Compounds, liquid crystal compositions, and liquid crystal display elements

Abstract

The present invention provides a liquid crystalline compound that satisfies at least one of the following physical properties: high stability against heat and light, a high transparency point (or a high upper temperature limit for the nematic phase), a low lower temperature limit for the nematic phase, low viscosity, appropriate optical anisotropy, large positive or negative dielectric anisotropy, appropriate elastic constants, and good compatibility with other liquid crystalline compounds. [Solution] The compound is represented by formula (1). TIFF2026085011000060.tif2495 Here, for example, R 1 and R 2 These are alkyl groups having 1 to 20 carbon atoms, and ring A 1 is 1,4-cyclohexylene, 1,4-cyclohexenylene, or 1,4-phenylene, Z 1 a is a single bond, -(CH2)2-, -CH2O-, or -OCH2-, and a is 0, 1, 2, or 3.

Description

[Technical Field]

[0001] The present invention relates to liquid crystalline compounds, liquid crystalline compositions, and liquid crystalline display elements. More specifically, it relates to compounds having benzothiophene, liquid crystalline compositions containing this compound and having a nematic phase, and liquid crystalline display elements containing this composition. [Background technology]

[0002] In liquid crystal display elements, classifications based on the operating modes of liquid crystal molecules include modes such as PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS (in-plane switching), VA (vertical alignment), FFS (fringe field switching), and FPA (field-induced photo-reactive alignment). Classifications based on the element's driving method are PM (passive matrix) and AM (active matrix). PM is further classified into static and multiplex, while AM ​​is further classified into TFT (thin film transistor) and MIM (metal insulator metal).

[0003] A liquid crystal composition is encapsulated within this element. The physical properties of this composition are related to the characteristics of the element. Examples of physical properties in the composition include stability against heat and light, temperature range of the nematic phase, viscosity, optical anisotropy, dielectric anisotropy, resistivity, and elastic constants. The composition is prepared by mixing many liquid crystalline compounds. The physical properties required of a liquid crystalline compound include high stability against environmental factors such as water, air, heat, and light, a wide temperature range of the liquid crystal phase, low viscosity, appropriate optical anisotropy, high dielectric anisotropy, appropriate elastic constants, and good compatibility with other liquid crystalline compounds. Compounds with a high upper limit temperature of the nematic phase are preferred. Compounds with a low lower limit temperature in the liquid crystal phase, such as the nematic phase or smectic phase, are preferred as liquid crystalline compounds. Liquid crystalline compounds with low viscosity contribute to the short response time of the element. The appropriate value of optical anisotropy depends on the type of operating mode of the element. To drive the element at low voltage, liquid crystalline compounds with large positive or negative dielectric anisotropy are preferred. To prepare a liquid crystal composition, compounds with good compatibility with other liquid crystalline compounds are preferred. Since the device may be used at sub-zero temperatures, a liquid crystalline compound that has good compatibility at low temperatures is preferred.

[0004] Several liquid crystalline compounds having a benzothiophene skeleton have been synthesized to date. Compounds (A), (B), etc., are shown in Patent Documents 1 and 2. However, there has been a need to further optimize the properties of these compounds by optimizing the type, number, and position of substituents on the benzothiophene ring.

[0005] TIFF2026085011000001.tif17163 [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2016 / 132998 [Patent Document 2] International Publication No. 2017 / 064892 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The first objective is to provide a liquid crystalline compound that satisfies at least one of the following physical properties: high stability against heat and light, a high transparency point (or a high upper temperature limit for the nematic phase), a low lower temperature limit for the nematic phase, low viscosity, appropriate optical anisotropy, large positive or negative dielectric anisotropy, appropriate elastic constants, and good compatibility with other liquid crystalline compounds. The objective is to provide a compound that has large positive or negative dielectric anisotropy compared to similar compounds. The second objective is to provide a liquid crystalline composition containing this compound that satisfies at least one of the following physical properties: high stability against heat and light, a high upper temperature limit for the nematic phase, a low lower temperature limit for the nematic phase, low viscosity, appropriate optical anisotropy, large positive or negative dielectric anisotropy, large resistivity, and appropriate elastic constants. The objective is to provide a liquid crystalline composition that has an appropriate balance with respect to at least two of these physical properties. The third objective is to provide a liquid crystal display element comprising this composition that satisfies at least one of the following characteristics: a wide temperature range over which the element can be used, a short response time, a large voltage retention rate, a low threshold voltage, a large contrast ratio, a low flicker rate, and a long lifespan. [Means for solving the problem]

