions of the liquid crystal molecules 10 are aligned in a parallel direction.

[0152] The following describes each component of the differential delay measurement system 100 in this embodiment.

[0153] <Differential Delay Measurement Agency>

[0154] The differential delay measurement mechanism in this embodiment includes a coaxial tube 6 comprising a linear inner conductor 8 and an outer conductor 9 having a gap for inserting the inner conductor 8, and a mechanism for calculating the differential delay value of the liquid crystal material. The differential delay value of the liquid crystal material is the difference between the transmission delay time t0 and the transmission delay time tv. The transmission delay time t0 is measured by allowing an electromagnetic wave with a continuously changing frequency to propagate in the liquid crystal material filling the gap between the inner conductor 8 and the outer conductor 9 while a reference voltage V0 is applied between the inner conductor 8 and the outer conductor 9. The transmission delay time tv is measured by allowing the electromagnetic wave to propagate in the liquid crystal material while an execution voltage V greater than the reference voltage V0 is applied between the inner conductor 8 and the outer conductor 9.

[0155] That is, the differential delay measurement mechanism in this embodiment includes a coaxial tube 6 that can be filled with liquid crystal material as a measurement sample, and has a mechanism for calculating the differential delay value of the liquid crystal material. This differential delay value is the difference between the propagation delay time t0 and the propagation delay time tv. The propagation delay time t0 is measured by propagation in the liquid crystal material under a reference voltage V0, and the propagation delay time tv is measured by propagation in the liquid crystal material under an execution voltage V. Furthermore, this difference in propagation delay time corresponds to the difference in the set delay amount.

[0156] As described above, since the differential delay measurement mechanism uses only one coaxial tube 6, the problems of the accumulation of measurement errors (electromagnetic wave reflection or electromagnetic wave intensity loss error) and the reduction of measurement reproducibility caused by the desorption of the coaxial tube 6 can be solved.

[0157] -Coaxial tube-

[0158] In this embodiment, the coaxial tube 6 is as follows: Figure 1 and Figure 2 As shown, the coaxial tube 6 has a tubular outer conductor 9 with openings at both ends, and a solid linear body, namely an inner conductor 8, which is inserted through the outer conductor 9 but does not abut against the inner wall of the outer conductor 9. Therefore, by separating the inner wall of the outer conductor 9 and the inner conductor 8 at a specific interval, the coaxial tube 6 has a gap that allows liquid crystal material to be filled into the coaxial tube 6.

[0159] Furthermore, the coaxial tube 6 consists of a coaxial tube body and coaxial tube connectors located at both ends of the coaxial tube body to support the inserted internal conductor 8. There are no particular limitations on the material used to construct the coaxial tube 6, but a metal with excellent machinability and corrosion resistance is preferred. For example, brass or brass (solid brass) is preferred as the material for constructing the coaxial tube 6.

[0160] Furthermore, the shape of the coaxial tube 6 can be cylindrical or polygonal, etc., preferably cylindrical.

[0161] Furthermore, in Figure 1 For ease of explanation, the diagram shows the coaxial tube body and the pair of coaxial tube connectors separated, but the actual coaxial tube 6 connects the coaxial tube body and the coaxial tube connectors. Furthermore, to indicate that the coaxial tube body and the coaxial tube connectors are components of the coaxial tube 6, they are surrounded by solid lines.

[0162] In this embodiment, the inner conductor 8 is a solid wire, also known as a central conductor. The material constituting the inner conductor 8 is preferably a conductor with excellent conductivity and high rigidity, such as hard steel wire or piano wire. Ideally, the inner conductor 8 is housed within the center of the cross-section of the coaxial tube 6, and the long axis of the inner conductor 8 is preferably straight.

[0163] In this embodiment, it is essential to ensure that the object to be measured (liquid crystal material) completely fills the gap between the outer conductor 9 and the inner conductor 8. Therefore, the outer diameter of the inner conductor 8 must be smaller than the inner diameter of the coaxial tube 6 (equal to the inner diameter of the outer conductor 9). The width of the gap filling the object to be measured, i.e., the shortest distance between the outer conductor 9 and the inner conductor 8 (inner diameter of the outer conductor 9 - outer diameter of the inner conductor 8), is approximately 1 mm, and more specifically, preferably 0.5 to 1.5 mm. Furthermore, the inner diameter of the outer conductor 9, which is also the inner diameter of the coaxial tube 6, is approximately 3 mm, and more specifically, preferably approximately 2.5 to 3.5 mm. Moreover, the outer diameter of the inner conductor 8 is approximately 1 mm, and more specifically, preferably 0.5 to 1.5 mm.

[0164] In this embodiment, the length of the internal conductor 8 along its major axis is preferably the same as the length including the coaxial tube body and the coaxial tube connectors provided at both ends thereon. The length along the major axis of the liquid crystal material filling portion in the coaxial tube body is preferably 10 to 100 mm, more preferably 10 to 50 mm. In addition, the number of internal conductors 8 is preferably one.

[0165] In this embodiment, the outer conductor 9 must be electrically insulated from the inner conductor 8, and the fluid-flowing test substance must not leak out from the gap. Therefore, it is preferable to use a sealing material such as Teflon resin inside the coaxial tube connector supporting the inner conductor 8.

[0166] -Transmission delay-

[0167] In this embodiment, a circuit network analyzer, such as a vector network analyzer 2, can be used as a mechanism to calculate the difference between the aforementioned propagation delay time t0 and the aforementioned propagation delay time tv, which is the differential delay value of the liquid crystal material. Generally, the vector network analyzer 2 is developed as a device for analyzing electronic circuit networks, and is basically a device for measuring impedance and attenuation. Since it can measure amplitude and phase, it can measure the high-frequency characteristics of various samples.

[0168] Furthermore, the aforementioned transmission delay time t0 and the aforementioned transmission delay time t v The determination was carried out under the condition that the liquid crystal material was at room temperature (25°C).

[0169] The following describes the measurement of S21, which is used to calculate the group delay amount corresponding to the transmission delay time, using the measurement mechanism of such a vector network analyzer 2. Furthermore, the S-parameter varies depending on the definition of the port; therefore, for ease of explanation, the case where each port of the object under test has two ports is designated as port 1 and port 2 will be described below. Moreover, port 1 and port 2 can also be used as two ports of the vector network analyzer 2.

[0170] The vector network analyzer 2 consists of a signal source, a power splitter, a coupler, and at least three receivers (here, a reference receiver (R), a reflector receiver (A), and a transmitter receiver (B)). The electromagnetic wave signal output from the signal source is split into two by the power splitter. One signal is input to the reference receiver (R), and the other signal is output as an incident signal from port 1. This incident signal (e.g., from the signal transmission terminal L side) is input to the liquid crystal material filled in the coaxial tube 6, which is the object to be measured. The reflected signal reflected by the coaxial tube 6 (liquid crystal material) is received by the reflector receiver (A). Next, the transmitted signal (i.e., the incident signal propagating and passing through the liquid crystal material) through the coaxial tube 6 (liquid crystal material) is received by the transmitter receiver (B). The phase is detected by comparing the transmitted signal received by the transmitter receiver (B) and the reflected signal received by the reflector receiver (A) with the reference signal received by the reference receiver (R). Furthermore, the reflectance coefficient (S11) and transmission coefficient (S21) of the liquid crystal material filled in the coaxial tube 6 are calculated based on the difference with the reference signal. This process constitutes one cycle of forward transmission, and the cycle is repeated while varying the frequency within a set range (0.1–26.5 GHz). This cycle is also referred to as forward transmission output from port 1.

[0171] In this embodiment, the frequency of the continuous variation of the electromagnetic wave (incident signal) propagating in the liquid crystal material by the self-vector network analyzer 2 is as described below, preferably in the range of 0.1 to 26.5 GHz. Furthermore, in this embodiment, the frequency in the range of 0.1 to 26.5 GHz must be repeatedly varied multiple times (repeatedly increasing the frequency continuously from 0.1 to 26.5 GHz until it reaches 26.5 GHz, and then again continuously increasing the frequency from 0.1 to 26.5 GHz), while the electromagnetic wave (incident signal) at this frequency overlaps with the internal conductor 8, and DC power is applied to the internal conductor 8 from the DC power supply 7 using the coaxial components 4a and b.

[0172] In addition, in this embodiment, respectively for Figure 2 (a) shows that the liquid crystal molecule 10 is in a random orientation state (under the condition of a reference voltage Vo) and Figure 2 (b) The above cycle is performed with the liquid crystal molecules 10 shown in the diagram oriented in a specific direction along their long axis (under the condition of an execution voltage V or higher). This allows for the measurement of the transfer coefficient (S21) corresponding to cases where the orientation state of the liquid crystal molecules 10 differs from that in the liquid crystal material.

[0173] Therefore, by using the above general formula (I), it is possible to measure the transmission delay time t0 under conditions where the reference voltage Vo applied between the inner conductor 8 and the outer conductor 9 is below, and the transmission delay time t1 under conditions where the execution voltage V is above. v The difference delay value is determined based on the absolute value of the difference between the two.

[0174] Furthermore, the reflection coefficient (S11) and transmission coefficient (S21) mentioned here are called S-parameters. For example, S11 (reflection coefficient) represents the change in magnitude and phase of the reflected signal relative to the incident signal, and S21 (transmission coefficient) represents the change in magnitude and phase of the transmitted signal relative to the incident signal.

[0175] Furthermore, when the switch is switched to the opposite direction, similar to the forward transmission described above, an incident signal is input to the liquid crystal material (e.g., from the signal transmission terminal R side) filled in the coaxial tube 6, which is the object being measured, through the reverse transmission output from port 2, and the reverse characteristics are measured. From this, the reflection coefficient (S22) and transmission coefficient (S12) of the reverse transmission are calculated.

[0176] In this embodiment, the operating voltage V applied between the inner conductor 8 and the outer conductor 9 is preferably 5V or higher, and more preferably 50 to 150V. Furthermore, the transmission delay characteristic is measured after the applied voltage reaches a certain value (applied value).

[0177] In this embodiment, the frequency of the electromagnetic wave (incident signal) propagating through the liquid crystal material is preferably continuously varied by the vector network analyzer 2 within the range of 0.1 to 26.5 GHz, and the range of 0.1 to 26.5 GHz is repeated multiple times and overlapped with the internal conductor 8. This frequency range is determined based on the performance of the vector network analyzer 2 used for measurement, therefore, a vector network analyzer 2 that can use the frequency band for which the characteristics to be obtained must be selected.

[0178] <Other Components of the Differential Delay Measurement System 100>

[0179] In this embodiment, the capacitors 3a and 3b for the DC block are not particularly limited, as long as they can prevent DC current from flowing towards the vector network analyzer 2 when measuring signals with overlapping DC voltages. Similarly, the adapters 5a and 5b are not particularly limited, as long as they can be used to electrically connect the coaxial tube 6 to the coaxial assemblies 4a and 4b. Likewise, the DC voltage 7 is not particularly specific, but it must be applied via the coaxial assemblies 4a and 4b, and the DC power supply 7 must be selected to match the voltage applied to the internal conductor 8.