[0008] Let the compound be represented by formula (1). TIFF2026085011000002.tif2287 In equation (1), R 1 and R 2 These are independently alkyl groups having 1 to 20 carbon atoms, in which at least one -CH2- may be replaced with -O- or -S-, and at least one -(CH2)2- may be replaced with -CH=CH-, and in these groups, at least one hydrogen may be replaced with a halogen, provided that R 2 It is not methoxy; Ring A 1These are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,3-cyclohexadiene-1,4-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, 2,6,7-trioxabicyclo[2.2.2]octane-1,4-diyl, naphthalene-2,6-diyl, or pyridine-2,5-diyl, where at least one hydrogen on these rings may be replaced by a halogen; Z 1 These are independently single-bonded or C1-C4 alkylenes, in which at least one -CH2- may be replaced with -O- or -COO-, at least one -(CH2)2- may be replaced with -CH=CH- or -C≡C-, and in these groups, at least one hydrogen may be replaced with a halogen; a is 0, 1, 2, or 3. [Effects of the Invention]

[0009] The first advantage is to provide a liquid crystalline compound that satisfies at least one of the following physical properties: high stability against heat and light, a high transparency point (or a high upper temperature limit for the nematic phase), a low lower temperature limit for the nematic phase, low viscosity, appropriate optical anisotropy, large positive or negative dielectric anisotropy, appropriate elastic constants, and good compatibility with other liquid crystalline compounds. It also provides a compound having large positive or negative dielectric anisotropy compared to similar compounds. The second advantage is to provide a liquid crystal composition containing this compound that satisfies at least one of the following physical properties: high stability against heat and light, a high upper temperature limit for the nematic phase, a low lower temperature limit for the nematic phase, low viscosity, appropriate optical anisotropy, large positive or negative dielectric anisotropy, large resistivity, and appropriate elastic constants. This advantage is to provide a liquid crystal composition that has an appropriate balance with respect to at least two physical properties. A third advantage is to provide a liquid crystal display element comprising this composition that satisfies at least one of the following characteristics: a wide temperature range over which the element can be used, a short response time, a large voltage retention rate, a low threshold voltage, a large contrast ratio, a low flicker rate, and a long lifespan. [Modes for carrying out the invention]

[0010] The following terms are used in this specification: The terms "liquid crystal compound," "liquid crystal composition," and "liquid crystal display element" may be abbreviated as "compound," "composition," and "element," respectively. "Liquid crystal compound" is a general term for compounds having liquid crystal phases such as nematic phase and smectic phase, and compounds that do not have a liquid crystal phase but are added for the purpose of adjusting the physical properties of a composition, such as upper temperature limit, lower temperature limit, viscosity, and dielectric anisotropy. These compounds have a six-membered ring, such as 1,4-cyclohexylene and 1,4-phenylene, and their molecular structure is rod-like. "Liquid crystal display element" is a general term for liquid crystal display panels and liquid crystal display modules. "Polymerizable compound" is a compound added to a composition for the purpose of generating polymers. Liquid crystal compound having an alkenil is not polymerizable in that sense.

[0011] Liquid crystal compositions are prepared by mixing multiple liquid crystalline compounds. Additives are added to these compositions to further adjust their properties. Additives such as polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, and defoamers are added as needed. Liquid crystalline compounds and additives are mixed in this manner. The proportion (content) of liquid crystalline compounds is expressed as a weight percentage (W%) based on the weight of the liquid crystal composition without additives, even when additives are added. The proportion (amount added) of additives is expressed as a weight percentage (W%) based on the weight of the liquid crystal composition without additives. In other words, the proportion of liquid crystalline compounds and additives is calculated based on the total weight of the liquid crystalline compounds. Parts per million (ppm) may also be used. The proportions of polymerization initiators and polymerization inhibitors are exceptionally expressed based on the weight of the polymerizable compounds.

[0012] The "transparency point" is the transition temperature between the liquid crystal phase and the isotropic phase in a liquid crystalline compound. The "lower limit temperature of the liquid crystal phase" is the transition temperature between the solid and the liquid crystal phase (smectic phase, nematic phase, etc.) in a liquid crystalline compound. The "upper limit temperature of the nematic phase" is the transition temperature between the nematic phase and the isotropic phase in a mixture of a liquid crystalline compound and a mother liquid crystal or in a liquid crystal composition, and is sometimes abbreviated as "upper limit temperature". The "lower limit temperature of the nematic phase" is sometimes abbreviated as "lower limit temperature". The expression "increase dielectric anisotropy" means that for compositions with positive dielectric anisotropy, the value increases positively, and for compositions with negative dielectric anisotropy, the value increases negatively. "Large voltage retention rate" means that the element has a large voltage retention rate not only at room temperature but also at temperatures close to the upper limit temperature in the initial stage, and that it has a large voltage retention rate not only at room temperature but also at temperatures close to the upper limit temperature after prolonged use. The characteristics of compositions and elements may be examined before and after aging tests (including accelerated degradation tests).