[0180] [Methods for determining differential delay]

[0181] This disclosure discloses a method for measuring differential delay, wherein the differential delay is the change in the propagation delay time of an electromagnetic wave propagating in a liquid crystal material filled in the gap between the inner conductor 8 and the outer conductor 9, using a coaxial tube 6 having a linear inner conductor 8 and an outer conductor 9 for inserting the inner conductor 8. Furthermore, the method for measuring differential delay includes the following steps: a step of preparing liquid crystal material; a step of filling the liquid crystal material between the inner conductor 8 and the outer conductor 9; and a step of calculating the differential delay value of the liquid crystal material, wherein the differential delay value is the difference between the propagation delay time t0 and the propagation delay time tv. The propagation delay time t0 is measured by allowing an electromagnetic wave (incident signal) with a continuously changing frequency to propagate in the liquid crystal material while a reference voltage V0 is applied between the inner conductor 8 and the outer conductor 9, and the propagation delay time tv is measured by applying an execution voltage V greater than the reference voltage V0 between the inner conductor 8 and the outer conductor 9, allowing the propagation of the electromagnetic wave (incident signal) in the liquid crystal material.

[0182] The differential delay measurement method in this embodiment only requires filling the gap between the inner conductor 8 and the outer conductor 9 of the coaxial tube 6 with liquid crystal material after preparing the liquid crystal material, ensuring that air bubbles do not enter the gap between the inner conductor 8 and the outer conductor 9. Furthermore, the liquid crystal material is the same as the material described in the section of step (I) above. In the differential delay measurement method of this embodiment, the liquid crystal material can be a commercially available compound or a synthesized compound.

[0183] As part of the sequence of the differential delay measurement method in this embodiment, firstly, a voltage less than or equal to a reference voltage V0 (e.g., no voltage applied (no bias)) is applied between the inner conductor 8 and the outer conductor 9. After calculating S21 using the differential delay measurement system 100 described above, the transmission delay time t0 is calculated according to the above formula (I). Next, a voltage greater than or equal to the execution voltage V is applied, and after calculating S21 using the differential delay measurement system 100 described above, the transmission delay time t0 is calculated according to the above formula (I). v Subsequently, the transmission delay time t0 and the transmission delay time t are calculated. v The absolute value of the difference is used to determine the difference delay value.

[0184] [Apparatus for measuring differential delay]

[0185] This disclosure discloses a device for measuring differential delay values, characterized by comprising: a coaxial tube 6 having a linear inner conductor 8, an outer conductor 9 through which the inner conductor 8 is inserted, and a gap between the inner conductor 8 and the outer conductor 9 that can be filled with liquid crystal material; an electrical signal transceiver unit (i.e., a reflection receiver (A) and a transmission receiver (B)) that inputs an electrical signal (i.e., an incident signal) of an electromagnetic wave into the coaxial tube 6 and receives an output signal (i.e., a transmission signal) of an electromagnetic wave output in response to the electrical signal; and an analysis processing unit (i.e., a vector network analyzer 2 and a processing device) that analyzes and processes the electrical signal and the output signal received and transmitted by the electrical signal transceiver unit.

[0186] The aforementioned analysis processing unit calculates the differential delay value of the liquid crystal material. The differential delay value of the liquid crystal material is the difference between the transmission delay time t0 and the transmission delay time tv. The transmission delay time t0 is measured by allowing an electromagnetic wave (= incident signal) with a continuously changing frequency to propagate in the liquid crystal material while a reference voltage V0 is applied between the inner conductor 8 and the outer conductor 9. The transmission delay time tv is measured by allowing an electromagnetic wave (= incident signal) to propagate in the liquid crystal material while an execution voltage V greater than the reference voltage V0 is applied between the inner conductor 8 and the outer conductor 9.

[0187] Therefore, the device for measuring the differential delay value corresponds to the differential delay measurement system 100 described above, and therefore the description here is omitted.

[0188] [Physical properties of liquid crystal materials and compounds used in liquid crystal materials]

[0189] Liquid crystal phase upper limit temperature (T) ni () is the temperature at which the self-nematic phase of the liquid crystal composition undergoes a phase transition to the isotropic phase.

[0190] T niThe determination is made by preparing a microscope specimen by clamping a liquid crystal composition between a glass slide and a coverslip, and observing it under a polarizing microscope while heating it on a heating stage.

[0191] Alternatively, it can also be measured by differential scanning calorimetry (DSC).

[0192] The unit is "℃".

[0193] T ni The higher the temperature, the more likely it is to maintain the nematic phase at high temperatures, thus allowing for a wider range of driving temperatures.

[0194] The upper limit temperature (T) of the liquid crystal phase of the liquid crystal material in this embodiment ni The temperature can be appropriately set to correspond to situations where the external temperature of the liquid crystal display element can be controlled, such as indoors or in a car, or when it is used outdoors. However, from the viewpoint of the driving temperature range, it is preferable to be 50°C or higher, preferably 100 to 200°C, and preferably 110°C to 180°C.

[0195] Liquid crystal phase lower limit temperature (T) →n The temperature at which a liquid crystal composition transforms from other phases (glass, smectic, crystalline) into a nematic phase is called the liquid crystal composition.

[0196] T →n The liquid crystal composition was filled into a glass capillary, which was then immersed in a refrigerant at -70°C. This caused the liquid crystal composition to transform into other phases, raising the temperature, and the results were observed and measured simultaneously.

[0197] Alternatively, it can also be measured by differential scanning calorimetry (DSC).

[0198] The unit is "℃".

[0199] T →n The lower the temperature, the better the nematic phase can be maintained at low temperatures, thus allowing for a wide range of driving temperatures.

[0200] From the viewpoint of driving temperature, the lower limit temperature of the liquid crystal phase of the liquid crystal material in this embodiment (T) →n The temperature is preferably below 10℃, preferably -70 to 0℃, and preferably -45 to -5℃.

[0201] Δn (refractive index anisotropy) is an indicator related to the phase modulation power of light at the wavelength of the object.

[0202] At 25°C and 589 nm, an Abbe refractometer was used to measure Δn, and the anomalous refractive index (n) of the liquid crystal composition was considered. e ) and ordinary refractive index (n o The difference (n) e -no Find the answer.

[0203] Alternatively, Δn can be determined using a phase difference measuring device.

[0204] The relationship Δn = Re / d holds true between the phase difference Re, the thickness d of the liquid crystal layer, and Δn.

[0205] A liquid crystal composition was injected into a glass cell with a polyimide alignment film and an anti-parallel friction treatment, with a cell gap (d) of approximately 3.0 μm. The in-plane Re was measured using a RETS-100 phase difference film and optical material inspection device (manufactured by Otsuka Electron Co., Ltd.).

[0206] The measurements were performed at 25°C and 589 nm, and no units were specified.

[0207] From the viewpoint of the phase modulation power of light of wavelength, the liquid crystal material in this embodiment preferably has a Δn of 0.20 or more at 25°C and 589nm, preferably 0.25 to 0.60, preferably 0.30 to 0.55, and preferably 0.35 to 0.50.

[0208] Rotational viscosity (γ1) is the viscosity rate related to the rotation of liquid crystal molecules.

[0209] γ1 can fill the liquid crystal composition into glass cells with a cell gap of about 10 μm and measure it using LCM-2 (manufactured by Dongyang Technology).

[0210] In the case of a liquid crystal composition with positive dielectric anisotropy, a horizontal alignment unit is used; in the case of a liquid crystal composition with negative dielectric anisotropy, a vertical alignment unit is used.

[0211] The measurements were performed at 25°C, and the units are measured in mPa·s.

[0212] The smaller γ1 is, the faster the response speed of the liquid crystal composition, and therefore it is preferred in any liquid crystal display element.

[0213] From the viewpoint of response speed, the rotational viscosity (γ1) of the liquid crystal material in this embodiment at 25°C is preferably 150 to 2000 mPa·s, preferably 200 to 1500 mPa·s, and preferably 250 to 1000 mPa·s.

[0214] Threshold voltage (V) th It is related to the driving voltage of the liquid crystal composition.

[0215] V th It can be determined based on the transmittance when the liquid crystal composition is filled into a TN cell with a gap of 8.3 μm and a voltage is applied.

[0216] The measurement was performed at a temperature of 25°C, and the unit is "V".

[0217] V th The lower the value, the more it can be driven at a lower voltage.

[0218] From the viewpoint of driving voltage, the liquid crystal material in this embodiment is at 25°C with a V0. th Preferably, the voltage is below 3.0V, preferably 0.3 to 3.0V, preferably 0.5 to 2.7V, preferably 0.7 to 2.5V, preferably 0.9 to 2.3V, preferably 1.1 to 2.1V, and preferably 1.3 to 2.1V.

[0219] Δε(1kHz) is represented by Δε(1kHz)=ε∥-ε⊥.

[0220] That is, Δε (1kHz) is the difference between the dielectric constant ε∥ and the dielectric constant ε⊥, and the dielectric constant is an indicator of the ease of polarization.

[0221] Δε (1 kHz) was determined by the following method.

[0222] First, the liquid crystal material to be measured is encapsulated in a cell that has undergone vertical alignment treatment, and the dielectric constant ε∥ of the long axis of the liquid crystal molecules is measured. Then, the liquid crystal material to be measured is encapsulated in a cell that has undergone horizontal alignment treatment, and the dielectric constant ε⊥ of the short axis of the liquid crystal molecules is measured.

[0223] The dielectric anisotropy Δε (1kHz) can be calculated from the difference between these measured values.

[0224] Furthermore, the dielectric constant can be measured using a dielectric constant measuring device called an LCR meter and with the measuring frequency set to 1 kHz.

[0225] In addition, the measurement was conducted at a temperature of 25°C and has no unit.

[0226] From the viewpoint of driving voltage, the liquid crystal material in this embodiment preferably has a Δε (1kHz) of 1 to 25 at 25°C, preferably 3 to 20, and preferably 5 to 15.

[0227] The liquid crystal material in this embodiment has a differential retardation value of 0.01 or higher, preferably 0.01 to 0.05, preferably 0.015 to 0.045, preferably 0.015 to 0.040, preferably 0.020 to 0.035, and preferably 0.025 to 0.325. Liquid crystal materials with a differential retardation value of 0.01 or higher tend to exhibit excellent electrical properties.

[0228] To achieve a differential retardation value of 0.01 or higher, it is necessary to combine compounds with groups having greater electronic polarization in an electric field than fluorine or cyano groups. Therefore, liquid crystal materials preferably have isothiocyanate groups (-NCS).

[0229] The liquid crystal material having a differential delay value of 0.01 or more is preferably composed of one or more compounds selected from the group consisting of compounds represented by the following general formulas (i) to (ii).

[0230] The liquid crystal material, or the liquid crystal material in this embodiment, may be one liquid crystal compound selected from the group consisting of compounds represented by general formulas (i) to (ii), or it may be a liquid crystal composition formed by mixing two or more liquid crystal compounds.

[0231] The liquid crystal material disclosed herein is preferably a compound represented by the following general formula (i) containing one or more compounds having an indane structure or a tetrahydronaphthalene structure and an isothiocyanate group (-NCS).

[0232] [Chemistry 3]

[0233]

[0234] In general formula (i), R i1 An alkyl group having 1 to 20 hydrogen or carbon atoms.

[0235] The alkyl group having 1 to 20 carbon atoms is a straight-chain, branched, or cyclic alkyl group, preferably a straight-chain alkyl group.

[0236] 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.

[0237] One or more of the -CH2- groups in the alkyl group can be independently replaced by -O-, -S-, -CO- and / or -CS-.

[0238] In addition, one or more of the -CH2-CH2- groups in the alkyl group may be independently replaced by -CO-O-, -O-CO-, -CO-S-, -S-CO-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- and / or -C≡C-.

[0239] In addition, one or more of the -CH2-CH2-CH2- alkyl groups can be independently replaced by -O-CO-O-.

[0240] In addition, one or more of the -CH2-CH2-CH2-CH2- alkyl groups can be independently replaced by -CH=CH-CO-O-, -CH=CH-O-CO-, -CO-O-CH=CH-, or -O-CO-CH=CH-.

[0241] In addition, one or more hydrogen atoms in the alkyl group can be independently replaced by halogen atoms.

[0242] Examples of halogen atoms include fluorine, chlorine, and bromine.

[0243] In cases where the alkyl group is substituted with a specific group, oxygen atoms do not bond directly to each other.

[0244] Furthermore, from the viewpoint of compound stability, it is preferable that sulfur atoms do not directly bond with sulfur atoms and / or oxygen atoms do not directly bond with sulfur atoms.

[0245] For example, R i1 By replacing one of the -CH2- atoms in the alkyl group with -O-, an alkoxy group with 1 to 19 carbon atoms can be represented.

[0246] The alkoxy group can be a straight-chain, branched, or cyclic alkoxy group, preferably a straight-chain alkoxy group.

[0247] The number of carbon atoms in the alkoxy group is preferably 2 to 10, and more preferably 2 to 6.

[0248] Additionally, R i1 By replacing one of the -CH2- atoms in the alkyl group with -S-, thioalkoxy groups (alkathiol, alkylthiol) with 1 to 19 carbon atoms can be represented.

[0249] The thioalkoxy group can be linear, branched, or cyclic, with linear thioalkoxy groups being preferred.

[0250] The number of carbon atoms in the thioalkoxy group is preferably 2 to 10, and more preferably 2 to 6.

[0251] Additionally, R i1 Alkenes with 2 to 20 carbon atoms can be represented by replacing one or more of the -CH2-CH2- atoms in the alkyl group with -CH=CH- atoms.

[0252] The alkenyl group can be linear, branched, or cyclic, with linear alkenyl groups being preferred.

[0253] The number of carbon atoms in the alkenyl group is preferably 2 to 10, and more preferably 2 to 6.

[0254] Additionally, R i1By replacing one or more of the -CH2-CH2- groups in the alkyl group with -C≡C-, an alkynyl group with 2 to 20 carbon atoms can be represented.

[0255] The alkynyl group can be linear, branched, or cyclic, with linear alkynyl groups being preferred.

[0256] The number of carbon atoms in the alkynyl group is preferably 2 to 10, and more preferably 2 to 6.

[0257] Additionally, R i1 An alkyl group with 2 to 19 carbon atoms can be represented by replacing one -CH2- in the alkyl group with -O- and replacing one or more -CH2-CH2- with -CH=CH-.

[0258] The olefinic group can be linear, branched, or cyclic, with linear olefinic groups being preferred.

[0259] The number of carbon atoms in the olefinic group is preferably 2 to 10, and more preferably 2 to 6.

[0260] Additionally, R i1 By replacing one or more hydrogen atoms in the alkyl group with halogen atoms, alkyl halides with 1 to 20 carbon atoms can be represented.

[0261] The alkyl halide is a straight-chain, branched, or cyclic alkyl halide, preferably a straight-chain alkyl halide.

[0262] The number of carbon atoms in the alkyl halide is preferably 2 to 10, and more preferably 2 to 6.

[0263] Additionally, R i1 By replacing one -CH2- atom in the alkyl group with -O- atom and replacing one or more hydrogen atoms in the alkyl group with halogen atoms, a halogenated alkoxy group with 1 to 19 carbon atoms can be represented.

[0264] The halogenated alkoxy group can be linear, branched, or cyclic, with linear halogenated alkoxy groups being preferred.

[0265] The number of carbon atoms in the halogenated alkoxy group is preferably 2 to 10, and more preferably 2 to 6.

[0266] As R i1 Specific examples of alkyl groups having 1 to 20 carbon atoms (including substituted cases) can be listed in formula (R). i1 -1)~(R i1 -36) represents groups, etc.

[0267] [Chemistry 4]

[0268]

[0269] Formula (R) i1 -1)~(R i1 In -36), the black dots represent bonding bonds to the indene or tetrahydronaphthalene structures.

[0270] Furthermore, as R i1 From the viewpoint of compatibility with other liquid crystal compounds, linear alkyl groups with 2 to 6 carbon atoms are preferred.

[0271] In general formula (i), A i1 and A i2 Each can be independently represented as either a hydrocarbon ring with 3 to 16 carbon atoms or a heterocycle with 3 to 16 carbon atoms.

[0272] More specifically, the hydrocarbon ring or heterocycle having 3 to 16 carbon atoms is preferably a group selected from the group consisting of the following groups (a), (b), (c), and (d):

[0273] (a) 1,4-cyclohexylene (one -CH2- or two or more non-adjacent -CH2- groups may be replaced with -O- or -S-).

[0274] (b) 1,4-Phenylidene (one -CH= or two or more non-adjacent -CH= groups may be substituted with -N=)

[0275] (c) 1,4-cyclohexenyl, bicyclo[2.2.2]octane-1,4-diyl, naphth-2,6-diyl, naphth-1,4-diyl, 1,2,3,4-tetrahydronaphth-2,6-diyl, 5,6,7,8-tetrahydronaphth-1,4-diyl, decahydronaphth-2,6-diyl, anthracene-2,6-diyl, anthracene-1,4-diyl, anthracene-9,10-diyl, phenanthrene- 2,7-Diyl (one or more -CH= in naphthalene-2,6-diyl, naphthalene-1,4-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, 5,6,7,8-tetrahydronaphthalene-1,4-diyl, anthracene-2,6-diyl, anthracene-1,4-diyl, anthracene-9,10-diyl, or phenanthrene-2,7-diyl can be replaced with -N=),

[0276] (d) Thiophene-2,5-diyl, benzothiophene-2,5-diyl, benzothiophene-2,6-diyl, dibenzothiophene-3,7-diyl, dibenzothiophene-2,6-diyl, thieno[3,2-b]thiophene-2,5-diyl (one -CH= or two or more non-adjacent -CH= in this group may be replaced with -N=).

[0277] A i1 and A i2One or more hydrogen atoms in the form can be independently substituted by the S group. i1 replace.

[0278] Substituent S i1 It represents any one of the following: fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluoromethylthioalkyl, nitro, cyano, isocyano, amino, hydroxyl, mercapto, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyano, or alkyl with 1 to 20 carbon atoms.

[0279] The alkyl group can be a straight-chain, branched, or cyclic alkyl group, preferably a straight-chain alkyl group.

[0280] The alkyl group preferably has 2 to 10 carbon atoms, and more preferably 3 to 6.

[0281] One or more of the -CH2- groups in the alkyl group can be independently replaced by -O-, -S- and / or -CO-.

[0282] In addition, one or more of the -CH2-CH2- groups in the alkyl group may be independently replaced by -CH=CH-, -CF=CF-, -C≡C-, -CO-O-, -O-CO-, -CO-S-, -S-CO-, -CO-NH- and / or -NH-CO-.

[0283] In addition, one or more of the -CH2-CH2-CH2- alkyl groups can be replaced by -O-CO-O-.

[0284] In addition, one or more of the -CH2-CH2-CH2-CH2- alkyl groups can be independently replaced by -CH=CH-CO-O-, -CH=CH-O-CO-, -CO-O-CH=CH- and / or -O-CO-CH=CH-.

[0285] One or more hydrogen atoms in the alkyl group can be independently replaced by halogen atoms.

[0286] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0287] In cases where the alkyl group is substituted with a specific group, oxygen atoms do not bond directly to each other.

[0288] Furthermore, from the viewpoint of compound stability, it is preferable that sulfur atoms do not directly bond with sulfur atoms and / or oxygen atoms do not directly bond with sulfur atoms.

[0289] As a substituent S i1 Preferably, it is a straight-chain alkyl group with fluorine atoms or 1 to 3 carbon atoms.

[0290] In addition, A is preferred. i1 and A i2 At least one of the S substituents i1 replace.

[0291] In addition, A is preferred. i2 With at least one substituent S i1 replace.

[0292] Furthermore, in the substituent S i1 When multiple cases exist, they can be the same or different.

[0293] As A i1 The substituent S in i1 The replacement position is preferably that of the following formula (A) i1 -SP-1)~(A i1 Either of the following (-SP-2).

[0294] [Chemistry 5]

[0295]

[0296] Formula (A) i1 -SP-1)~(A i1 In -SP-2), the white dot indicates the direction of Z. i1 The bond is a combination of two bonds, and the black dots represent the bonds to Z. i2 Or the bonding bond of isothiocyanate group (-NCS).

[0297] As A i2 The substituent S in i1 The replacement position is preferably that of the following formula (A) i2 -SP-1)~(A i2 Either of the following (-SP-2).

[0298] [Chemistry 6]

[0299]

[0300] Formula (A) i2 -SP-1)~(A i2 In -SP-2), the white dot indicates the direction of Z. i2 The bond is a combination of two bonds, and the black dots represent the bonds to Z. i2 Or the bonding bond of isothiocyanate group (-NCS).

[0301] More specifically, A i1 Preferably, it represents the following formula (A) i1 -1)~(A i1 Any one of -4).

[0302] [Chemistry 7]

[0303]

[0304] Formula (A) i1 -1)~(A i1 In -4), the white dot represents the direction of Z. i1 The bond is a combination of two bonds, and the black dots represent the bonds to Z. i2 Or the bonding bond of isothiocyanate group (-NCS).

[0305] More specifically, A i2 Preferably, it represents the following formula (A) i2 -1)~(A i2 -3) any one of them.

[0306] [Chemistry 8]

[0307]

[0308] Formula (A) i2 -1)~(A i2 In -3), the white dot represents the direction of Z. i2 The bond is a combination of two bonds, and the black dots represent the bonds to Z. i2 Or the bonding bond of isothiocyanate group (-NCS).

[0309] In general formula (i), L i1 and L i2 Each of the following can be independently represented as a hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluoromethylthioalkyl, nitro, cyano, isocyano, amino, hydroxyl, mercapto, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyano, or any alkyl group having 1 to 20 carbon atoms.

[0310] The alkyl group having 1 to 20 carbon atoms is a straight-chain, branched, or cyclic alkyl group, preferably a straight-chain alkyl group.

[0311] 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.

[0312] One or more of the -CH2- groups in the alkyl group can be independently replaced by -O-, -S-, -CO- and / or -CS-.

[0313] In addition, one or more of the -CH2-CH2- groups in the alkyl group may be independently replaced by -CH=CH-, -CF=CF-, -C≡C-, -CO-O-, -O-CO-, -CO-S-, -S-CO-, -CO-NH- and / or -NH-CO-.

[0314] In addition, one or more of the -CH2-CH2-CH2- alkyl groups can be replaced by -O-CO-O-.

[0315] In addition, one or more of the -CH2-CH2-CH2-CH2- alkyl groups can be independently converted by -CH=CH-CO-O-, -CH=CH-O-CO-, -CO-O-CH=CH- and / or -O-CO-CH=CH-.

[0316] In addition, one or more hydrogen atoms in the alkyl group can be independently replaced by halogen atoms.

[0317] Examples of halogen atoms include fluorine, chlorine, and bromine.

[0318] In cases where the alkyl group is substituted with a specific group, oxygen atoms do not bond directly to each other.

[0319] Furthermore, from the viewpoint of compound stability, it is preferable that sulfur atoms do not directly bond with sulfur atoms and / or oxygen atoms do not directly bond with sulfur atoms.

[0320] For example, L i1 and L i2 By replacing one of the -CH2- atoms in the alkyl group with -O-, an alkoxy group with 1 to 19 carbon atoms can be represented.

[0321] The alkoxy group can be a straight-chain, branched, or cyclic alkoxy group, preferably a straight-chain alkoxy group.

[0322] The number of carbon atoms in the alkoxy group is preferably 2 to 10, and more preferably 2 to 6.