[0013] The compound represented by formula (1) may be abbreviated as compound (1). At least one compound selected from the group of compounds represented by formula (1) may be abbreviated as compound (1). "Compound (1)" means one compound represented by formula (1), a mixture of two compounds, or a mixture of three or more compounds. These rules also apply to compounds represented by other formulas. In formulas (1) to (15), N enclosed in a hexagon 1 , B 1 , C 1 and other symbols respectively correspond to ring N 1 , ring B 1 , ring C 1 and other rings. The hexagon represents a six-membered ring such as cyclohexane or benzene. The hexagon may represent a fused ring such as naphthalene or a bridged ring such as adamantane.

[0014] In the chemical formula of the component compound, the symbol of the terminal group R 11 is used for a plurality of compounds. In these compounds, the two groups represented by any two R 11 may be the same or different. For example, there is a case where R[[ID=2`1]] 11 of compound (2) is ethyl and R 11 [[ID=`24]] of compound (3) is ethyl. There is also a case where R 11 of compound (2) is ethyl and R 11 of compound (3) is propyl. This rule also applies to symbols such as R 12 , R 13 , Z 11 and others. In compound (24), when i is 2, two rings E 1 exist. In this compound, the two groups represented by the two rings E 1 may be the same or different. When i is greater than 2, it also applies to any two rings E 1 . This rule also applies to other symbols. <~

[0015] The expression "at least one 'A'" means that the number of 'A's is arbitrary. The expression "at least one 'A' may be replaced by a 'B'" means that when there is one 'A', the position of the 'A' is arbitrary, and when there are two or more 'A's, their positions can be chosen without restriction. This rule also applies to the expression "at least one 'A' is replaced by a 'B'". The expression "at least one 'A' may be replaced by a 'B', 'C', or 'D'" means that any 'A' is replaced by a 'B', any 'A' is replaced by a 'C', any 'A' is replaced by a 'D', and further includes cases where multiple 'A's are replaced by at least two of 'B', 'C', or 'D'. For example, "an alkyl in which at least one -CH2- may be replaced by -O- or -CH=CH-" includes alkyl, alkoxy, alkoxyalkyl, alkenyl, alkoxyalkenyl, and alkenyloxyalkyl. Furthermore, it is preferable that two consecutive -CH2- groups are not replaced by -O- groups, resulting in -OO- groups. In alkyl groups, it is also preferable that the -CH2- group of the methyl group (-CH2-H) is not replaced by -O- groups, resulting in -OH groups.

[0016] "R 11 and R 12 The expression "These groups are independently alkyl groups having 1 to 10 carbon atoms or alkenyl groups having 2 to 10 carbon atoms, in which at least one -CH2- may be replaced by -O-, and in which at least one hydrogen may be replaced by fluorine" is sometimes used. In this expression, "in which these groups" should be interpreted literally. In this expression, "these groups" means alkyl groups, alkenyl groups, alkoxy groups, alkenyloxy groups, etc. That is, "these groups" refers to all the groups listed before the phrase "in which these groups". This common-sense interpretation also applies to the phrases "in which these monovalent groups" and "in which these divalent groups". For example, "these monovalent groups" refers to all the groups listed before the phrase "in which these monovalent groups".

[0017] Halogen refers to fluorine, chlorine, bromine, and iodine. Preferred halogens are fluorine and chlorine. A more preferred halogen is fluorine. Hydrogen refers to a hydrogen atom. Alkyl groups in liquid crystalline compounds are linear or branched and do not include cyclic alkyl groups. Linear alkyl groups are generally preferred over branched alkyl groups. These also apply to terminal groups such as alkoxy and alkenyl groups. For 1,4-cyclohexylene, trans configuration is preferred over cis to increase the upper temperature limit. 2-Fluoro-1,4-phenylene refers to the following two divalent groups. In the chemical formula, fluorine may be left-facing (L) or right-facing (R). This rule also applies to asymmetric divalent groups produced by removing two hydrogens from a ring, such as tetrahydropyran-2,5-diyl.

[0018] TIFF2026085011000003.tif2564

[0019] Equation (PN-4) for the ring PN may be in the orientation of equation (PN-4-1) or equation (PN-4-2). This rule also applies to equation (PN-5). TIFF2026085011000004.tif3084

[0020] The present invention includes the following items, among others.