[0323] In addition, L i1 and L i2 By replacing one of the -CH2- atoms in the alkyl group with -S-, thioalkoxy groups (alkathiol, alkylthiol) with 1 to 19 carbon atoms can be represented.

[0324] The thioalkoxy group can be linear, branched, or cyclic, with linear thioalkoxy groups being preferred.

[0325] The number of carbon atoms in the thioalkoxy group is preferably 2 to 10, and more preferably 2 to 6.

[0326] In addition, L i1 and L i2 Alkenes with 2 to 20 carbon atoms can be represented by replacing one or more of the -CH2-CH2- atoms in the alkyl group with -CH=CH- atoms.

[0327] The alkenyl group can be linear, branched, or cyclic, with linear alkenyl groups being preferred.

[0328] The number of carbon atoms in the alkenyl group is preferably 2 to 10, and more preferably 2 to 6.

[0329] In addition, L i1 and L i2 By replacing one or more of the -CH2-CH2- groups in the alkyl group with -C≡C-, an alkynyl group with 2 to 20 carbon atoms can be represented.

[0330] The alkynyl group can be linear, branched, or cyclic, with linear alkynyl groups being preferred.

[0331] The number of carbon atoms in the alkynyl group is preferably 2 to 10, and more preferably 2 to 6.

[0332] In addition, L i1 and L i2 An alkyl group with 2 to 19 carbon atoms can be represented by replacing one -CH2- in the alkyl group with -O- and replacing one or more -CH2-CH2- with -CH=CH-.

[0333] The olefinic group can be linear, branched, or cyclic, with linear olefinic groups being preferred.

[0334] The number of carbon atoms in the olefinic group is preferably 2 to 10, and more preferably 2 to 6.

[0335] In addition, L i1 and L i2 By replacing one or more hydrogen atoms in the alkyl group with halogen atoms, alkyl halides with 1 to 20 carbon atoms can be represented.

[0336] The alkyl halide is a straight-chain, branched, or cyclic alkyl halide, preferably a straight-chain alkyl halide.

[0337] The number of carbon atoms in the alkyl halide is preferably 2 to 10, and more preferably 2 to 6.

[0338] L i1 and L i2 Halogenated alkoxy groups with 1 to 19 carbon atoms can be represented by replacing one -CH2- atom in the alkyl group with -O- atom and replacing one or more hydrogen atoms in the alkyl group with halogen atoms.

[0339] The halogenated alkoxy group can be linear, branched, or cyclic, with linear halogenated alkoxy groups being preferred.

[0340] The number of carbon atoms in the halogenated alkoxy group is preferably 2 to 10, and more preferably 2 to 6.

[0341] As L i1 and L i2 Specific examples of alkyl groups having 1 to 20 carbon atoms (including substituted cases) can be listed in formula (L). i1 / 2 -1)~(L i1 / 2-36) represents groups, etc.

[0342] [Chemistry 9]

[0343]

[0344] Formula (L) i1 / 2 -1)~(L i1 / 2 In -36), the black dots represent bonding bonds to the indene or tetrahydronaphthalene structures.

[0345] From the viewpoint of compatibility with other liquid crystal compounds, L is preferred. i1 and L i2 At least one of them is a fluorine atom, preferably L. i1 and L i2 All are fluorine atoms.

[0346] Z i1 and Z i2 Each can be independently represented as a single bond or an alkylene group having 1 to 20 carbon atoms.

[0347] The alkylene group is a straight-chain, branched, or cyclic alkylene group, preferably a straight-chain alkylene group.

[0348] The number of carbon atoms in the alkylene group is preferably 2 to 10, and more preferably 2 to 6.

[0349] One or more of the -CH2- groups in the alkylene group can be independently replaced by -O-, -CF2- and / or -CO-.

[0350] In addition, one or more of the -CH2-CH2- in the alkylene group can be independently replaced by -CH2-CH(CH3)-, -CH(CH3)-CH2-, -CH=CH-, -CF=CF-, -CH=C(CH3)-, -C(CH3)=CH-, -CH=N-, -N=CH-, -N=N-, -C≡C-, -CO-O- and / or -O-CO-.

[0351] In addition, one or more of the -CH2-CH2-CH2-CH2- groups in the alkylene group can be independently replaced by -CH=NN=CH-.

[0352] In cases where the alkylene group is substituted with a specific group, oxygen atoms do not bond directly to each other.

[0353] Specific examples of alkylene groups having 2 to 20 carbon atoms (including substituted cases) can be enumerated as (Z i1 / 2 -1)~(Z i1 / 2 -24) represents groups, etc.

[0354] [Chemistry 10]

[0355]

[0356] Formula (Z) i1 / 2 -1)~(Z i1 / 2 In -24), the white dots represent the indenmann structure, the tetrahydronaphthalene structure, and A. i1 Or A i2 The bond is a combination of two bonds, and the black dots represent the bonds to A. i1 Or A i2 The bonding bonds.

[0357] Z is preferred i1 and Z i2 At least one of them is the formula (Z) i1 / 2 -4)(-C≡C-), preferably Z i1 and Z i2 All are formulas (Z) i1 / 2 -4)(-C≡C-).

[0358] In general formula (i), m i1 Represents integers from 0 to 1.

[0359] From the perspective of compatibility with other liquid crystal compounds, ease of synthesis, and availability of raw materials, m i1 Preferably, it represents 1.

[0360] In general formula (i), n i1 Represents integers from 0 to 3.

[0361] From the perspective of compatibility with other liquid crystal compounds, ease of synthesis, and availability of raw materials, n i1 Preferably 1 or 2.

[0362] In A i2 or Z i2 When multiple cases exist, they can be the same or different.

[0363] The compounds represented by general formula (i) are preferably those represented by general formulas (i-1) to (i-3) below.

[0364] [Chemistry 11]

[0365]

[0366] In general formulas (i-1) to (i-3), R i1 A i1 A i2 Z i1 L i1 and L i2 R represents the expression in the above general formula (i). i1 A i1A i2 Z i1 L i1 and L i2 Each has the same meaning, and preferred groups also represent the same situation.

[0367] The compounds represented by the general formula (i-1) are preferably those represented by the following general formulas (i-1-a) to (i-1-f).

[0368] [Chemistry 12]

[0369]

[0370] [Chemistry 13]

[0371]

[0372] In the general formulas (i-1-a) to (i-1-f), R i1 S i1 L i1 and L i2 Represent R independently as in the above general formula (i). i1 S i1 L i1 and L i2 The same meaning applies to preferred functional groups.

[0373] Specific examples of compounds represented by the general formula (i-1-a) include compounds represented by the following structural formulas (i-1-a.1) to (i-1-a.3).

[0374] [Chemistry 14]

[0375]

[0376] Specific examples of compounds represented by the general formula (i-1-b) include compounds represented by the following structural formulas (i-1-b.1) to (i-1-b.3).

[0377] [Chemistry 15]

[0378]

[0379] Specific examples of compounds represented by the general formula (i-1-c) include compounds represented by the following structural formulas (i-1-c.1) to (i-1-c.3).

[0380] [Chemistry 16]

[0381]

[0382] Specific examples of compounds represented by the general formula (i-1-d) include compounds represented by the following structural formulas (i-1-d.1) to (i-1-d.3).

[0383] [Chemistry 17]

[0384]

[0385] Specific examples of compounds represented by the general formula (i-1-e) include compounds represented by the following structural formulas (i-1-e.1) to (i-1-e.3).

[0386] [Chemistry 18]

[0387]

[0388] Specific examples of compounds represented by the general formula (i-1-f) include compounds represented by the following structural formulas (i-1-f.1) to (i-1-f.3).

[0389] [Chemistry 19]

[0390]

[0391] The compounds represented by the general formula (i-2) are preferably those represented by the following general formulas (i-2-a) to (i-2-d).

[0392] [Chemistry 20]

[0393]

[0394] In the general formula (i-2-a) ~ (i-2-d), R i1 S i1 L i1 and L i2 Represent R independently as in the above general formula (i). i1 S i1 L i1 and L i2 The same meaning applies to preferred functional groups.

[0395] Specific examples of compounds represented by the general formula (i-2-a) include compounds represented by the following structural formulas (i-2-a.1) to (i-2-a.3).

[0396] [Chemistry 21]

[0397]

[0398] Specific examples of compounds represented by the general formula (i-2-b) include compounds represented by the following structural formulas (i-2-b.1) to (i-2-b.3).

[0399] [Chemistry 22]

[0400]

[0401] Specific examples of compounds represented by the general formula (i-2-c) include compounds represented by the following structural formulas (i-2-c.1) to (i-2-c.3).

[0402] [Chemistry 23]

[0403]

[0404] Specific examples of compounds represented by the general formula (i-2-d) include compounds represented by the following structural formulas (i-2-d.1) to (i-2-d.3).

[0405] [Chemistry 24]

[0406]

[0407] The compounds represented by the general formula (i-3) are preferably those represented by the following general formulas (i-3-a) to (i-3-b).

[0408] [Chemistry 25]

[0409]

[0410] Specific examples of compounds represented by the general formula (i-3-a) include compounds represented by the following structural formulas (i-3-a.1) to (i-3-a.3).

[0411] [Chemistry 26]

[0412]

[0413] Specific examples of compounds represented by the general formula (i-3-b) include compounds represented by the following structural formulas (i-3-b.1) to (i-3-b.3).

[0414] [Chemistry 27]

[0415]

[0416] General formula (i), general formula (i-1)~(i-3), general formula (i-1-a)~(i-1-f), general formula (i-2-a)~(i-2-d), general formula (i-3-a)~(i-3-b), structural formula (i-1-a.1)~(i-1-a.3), structural formula (i-1-b.1)~(i-1-b.3), structural formula (i-1-c.1)~(i-1-c.3), structural formula (i-1-d.1)~(i-1-d.3), structural formula (i-1-e.1)~(i-1-e.3), structural formula (i-1-f.1)~(i-1-f 3) The compounds represented by structural formulas (i-2-a.1) to (i-2-a.3), (i-2-b.1) to (i-2-b.3), (i-2-c.1) to (i-2-c.3), (i-2-d.1) to (i-2-d.3), (i-3-a.1) to (i-3-a.3), or (i-3-b.1) to (i-3-b.3) are used in the liquid crystal composition in one or more types, preferably one to five types, preferably one to four types, preferably one to three types, preferably one to two types, and preferably one type.

[0417] General formula (i), general formula (i-1)~(i-3), general formula (i-1-a)~(i-1-f), general formula (i-2-a)~(i-2-d), general formula (i-3-a)~(i-3-b), structural formula (i-1-a.1)~(i-1-a.3), structural formula (i-1-b.1)~(i-1-b.3), structural formula (i-1-c.1)~(i-1-c.3), structural formula (i-1-d.1)~(i-1-d.3), structural formula (i-1-e.1)~(i-1-e.3), structural formula (i-1-f.1)~(i-1 The total content of the compounds represented by the structural formulas (i-2-a.1) to (i-2-a.3), (i-2-b.1) to (i-2-b.3), (i-2-c.1) to (i-2-c.3), (i-2-d.1) to (i-2-d.3), (i-3-a.1) to (i-3-a.3), or (i-3-b.1) to (i-3-b.3) in 100% by mass of the liquid crystal composition is preferably 0.5 to 100% by mass, preferably 1 to 50% by mass, and preferably 1.5 to 25% by mass.

[0418] General formula (i), general formula (i-1)~(i-3), general formula (i-1-a)~(i-1-f), general formula (i-2-a)~(i-2-d), general formula (i-3-a)~(i-3-b), structural formula (i-1-a.1)~(i-1-a.3), structural formula (i-1-b.1)~(i-1-b.3), structural formula (i-1-c.1)~(i-1-c.3), structural formula (i-1-d.1)~(i-1-d.3), structural formula (i-1-e.1)~(i-1- Compounds represented by structural formulas (i-1-f.1) to (i-1-f.3), (i-2-a.1) to (i-2-a.3), (i-2-b.1) to (i-2-b.3), (i-2-c.1) to (i-2-c.3), (i-2-d.1) to (i-2-d.3), (i-3-a.1) to (i-3-a.3), or (i-3-b.1) to (i-3-b.3) can be synthesized using known synthetic methods.

[0419] (The compound represented by general formula (ii))

[0420] The liquid crystal material disclosed herein is preferably a compound containing one or more compounds represented by the following general formula (ii) having an isothiocyanate group (-NCS).

[0421] [Chemistry 28]

[0422]

[0423] In general formula (ii), R ii1 Alkyl groups having 1 to 20 carbon atoms.

[0424] The alkyl group can be a straight-chain, branched, or cyclic alkyl group, preferably a straight-chain alkyl group.

[0425] The alkyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 6.

[0426] One or more of the -CH2- groups in the alkyl group can be independently replaced by -O-, -S-, -CO- and / or -CS-.

[0427] In addition, one or more of the -CH2-CH2- groups in the alkyl group may be independently replaced by -CH=CH-, -CO-O-, -O-CO-, -CO-S-, -S-CO-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- and / or -C≡C-.

[0428] In addition, one or more of the -CH2-CH2-CH2- alkyl groups can be replaced by -O-CO-O-.

[0429] In addition, one or more hydrogen atoms in the alkyl group can be independently replaced by halogen atoms.

[0430] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0431] In cases where the alkyl group is substituted with a specific group, oxygen atoms do not bond directly to each other.

[0432] Furthermore, from the viewpoint of compound stability, it is preferable that sulfur atoms do not directly bond with sulfur atoms and / or oxygen atoms do not directly bond with sulfur atoms.

[0433] For example, R ii1 By replacing one of the -CH2- atoms in the alkyl group with -O-, an alkoxy group with 1 to 19 carbon atoms can be represented.

[0434] The alkoxy group can be a straight-chain, branched, or cyclic alkoxy group, preferably a straight-chain alkoxy group.

[0435] The number of carbon atoms in the alkoxy group is preferably 2 to 10, and more preferably 2 to 6.

[0436] Additionally, R ii1 By replacing one of the -CH2- atoms in the alkyl group with -S-, thioalkoxy groups (alkathiol, alkylthiol) with 1 to 19 carbon atoms can be represented.

[0437] The thioalkoxy group can be linear, branched, or cyclic, with linear thioalkoxy groups being preferred.

[0438] The number of carbon atoms in the thioalkoxy group is preferably 2 to 10, and more preferably 2 to 6.

[0439] Additionally, R ii1 Alkenes with 2 to 20 carbon atoms can be represented by replacing one or more of the -CH2-CH2- atoms in the alkyl group with -CH=CH- atoms.

[0440] The alkenyl group can be linear, branched, or cyclic, with linear alkenyl groups being preferred.

[0441] The number of carbon atoms in the alkenyl group is preferably 2 to 10, and more preferably 2 to 6.

[0442] Additionally, R ii1 By replacing one or more of the -CH2-CH2- groups in the alkyl group with -C≡C-, an alkynyl group with 2 to 20 carbon atoms can be represented.

[0443] The alkynyl group can be linear, branched, or cyclic, with linear alkynyl groups being preferred.

[0444] The number of carbon atoms in the alkynyl group is preferably 2 to 10, and more preferably 2 to 6.

[0445] Additionally, R ii1 An alkyl group with 2 to 19 carbon atoms can be represented by replacing one -CH2- in the alkyl group with -O- and replacing one or more -CH2-CH2- with -CH=CH-.

[0446] The olefinic group can be linear, branched, or cyclic, with linear olefinic groups being preferred.

[0447] The number of carbon atoms in the olefinic group is preferably 2 to 10, and more preferably 2 to 6.

[0448] Additionally, R ii1 By replacing one or more hydrogen atoms in the alkyl group with halogen atoms, alkyl halides with 1 to 20 carbon atoms can be represented.

[0449] The alkyl halide is a straight-chain, branched, or cyclic alkyl halide, preferably a straight-chain alkyl halide.

[0450] The number of carbon atoms in the alkyl halide is preferably 2 to 10, and more preferably 2 to 6.

[0451] Additionally, R ii1 Halogenated alkoxy groups with 1 to 19 carbon atoms can be represented by replacing one -CH2- atom in the alkyl group with -O- atom and replacing one or more hydrogen atoms in the alkyl group with halogen atoms.

[0452] The halogenated alkoxy group can be linear, branched, or cyclic, with linear halogenated alkoxy groups being preferred.

[0453] The number of carbon atoms in the halogenated alkoxy group is preferably 2 to 10, and more preferably 2 to 6.

[0454] As R ii1 Specific examples of alkyl groups having 1 to 20 carbon atoms (including substituted cases) can be listed in formula (R). ii1 -1)~(R ii1 -36) represents groups, etc.

[0455] [Chemistry 29]

[0456]

[0457] Formula (R) ii1 -1)~(R ii1 In -36), the black dot represents the direction to A. ii1 The bonding bonds.

[0458] In R ii1When the bonded ring structure is phenyl (aromatic), it is preferably an alkyl group with 1 to 5 straight-chain carbon atoms, an alkoxy group with 1 to 4 straight-chain carbon atoms, or an alkenyl group with 4 to 5 carbon atoms. ii1 When the combined ring structure is a saturated ring structure such as cyclohexane, pyran, or dioxane, it is preferably an alkyl group with 1 to 5 straight-chain carbon atoms, an alkoxy group with 1 to 4 straight-chain carbon atoms, or an alkenyl group with 2 to 5 straight-chain carbon atoms.

[0459] Additionally, as R ii1 In order to stabilize the nematic phase, the total number of carbon atoms and oxygen atoms in the presence of carbon atoms is preferably 5 or less, and preferably linear.

[0460] Furthermore, as R ii1 From the viewpoint of compatibility with other liquid crystal compounds, linear alkyl groups with 2 to 8 carbon atoms or linear alkoxy groups with 2 to 8 carbon atoms are preferred.

[0461] In general formula (ii), A ii1 and A ii2 Each of the following groups (a), (b), (c), and (d) can be represented independently:

[0462] (a) 1,4-cyclohexylene (one -CH2- or two or more non-adjacent -CH2- groups may be replaced with -O- and / or -S-).

[0463] (b) 1,4-Phenylidene (one -CH= or two or more non-adjacent -CH= groups may be substituted with -N=)

[0464] (c) Naphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl (one -CH= or two or more non-adjacent -CH= in naphthalene-2,6-diyl may be replaced by -N=),

[0465] (d) Thiophene-2,5-diyl, benzothiophene-2,5-diyl, benzothiophene-2,6-diyl, dibenzothiophene-3,7-diyl, dibenzothiophene-2,6-diyl, thieno[3,2-b]thiophene-2,5-diyl (one -CH= or two or more non-adjacent -CH= in this group may be replaced with -N=).

[0466] A ii1 and A ii2 One or more hydrogen atoms can be independently substituted by the S group. ii1 replace.

[0467] Substituent S ii1It represents any one of the following: halogen atom, pentafluoromethylthioalkyl, nitro, cyano, isocyano, amino, hydroxyl, mercapto, methylamino, dimethylamino, diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, thioisocyano, or alkyl group having 1 to 20 carbon atoms.

[0468] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0469] The alkyl group having 1 to 20 carbon atoms is a straight-chain, branched, or cyclic alkyl group, preferably a straight-chain alkyl group.

[0470] 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.

[0471] One or more of the -CH2- groups in the alkyl group can be independently replaced by -O-, -S-, -CO- and / or -CS-.

[0472] In addition, one or more of the -CH2-CH2- groups in the alkyl group may be independently replaced by -CO-O-, -O-CO-, -CO-S-, -S-CO-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- and / or -C≡C-.

[0473] One or more of the -CH2-CH2-CH2- groups in the alkyl group can be independently replaced by -O-CO-O- groups.

[0474] One or more of the -CH2-CH2-CH2-CH2- alkyl groups can be independently replaced by -CH=CH-CO-O-, -CH=CH-O-CO-, -CO-O-CH=CH-, or -O-CO-CH=CH-.

[0475] In addition, one or more hydrogen atoms in the alkyl group can be independently replaced by halogen atoms.

[0476] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0477] In cases where the alkyl group is substituted with a specific group, oxygen atoms do not bond directly to each other.

[0478] Furthermore, from the viewpoint of compound stability, it is preferable that sulfur atoms do not directly bond with sulfur atoms and / or oxygen atoms do not directly bond with sulfur atoms.

[0479] As a substituent S ii1 Preferably, it contains fluorine or chlorine atoms.

[0480] In addition, A is preferred. ii1 At least one or Aii2 With at least one substituent S ii1 replace.

[0481] Furthermore, in the substituent S ii1 When multiple cases exist, they can be the same or different.

[0482] As A ii1 The substituent S in ii1 The replacement position is preferably that of the following formula (A) ii1 -SP-1)~(A ii1 Any of (-SP-4).

[0483] [Chemistry 30]

[0484]

[0485] Formula (A) ii1 -SP-1)~(A ii1 In -SP-4), the white dot indicates the direction to R. ii1 or Z ii1 The bond is a combination of two bonds, and the black dots represent the bonds to Z. ii1 The bonding bonds.

[0486] As A ii2 The substituent S in ii1 The replacement position is preferably that of the following formula (A) ii2 -SP-1)~(A ii2 Either of the following (-SP-7).

[0487] [Chemistry 31]

[0488]

[0489] Formula (A) ii2 -SP-1)~(A ii2 In -SP-7), the white dot indicates the direction of Z. ii1 The black dots represent the bonds that bind to the isothiocyanate group (-NCS).

[0490] More specifically, A ii1 Preferably, it represents the following formula (A) ii1 -1)~(A ii1 Any one of -6).

[0491] [Chemistry 32]

[0492]

[0493] Formula (A) ii1 -1)~(A ii1 In -6), the white dot represents the direction to R. ii1 or Zii1 The bond is a combination of two bonds, and the black dots represent the bonds to Z. ii1 The bonding bonds.

[0494] More specifically, A ii2 Preferably, it represents the following formula (A) ii2 -1)~(A ii2 Any one of -5).

[0495] [Chemistry 33]

[0496]

[0497] Formula (A) ii2 -1)~(A ii2 In -5), the white dot represents the direction of Z. ii1 The black dots represent the bonds that bind to the isothiocyanate group (-NCS).

[0498] In general formula (ii), Z ii1 It refers to any single bond or alkylene group having 1 to 20 carbon atoms.

[0499] One or more of the -CH2- groups in the alkylene group can be independently replaced by -O- groups.

[0500] In addition, one or more of the -CH2-CH2- in the alkylene group can be independently replaced by -CH2-CH(CH3)-, -CH(CH3)-CH2-, -CH=CH-, -CF=CF-, -CH=C(CH3)-, -C(CH3)=CH-, -CH=N-, -N=CH-, -N=N-, -C≡C-, -CO-O- and / or -O-CO-.

[0501] In addition, one or more of the -CH2-CH2-CH2- alkyl groups can be independently replaced by -O-CO-O-.

[0502] Furthermore, one or more -CH2-CH2-CH2-CH2- in the alkylene group can be independently converted by -C(R) ia )=NN=C(R ib )-replace.

[0503] In cases where alkyl groups with 1 to 10 carbon atoms are substituted with specific groups, oxygen atoms do not bond directly to each other.

[0504] Furthermore, from the viewpoint of compound stability, it is preferable that sulfur atoms do not directly bond with sulfur atoms and / or oxygen atoms do not directly bond with sulfur atoms.

[0505] R ia and R ibEach of the following can be independently represented: hydrogen atom, halogen atom, and alkyl group with 1 to 10 carbon atoms.

[0506] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0507] The alkyl group can be a straight-chain, branched, or cyclic alkyl group, preferably a straight-chain alkyl group.

[0508] The alkyl group preferably has 2 to 8 carbon atoms, and more preferably 2 to 6.

[0509] One or more of the -CH2- groups in the alkyl group can be independently replaced by -O-, -CO- and / or -S-.

[0510] One or more of the -CH2-CH2- in the alkyl group can be substituted by -CH=CH-, -CO-O-, -O-CO- and / or -C≡C-.

[0511] In cases where alkyl groups with 1 to 10 carbon atoms are substituted with specific groups, oxygen atoms do not bond directly to each other.

[0512] Furthermore, from the viewpoint of compound stability, it is preferable that sulfur atoms do not directly bond with sulfur atoms and / or oxygen atoms do not directly bond with sulfur atoms.

[0513] Specific examples of alkylene groups having 1 to 20 carbon atoms (including substituted cases) can be enumerated as (Z ii1 -1)~(Z ii1 -24) represents groups, etc.

[0514] [Chemistry 34]

[0515]

[0516] Formula (Z) ii1 -1)~(Z ii1 In -24), the white dot represents the direction to A. ii1 The bond is a combination of two bonds, and the black dots represent the bonds to A. ii1 Or A ii2 The bonding bonds.

[0517] In general formula (ii), n ii1 It represents an integer from 1 to 4, preferably from 1 to 2.

[0518] In n ii1 When Z is 1, ii1 Preferably, it represents a single bond or -C≡C-.

[0519] Additionally, in n ii1 When the value is 2, Z is preferred. ii1 At least one of the following is represented as -C≡C-.

[0520] Furthermore, in general formula (ii), in A ii1 and Z ii1 When multiple cases exist, they can be the same or different.

[0521] The compounds represented by general formula (ii) are preferably those represented by the following general formulas (ii-1) to (ii-5).

[0522] [Chemistry 35]

[0523] R ii1 -A ii1 -A ii2 -NCS (ii-1)

[0524]

[0525]

[0526]

[0527] R ii1 -A ii1 -A ii2 -NCS (ii-5)

[0528]

[0529] In general formulas (ii-1) to (ii-5), R ii1 A ii1 and A ii2 This indicates that R is the same as in the above general formula (ii). ii1 A ii1 and A ii2 They have the same meaning, respectively.

[0530] In general formulas (ii-3) to (ii-6), A ii1-2 The definition of A is the same as in the above general formula (ii). ii1 The definitions are the same.

[0531] The compound represented by general formula (ii-1) is preferably the compound represented by the following general formula (ii-1-a).

[0532] [Chemistry 36]

[0533]

[0534] In the general formula (ii-1-a), R ii1 Represent R independently as in the above general formula (ii). ii1 They have the same meaning, respectively.

[0535] Specific examples of compounds represented by the general formula (ii-1-a) include compounds represented by the following structural formulas (ii-1-a.1) to (ii-1-a.4).

[0536] [Chemistry 37]

[0537]

[0538] The compounds represented by the general formula (ii-2) are preferably those represented by the following general formulas (ii-2-a) to (ii-2-c).

[0539] [Chemistry 38]

[0540]

[0541] In the general formulas (ii-2-a) to (ii-2-c), R ii1 and S ii1 Represent R independently as in the above general formula (i). ii1 and S ii1 They have the same meaning, respectively.

[0542] Specific examples of compounds represented by the general formula (ii-2-a) include compounds represented by the following structural formulas (ii-2-a.1) to (ii-2-a.5).

[0543] [Chemistry 39]

[0544]

[0545] Specific examples of compounds represented by the general formula (ii-2-b) include compounds represented by the following structural formulas (ii-2-b.1) to (ii-2-b.3).

[0546] [Chemistry 40]

[0547]

[0548] Specific examples of compounds represented by the general formula (ii-2-c) include compounds represented by the following structural formulas (ii-2-c.1) to (ii-2-c.3).

[0549] [Chemistry 41]

[0550]

[0551] The compounds represented by the general formula (ii-3) are preferably those represented by the following general formulas (ii-3-a) to (ii-3-d).

[0552] [Chemistry 42]

[0553]

[0554] In the general formulas (ii-3-a) to (ii-3-d), R ii1 and S ii1 Represent R independently as in the above general formula (ii). ii1 and S ii1 They have the same meaning, respectively.

[0555] Specific examples of compounds represented by the general formula (ii-3-a) include compounds represented by the following structural formulas (ii-3-a.1) to (ii-3-a.4).

[0556] [Chemistry 43]

[0557]

[0558] Specific examples of compounds represented by the general formula (ii-3-b) include compounds represented by the following structural formulas (ii-3-b.1) to (ii-3-b.3).

[0559] [Chemistry 44]

[0560]

[0561] Specific examples of compounds represented by the general formula (ii-3-c) include compounds represented by the following structural formulas (ii-3-c.1) to (ii-3-c.3).

[0562] [Chemistry 45]

[0563]

[0564] Specific examples of compounds represented by the general formula (ii-3-d) include compounds represented by the following structural formula (ii-3-d.1).

[0565] [Chemistry 46]

[0566]

[0567] The compounds represented by the general formula (ii-4) are preferably those represented by the following general formulas (ii-4-a) to (ii-4-d).

[0568] [Chemistry 47]

[0569]

[0570] In the general formulas (ii-4-a) to (ii-4-d), R ii1 and Sii1 Represent R independently as in the above general formula (ii). ii1 and S ii1 They have the same meaning, respectively.

[0571] Specific examples of compounds represented by the general formula (ii-4-a) include compounds represented by the following structural formulas (ii-4-a.1) to (ii-4-a.3).

[0572] [Chemistry 48]

[0573]

[0574] Specific examples of compounds represented by the general formula (ii-4-b) include compounds represented by the following structural formulas (ii-4-b.1) to (ii-4-b.3).

[0575] [Chemistry 49]

[0576]

[0577] Specific examples of compounds represented by the general formula (ii-4-c) include compounds represented by the following structural formulas (ii-4-c.1) to (ii-4-c.3).

[0578] [Transformation 50]

[0579]

[0580] Specific examples of compounds represented by the general formula (ii-4-d) include compounds represented by the following structural formulas (ii-4-d.1) to (ii-4-d.3).

[0581] [Chemistry 51]

[0582]

[0583] The compounds represented by the general formula (ii-5) are preferably those represented by the following general formulas (ii-5-a) to (ii-5-b).

[0584] [Chemistry 52]

[0585]

[0586] In general formulas (ii-5-a) to (ii-5-b), R ii1 and S ii1 Represent R independently as in the above general formula (ii). ii1 and S ii1 They have the same meaning, respectively.

[0587] Specific examples of compounds represented by the general formula (ii-5-a) include compounds represented by the following structural formulas (ii-5-a.1) to (ii-5-a.4).

[0588] [Chemistry 53]

[0589]

[0590] Specific examples of compounds represented by the general formula (ii-5-b) include compounds represented by the following structural formulas (ii-5-b.1) to (ii-5-b.4).

[0591] [Chemistry 54]

[0592]

[0593] The compounds represented by the general formula (ii-6) are preferably those represented by the following general formulas (ii-6-a) to (ii-6-b).

[0594] [Chemistry 55]

[0595]

[0596] In general formulas (ii-6-a) to (ii-6-b), R ii1 and S ii1 Represent R independently as in the above general formula (ii). ii1 and S ii1 They have the same meaning, respectively.

[0597] Specific examples of compounds represented by the general formula (ii-6-a) include compounds represented by the following structural formulas (ii-6-a.1) to (ii-6-a.4).

[0598] [Chemistry 56]

[0599]

[0600] Specific examples of compounds represented by the general formula (ii-6-b) include compounds represented by the following structural formulas (ii-6-b.1) to (ii-6-b.4).

[0601] [Chemistry 57]

[0602]

[0603] The compounds represented by general formula (ii-1), general formula (ii-1-a) or structural formula (ii-1-a.1) to (ii-1-a.4) are used in liquid crystal materials in one or more kinds, preferably 1 to 20 kinds, preferably 1 to 15 kinds, preferably 1 to 10 kinds, and preferably 1 to 5 kinds.

[0604] From the viewpoint of compatibility with other liquid crystal compositions, the total content of the compounds represented by general formula (ii-1), general formula (ii-1-a) or structural formulas (ii-1-a.1) to (ii-1-a.4) in 100% by mass of the liquid crystal material is preferably 1 to 40% by mass, preferably 2 to 35% by mass, and preferably 3 to 30% by mass.

[0605] The compounds represented by general formula (ii-2), general formula (ii-2-a) to (ii-2-c), structural formula (ii-2-a.1) to (ii-2-a.5), structural formula (ii-2-b.1) to (ii-2-b.3) or structural formula (ii-2-c.1) to (ii-2-c.3) are used in the liquid crystal material in one or more kinds, preferably 1 to 20 kinds, preferably 1 to 15 kinds, preferably 1 to 10 kinds, and preferably 1 to 5 kinds.

[0606] From the viewpoint of compatibility with other liquid crystal compositions, the total content of the compounds represented by general formula (ii-2), general formulas (ii-2-a) to (ii-2-c), structural formulas (ii-2-a.1) to (ii-2-a.5), structural formulas (ii-2-b.1) to (ii-2-b.3) or structural formulas (ii-2-c.1) to (ii-2-c.3) in 100% by mass of the liquid crystal material is preferably 5 to 70% by mass, preferably 10 to 65% by mass, and preferably 15 to 60% by mass.

[0607] The compounds represented by general formula (ii-3), general formula (ii-3-a) to (ii-3-d), structural formula (ii-3-a.1) to (ii-3-a.4), structural formula (ii-3-b.1) to (ii-3-b.3), structural formula (ii-3-c.1) to (ii-3-c.3) or structural formula (ii-3-d.1) are used in the liquid crystal material in one or more kinds, preferably 1 to 20 kinds, preferably 1 to 15 kinds, preferably 1 to 10 kinds, and preferably 1 to 5 kinds.

[0608] From the viewpoint of compatibility with other liquid crystal compositions, the total content of the compounds represented by general formula (ii-3), general formulas (ii-3-a) to (ii-3-d), structural formulas (ii-3-a.1) to (ii-3-a.4), structural formulas (ii-3-b.1) to (ii-3-b.3), structural formulas (ii-3-c.1) to (ii-3-c.3), or structural formula (ii-3-d.1) in 100% by mass of the liquid crystal material is preferably 20 to 65% by mass, preferably 25 to 60% by mass, and preferably 30 to 55% by mass.

[0609] The compounds represented by general formula (ii-4), general formula (ii-4-a) to (ii-4-d), structural formula (ii-4-a.1) to (ii-4-a.3), structural formula (ii-4-b.1) to (ii-4-b.3), structural formula (ii-4-c.1) to (ii-4-c.3) or structural formula (ii-4-d.1) to (ii-4-d.3) are used in the liquid crystal material in one or more types, preferably 1 to 20 types, preferably 1 to 15 types, preferably 1 to 10 types, and preferably 1 to 5 types.

[0610] From the viewpoint of compatibility with other liquid crystal compositions, the total content of the compounds represented by general formula (ii-4), general formulas (ii-4-a) to (ii-4-d), structural formulas (ii-4-a.1) to (ii-4-a.3), structural formulas (ii-4-b.1) to (ii-4-b.3), structural formulas (ii-4-c.1) to (ii-4-c.3) or structural formulas (ii-4-d.1) to (ii-4-d.3) in 100% by mass of the liquid crystal material is preferably 1 to 30% by mass, preferably 3 to 25% by mass, and preferably 5 to 20% by mass.

[0611] The compounds represented by general formula (ii-5), general formula (ii-5-a) to (ii-5-b), structural formula (ii-5-a.1) to (ii-5-a.4) or structural formula (ii-5-b.1) to (ii-5-b.4) are used in the liquid crystal material in one or more kinds, preferably 1 to 20 kinds, preferably 1 to 15 kinds, preferably 1 to 10 kinds, and preferably 1 to 5 kinds.

[0612] From the viewpoint of compatibility with other liquid crystal compositions, the total content of the compounds represented by general formula (ii-5), general formulas (ii-5-a) to (ii-5-b), structural formulas (ii-5-a.1) to (ii-5-a.4) or structural formulas (ii-5-b.1) to (ii-5-b.4) in 100% by mass of the liquid crystal material is preferably 5 to 45% by mass, preferably 10 to 40% by mass, and preferably 15 to 35% by mass.

[0613] The compounds represented by general formula (ii-6), general formula (ii-6-a) to (ii-6-b), structural formula (ii-6-a.1) to (ii-6-a.4) or structural formula (ii-6-b.1) to (ii-6-b.4) are used in the liquid crystal material in one or more kinds, preferably 1 to 20 kinds, preferably 1 to 15 kinds, preferably 1 to 10 kinds, and preferably 1 to 5 kinds.

[0614] From the viewpoint of compatibility with other liquid crystal compositions, the total content of the compounds represented by general formula (ii-6), general formulas (ii-6-a) to (ii-6-b), structural formulas (ii-6-a.1) to (ii-6-a.4) or structural formulas (ii-6-b.1) to (ii-6-b.4) in 100% by mass of the liquid crystal material is preferably 1 to 25% by mass, preferably 3 to 20% by mass, and preferably 5 to 15% by mass.

[0615] General formula (ii), general formulas (ii-1) to (ii-6), general formula (ii-1-a), general formula (ii-2-a) to (ii-2-c), general formula (ii-3-a) to (ii-3-d), general formula (ii-4-a) to (ii-4-d), general formula (ii-5-a) to (ii-5-b), general formula (ii-6-a) to (ii-6-b), structural formula (ii-1-a.1) to (ii-1-a.4), structural formula (ii-2-a.1) to (ii-2-a.5), structural formula (ii-2-b.1) to (ii-2-b.3), structural formula (ii-2-c.1) to (ii-2-c.3), structural formula (ii-3-a.1) to (ii-3-a.4), structural formula (ii-3-b.1) Compounds represented by the following structural formulas can be synthesized using known synthetic methods: (ii-3-b.3), (ii-3-c.1), (ii-3-c.3), (ii-3-d.1), (ii-4-a.1), (ii-4-a.3), (ii-4-b.1), (ii-4-b.3), (ii-4-c.1), (ii-4-c.3), (ii-4-d.1), (ii-4-d.3), (ii-5-a.1), (ii-5-a.4), (ii-5-b.1), (ii-5-b.4), (ii-6-a.1), or (ii-6-b.1) to (ii-6-b.4).

[0616] From the viewpoint of reducing rotational viscosity (γ1), the combination of compounds used in the liquid crystal material of this disclosure is preferably: A) a combination of compounds represented by general formula (i) (including subordinate concepts), compounds represented by general formula (ii-1) (including subordinate concepts), compounds represented by general formula (ii-2) (including subordinate concepts), compounds represented by general formula (ii-3) (including subordinate concepts), and compounds represented by general formula (ii-5) (including subordinate concepts); B) one or more compounds represented by general formula (ii-1) (including subordinate concepts), one or more compounds represented by general formula (ii-2) (including subordinate concepts), one or more compounds represented by general formula (ii-3) (including subordinate concepts), and compounds represented by general formula (ii-5) (including subordinate concepts). A) One or more combinations of compounds represented by general formula (ii-1), including subordinate concepts; B) One or more combinations of compounds represented by general formula (ii-2), including subordinate concepts, and one or more combinations of compounds represented by general formula (ii-5), including subordinate concepts; C) One or more combinations of compounds represented by general formula (ii-1), including subordinate concepts; D) One or more combinations of compounds represented by general formula (ii-2), including subordinate concepts; E) One or more combinations of compounds represented by general formula (ii-3), including subordinate concepts, and one or more combinations of compounds represented by general formula (ii-5), including subordinate concepts; D) One or more combinations of compounds represented by general formula (ii-6), including subordinate concepts.

[0617] Furthermore, the liquid crystal material disclosed herein is preferably a compound containing only a compound having an isothiocyanate group (-NCS) as the liquid crystal compound.

[0618] (Liquid crystal display elements, sensors, liquid crystal lenses, optical communication equipment and antennas)

[0619] The liquid crystal material manufactured by this invention can be used in liquid crystal display elements, sensors (preferably ranging sensors for LiDAR (Light Detection and Ranging)), liquid crystal lenses, optical communication equipment, antennas, etc. It is especially suitable for antenna applications in the microwave band.

[0620] Example

[0621] The present invention will be described in more detail below with reference to specific embodiments, but the present invention is not limited to any of the embodiments described below.

[0622] <Apparatus used for measurement and evaluation in the examples and comparative examples>

[0623] • First coaxial tube (coaxial tube 6 of the embodiment, comparative example (reference coaxial tube)):

[0624] The set consists of a length of 30mm (the length of the liquid crystal material filling part in the coaxial tube body), an inner diameter of 3mm, a center conductor diameter of 1mm, and an internal volume of 0.19cc.

[0625] • Coaxial tube (Comparative example (comparative coaxial tube)):

[0626] Sample sleeve length (length along the major axis of the liquid crystal material filling part in the coaxial tube body) (80mm), inner diameter Φ 3mm, center guide diameter φ 1mm, internal volume 0.50cc

[0627] • Vector network analyzer: The vector network analyzer used is the “P5005A” manufactured by Keysight Technologie Co., Ltd.

[0628] • Power supply: Uses a DC power supply of “PMX250” manufactured by Kikusui Electronics Industry Co., Ltd.

[0629] • Processing unit: A personal computer using the “Dynabook BZ55” manufactured by Toshiba Corporation.

[0630] • Capacitors for DC blocks: DC blocks using “PE8225” manufactured by Pasternack, Inc.

[0631] • Coaxial assembly: Bias Tee of “BT1026-1” manufactured by Auriga Microwave.

[0632] <Materials used in the Examples and Comparative Examples>

[0633] The compositions of the following examples and comparative examples contain each compound in the proportions shown in the table, and the content is stated in "mass %".

[0634] The following abbreviations are used to describe the compounds. Furthermore, compounds that can be described in both cis and trans forms are indicated as trans unless otherwise specified.

[0635] <Ring Structure>

[0636] [Chem.58]

[0637]

[0638] <End Structure>

[0639] [Table 1]

[0640] abbreviation Chemical structure -n <![CDATA[-C n H 2n+1 ]]> n- <![CDATA[C n H 2n+1 -]]> -On <![CDATA[-O-C n H 2n+1 ]]> nO- <![CDATA[C n H 2n+1 —O-]]> -Sn <![CDATA[—S—C n H 2n+1 ]]> nS- <![CDATA[C n H 2n+1 -S-]]> -V <![CDATA[-CH=CH2]]> V- <![CDATA[CH2=CH-]]> -V1 <![CDATA[-CH=CH-CH3]]> 1V- <![CDATA[CH3-CH=CH-]]> -2V <![CDATA[-CH2-CH2-CH=CH2]]> V2- <![CDATA[CH2=CH-CH2-CH2-]]> -2V1 <![CDATA[-CH2-CH2-CH=CH-CH3]]> 1V2- <![CDATA[CH3-CH=CH-CH2-CH2-]]> -OCF3 <![CDATA[-O-CF3]]> CF3O- <![CDATA[CF3-O-]]> -H -H H- H- -CN -CN CN- CN- -NCS -NCS NCS- NCS-

[0641] (where n in the table is a natural number).

[0642] <Connection Structure>

[0643] [Table 2]

[0644] abbreviation Chemical structure single bond -n- <![CDATA[-C n H 2n -]]> -nO- <![CDATA[-C n H 2n -O-]]> -On- <![CDATA[-O-C n H 2n -]]> -COO- -C(=O)-O- -OCO- -OC(=O)- -V- -CH=CH- -nV- <![CDATA[-C n H 2n -CH=CH-]]> -Vn- <![CDATA[-CH=CH-C n H 2n -]]> -T- -C≡C- -CF2O- <![CDATA[-CF2-O-]]> -OCF2- <![CDATA[-O-CF2- <!-- 47 -->]]> -Az- -N=N-

[0645] (where n in the table is a natural number).

[0646] (Example)

[0647] <Preparation or preparation of liquid crystal materials>

[0648] Liquid crystal materials (a) and (b) with the composition ratios recorded in Table 3 below were prepared as liquid crystal materials.

[0649] Furthermore, both liquid crystal materials (a) and (b) are liquid at 25°C, exhibiting a nematic phase.

[0650] [Table 3]

[0651] Table 3 Liquid crystal material (a) Liquid crystal material (b) 5-Ph-Ph-CN 100 95 3-Tet3-T-Ph-T-Ph1-NCS 0 5 Total [mass %] 100 100

[0652] <Determination of Differential Delay Value>

[0653] -Determination of the differential retardation value of liquid crystal material (a)-

[0654] Then, if it becomes with Figure 1 Similar to the circuit network, the devices listed in the "Equipment Used" section above, excluding the cylindrical coaxial tube 6, are configured and connected to form a differential delay measurement system (measurement mechanism). Next, the liquid crystal material (a) is filled into the gap of the coaxial tube 6, which contains a 1mm diameter center wire 8 inside a tubular outer conductor 9 with an inner diameter of 3mm and a length of 30mm along the long axis of the liquid crystal material filling part in the coaxial tube body, in a manner that prevents air bubbles from entering. Afterward, the coaxial tube 6 filled with liquid crystal material (a) is connected to the vector network analyzer 2, and the group delay amount in the state without applied voltage, i.e., the propagation delay time (t0) without bias voltage, is measured first. At this time, the propagation delay time (t0) without bias voltage at 13GHz is 0.3211 (nsec).

[0655] Subsequently, an execution voltage (100V DC) was applied between coaxial components (bias T) 4a and b, and the group delay at 100V DC, i.e., the propagation delay time (t) at the execution voltage, was measured in the same manner. v The result shows the propagation delay time (t) at an execution voltage of 13 GHz. v The value is 0.3290 nsec.

[0656] Subsequently, the same measurement was performed twice more, and the propagation delay time (t0) under no bias voltage and the propagation delay time (t) under the execution voltage were measured a total of three times. v ).

[0657] Next, the personal computer of processing device 1 is used to analyze the obtained propagation delay time (t0) under no bias voltage and propagation delay time (t) under execution voltage. v The value of ) is processed and analyzed to calculate the differential retardation value (Δt=|t) of the liquid crystal material (a). v -t0|). Furthermore, the transmission delay time (t) v The measurements of the propagation delay time (t0) were performed under conditions where the liquid crystal material was at room temperature (25°C). Furthermore, in the measurement of the differential delay value, a coaxial tube 6 filled with liquid crystal material (a) was connected to a vector network analyzer 2, and an electromagnetic wave (incident signal) with a frequency ranging from 0.1 to 26.5 GHz (repeatedly increasing the frequency continuously from 0.1 to 26.5 GHz, and then again continuously increasing the frequency from 0.1 to 26.5 GHz upon reaching 26.5 GHz) propagated through the vector network analyzer 2 through the liquid crystal material. The results are shown in Table 4 as Example 1.

[0658] -Determination of the differential retardation value of liquid crystal material (b)-

[0659] The liquid crystal material (b) was filled into the gap of the coaxial tube 6 in a manner that prevents air bubbles from entering. Otherwise, the propagation delay time (t0) under no bias voltage and the propagation delay time (t) under the execution voltage were measured three times in the same manner as the method used to measure the differential delay value of the liquid crystal material (a). v After that, the differential retardation value of liquid crystal material (b) (Δt=|t) is calculated. v -t0|). The results are shown in Table 5 as Example 2.

[0660] (Comparative Example)

[0661] -Method for determining the dielectric anisotropy (Δε) of liquid crystal materials (a)-

[0662] The dielectric anisotropy (Δε) measuring mechanism used in the comparative example is the same as the differential retardation value measuring mechanism used in the above embodiments, except for the coaxial tube 6. In the measurement of the dielectric anisotropy (Δε) of the liquid crystal material (a), two cylindrical coaxial tubes are used. One coaxial tube, with a length of 30 mm, is used as the reference coaxial tube, and the other, with the same diameter as the reference coaxial tube and a length of 80 mm, is used as the comparison coaxial tube. Next, after filling the two coaxial tubes with liquid crystal material (a), the dielectric anisotropy was calculated according to the coaxial tube method described in "A Small Collection of Papers on the Current Status and Future Prospects of Organic Molecular Electronic Devices (Dielectric Measurement of Nematic Liquid Crystals from 10kHz to 40GHz and Its Application to Variable Delay Lines), by Toshihisa Kamei, pp. 1150-1151". Specifically, the dielectric anisotropy was first measured by determining Δτ at 13GHz based on the measurement results of a 30mm and an 80mm coaxial tube without applying a voltage to the center conductor. g And L(ΔL). Then, with a DC voltage of 100V applied to the center conductor, Δτ at 13GHz is calculated in the same way. g The dielectric anisotropy (Δε) of the liquid crystal material (a) was calculated using L (ΔL). Furthermore, the dielectric anisotropy (Δε) was measured at room temperature (25°C) for the liquid crystal material. The results are shown in Table 4 as Comparative Example 1. Additionally, the dielectric anisotropy (Δε) of the liquid crystal material (a) was measured three times.

[0663] -Method for determining the dielectric anisotropy (Δε) of liquid crystal material (b)-

[0664] The liquid crystal material (b) was filled into the gap of the coaxial tube 6 in a manner that prevents air bubbles from entering. Otherwise, the dielectric constant anisotropy (Δε) was measured a total of 3 times in the same manner as the method for measuring the dielectric constant anisotropy (Δε) of the liquid crystal material (a). The results are shown in Table 5 as Comparative Example 2.

[0665] [Table 4]

[0666]

[0667] [Table 5]

[0668]

[0669] <Confirmation of Differential Delay Value>

[0670] Based on the results in Tables 2 and 3 above, it was confirmed that the coefficient of variation of the differential retardation value is extremely low compared to the value of dielectric constant anisotropy (Δε). Therefore, it was confirmed that the liquid crystal material with a specific differential retardation value is electrically homogeneous compared to the liquid crystal material with a specific dielectric constant anisotropy (Δε) value. In particular, it was confirmed that even if the differential retardation of the liquid crystal material (b) of Example 2 is larger than that of the liquid crystal material (a) of Example 1, the coefficient of variation of the differential retardation is still small, thus providing a liquid crystal material with more homogeneous electrical properties.

[0671] Furthermore, liquid crystal materials (c) to (h) with the composition ratios recorded in Table 6 were prepared as liquid crystal materials. Moreover, liquid crystal materials (c) to (h) are all liquid at 25°C, exhibiting a nematic phase.

[0672] Next, using liquid crystal materials (c) to (h), the differential retardation value and dielectric constant anisotropy (Δε) were measured in the same manner as for liquid crystal materials (a) and (b). The results are shown in Tables 6 to 12.

[0673] [Table 6]

[0674] Table 6 Liquid crystal material (c) Liquid crystal material (d) Liquid crystal materials (e) Liquid crystal material (f) Liquid crystal material (g) Liquid crystal material (h) <![CDATA[T ni [℃]]]> 149.5 154.8 71.1 157.3 153.7 156.8 <![CDATA[T →N [℃]]]> G-39 G-35 G-43 G-39 G-35 G-35 Δn 0.3679 0.3827 0.2975 0.3806 0.3670 0.3877 Δε(1kHz) 12.88 13.31 11.14 12.92 12.85 13.40 <![CDATA[γ1[mPa·s]]]> 512 529 216 600 549 606 <![CDATA[V th [V]]> 2.051 2.063 1.605 2.096 2.058 2.059 5-Cy-Ph-NCS 6 5.4 21 5.4 5.4 5.4 4-Ph-T-Pc1-NCS 11 9.9 11 9.9 9.9 9.9 5-Ph-T-Ph1-NCS 5 4.5 20 4.5 4.5 4.5 4O-Ph2-T-Ph-NCS 5 4.5 10 4.5 4.5 4.5 5O-Ph2-T-Ph-NCS 5 4.5 10 4.5 4.5 4.5 4-Cy-Ph-T-Ph1-NCS 16 14.4 14.4 14.4 14.4 5-Cy-Ph-T-Ph1-NCS 13 11.7 11.7 11.7 11.7 5-Ph-Ph5-T-Ph1-NCS 15 13.5 13.5 13.5 13.5 4-Ph-Ph-T-Ph3-NCS 10 2-Cy-Ph-Ph3-NCS 12 10.8 14 10.8 10.8 10.8 4-Cy-Ph-Ph3-NCS 12 10.8 14 10.8 10-8 10.8 4-Cy-T-Ph-Ph3-NCS 10 4-T-Ph-T-Ph-Ph3-NCS 10 3-Tet3-T-Ph-T-Ph1-NCS 10 Total [mass %] 100 100 100 100 100 100

[0675] [Table 7]

[0676]

[0677] [Table 8]

[0678]

[0679] [Table 9]

[0680]

[0681] [Table 10]

[0682]

[0683] [Table 11]

[0684]

[0685] [Table 12]

[0686]

[0687] The results in Tables 6-12 confirm that even with compositions using multiple compounds, the coefficient of variation of the differential retardation value is extremely low compared to the value of dielectric constant anisotropy (Δε). Therefore, it has been confirmed that liquid crystal materials with a specific differential retardation value are electrically homogeneous compared to liquid crystal materials with a specific dielectric constant anisotropy (Δε) value. In particular, it has been confirmed that the liquid crystal materials (c)-(h) of Examples 3-8 exhibit a small coefficient of variation for the differential retardation value even with increased differential retardation values, thus providing liquid crystal materials with even more homogeneous electrical properties. Furthermore, due to the larger differential retardation value (longer delay time), it is expected that a wider range of electromagnetic wave transmission and reception angles can be ensured.

[0688] Industrial availability

[0689] The method for manufacturing the liquid crystal material of this invention can be used in liquid crystal display elements, sensors, liquid crystal lenses, optical communication equipment, and antennas. It is particularly suitable for antenna applications in the microwave band.

[0690] Symbol Explanation

[0691] 1: Processing device

[0692] 2: Vector Network Analyzer

[0693] 3a, b: Capacitors for DC blocks

[0694] 4a, b: Coaxial components

[0695] 5a, b: Adapters

[0696] 6: Coaxial tube

[0697] 7: DC power supply

[0698] 8: Internal conductor

[0699] 9: External conductor

[0700] 10: Liquid crystal molecules

[0701] 100: Differential Delay Measurement System

Claims

1. A method for manufacturing a liquid crystal material, comprising the following steps: Process (I), preparation of liquid crystal material; and Step (II): The liquid crystal material is measured using a differential delay measuring mechanism that measures the differential delay value of the liquid crystal material. The differential delay measuring mechanism includes a coaxial tube comprising an inner conductor in the shape of a line and an outer conductor having a gap for inserting the inner conductor, and has a mechanism for calculating the differential delay value of the liquid crystal material; the differential delay value of the liquid crystal material is the difference between the transmission delay time t0 and the transmission delay time tv, the transmission delay time t0 being measured by allowing an electromagnetic wave with a continuously changing frequency to propagate in the liquid crystal material filling the gap between the inner conductor and the outer conductor while a reference voltage V0 is applied between the inner conductor and the outer conductor, and the transmission delay time tv being measured by allowing the electromagnetic wave to propagate in the liquid crystal material while an execution voltage V greater than the reference voltage V0 is applied between the inner conductor and the outer conductor.

2. The method for manufacturing liquid crystal material according to claim 1, wherein, The frequency of the electromagnetic wave varies continuously in the range of 0.1 to 26.5 GHz.

3. The method for manufacturing the liquid crystal material according to claim 1 or 2, wherein, The transmission delay time t0 is measured by allowing an electromagnetic wave with a continuously varying frequency to propagate in the liquid crystal material under conditions of no bias voltage between the inner conductor and the outer conductor.

4. The method for manufacturing liquid crystal material according to claim 1 or 2, wherein, The liquid crystal material contains a liquid crystal compound having an -NCS group.

5. A method for measuring differential delay, wherein the differential delay is the change in the propagation delay time of an electromagnetic wave propagating in a liquid crystal material filling the gap, using a coaxial tube having a linear inner conductor and an outer conductor having a gap for inserting the inner conductor. The method for determining the differential delay includes the following steps: The process of preparing the liquid crystal material; The process of filling the liquid crystal material between the inner conductor and the outer conductor; and The process of calculating the differential delay value of the liquid crystal material. The differential delay value of the liquid crystal material is the difference between the propagation delay time t0 and the propagation delay time tv. The propagation delay time t0 is measured by allowing an electromagnetic wave with a continuously changing frequency to propagate in the liquid crystal material while a reference voltage V0 is applied between the inner conductor and the outer conductor. The propagation delay time tv is measured by allowing the electromagnetic wave to propagate in the liquid crystal material while an execution voltage V greater than the reference voltage V0 is applied between the inner conductor and the outer conductor.

6. A device for measuring differential delay value, characterized in that, have: A coaxial tube having a linear inner conductor, an outer conductor through which the inner conductor is inserted, and a gap between the inner conductor and the outer conductor that can be filled with liquid crystal material; An electrical signal transceiver unit inputs an electrical signal of an electromagnetic wave into the coaxial tube and receives an output signal of an electromagnetic wave in response to the electrical signal. and The parsing and processing unit performs parsing and processing on the electrical signals transmitted and received by the electrical signal transceiver unit and the output signals; The analytical processing unit calculates the differential delay value of the liquid crystal material, which is the difference between the transmission delay time t0 and the transmission delay time tv. The transmission delay time t0 is measured by allowing an electromagnetic wave with a continuously changing frequency to propagate in the liquid crystal material while a reference voltage V0 is applied between the inner conductor and the outer conductor. The transmission delay time tv is measured by allowing the electromagnetic wave to propagate in the liquid crystal material while an execution voltage V greater than the reference voltage V0 is applied between the inner conductor and the outer conductor.

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