[0021] [1] A compound represented by formula (1). TIFF2026085011000005.tif2185 In equation (1), R 1 and R 2 These are independently alkyl groups having 1 to 20 carbon atoms, in which at least one -CH2- may be replaced with -O- or -S-, and at least one -(CH2)2- may be replaced with -CH=CH-, and in these groups, at least one hydrogen may be replaced with a halogen, provided that R 2It is not methoxy; Ring A 1 These are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,3-cyclohexadiene-1,4-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, 2,6,7-trioxabicyclo[2.2.2]octane-1,4-diyl, naphthalene-2,6-diyl, or pyridine-2,5-diyl, where at least one hydrogen on these rings may be replaced by a halogen; Z 1 These are independently single-bonded or C1-C4 alkylenes, in which at least one -CH2- may be replaced with -O- or -COO-, at least one -(CH2)2- may be replaced with -CH=CH- or -C≡C-, and in these groups, at least one hydrogen may be replaced with a halogen; a is 0, 1, 2, or 3.

[0022] [2] In formula (1) above, R 1 R is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is replaced by fluorine, 2 These are C1 to C10 alkyl groups, C2 to C9 alkoxy groups, C2 to C10 alkenyl groups, or C1 to C10 alkyl groups in which at least one hydrogen atom is replaced by fluorine; Ring A 1 These are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by a halogen, or tetrahydropyran-2,5-diyl; Z 1These are independently single bonds, -(CH2)2-, -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -(CH2)4-, -(CH2)2CF2O-, -(CH2)2OCF2-, -CF2O(CH2)2-, -OCF2(CH2)2-, -CH=CH-(CH2)2-, or -(CH2)2-CH=CH-; The compounds described in item [1], wherein a is 0, 1, 2, or 3.

[0023] [3] A compound described in item [1] that is represented by any one of formulas (1-1) to (1-4). TIFF2026085011000006.tif88105 In equations (1-1) through (1-4), R 1 R is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is replaced by fluorine; 2 These are C1 to C10 alkyl groups, C2 to C9 alkoxy groups, C2 to C10 alkenyl groups, or C1 to C10 alkyl groups in which at least one hydrogen atom is replaced by fluorine; Ring A 2 , ring A 3 and ring A 4 These are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by a halogen, and tetrahydropyran-2,5-diyl; Z 2 , Z 4 , and Z 5 These are independently single bonds, -(CH2)2-, -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -(CH2)4-, -(CH2)2CF2O-, -(CH2)2OCF2-, -CF2O(CH2)2-, -OCF2(CH2)2-, -CH=CH-(CH2)2-, or -(CH2)2-CH=CH-.

[0024] [4] In equations (1-1) to (1-4) above, R 1 R is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is replaced by fluorine; 2 These are C1 to C10 alkyl groups, C1 to C9 alkoxy groups, C2 to C10 alkenyl groups, or C1 to C10 alkyl groups in which at least one hydrogen atom is replaced by fluorine; Ring A 2 , ring A 3 , and ring A 4 These are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by a halogen, or tetrahydropyran-2,5-diyl; Z 2 , Z 4 , and Z 5 The compounds described in item [3], wherein each is independently a single bond, -(CH2)2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-, or -OCH2-.

[0025] [5] A compound described in item [4] that is represented by any one of formulas (1-1-1) to (1-4-1). TIFF2026085011000007.tif88108 From equation (1-1-1) to equation (1-4-1), R 1 R is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is replaced by fluorine; 2 These are C1 to C10 alkyl groups, C1 to C9 alkoxy groups, C2 to C10 alkenyl groups, or C1 to C10 alkyl groups in which at least one hydrogen atom is replaced by fluorine; Ring A 2 , ring A 3 , and ring A 4These are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene (where at least one hydrogen atom may be replaced by a halogen), or tetrahydropyran-2,5-diyl.

[0026] [6] A liquid crystal composition containing at least one of the compounds described in any one of items [1] to [5].

[0027] [7] The liquid crystal composition according to item [6], comprising at least one compound selected from the group of compounds represented by formulas (2) to (4). TIFF2026085011000008.tif45107 In equations (2) through (4), R 11 and R 12 R is independently an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and this R 11 and R 12 In this, at least one -CH2- may be replaced by -O-, and at least one hydrogen may be replaced by fluorine, but not -CF3, -CHF2, -CH2F, -OCF3, -OCHF2, -OCF2CHF2, or -OCF2CHFCF3; Ring B 1 , ring B 2 , ring B 3 , and ring B 4 These are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, or pyrimidine-2,5-diyl; Z 11 , Z 12 , and Z 13 These are independently single bonds, -COO-, -(CH2)2-, -CH=CH-, or -C≡C-.

[0028] [8] The liquid crystal composition according to item [6] or [7], further comprising at least one compound selected from the group of compounds represented by formula (5) to formula (13). TIFF2026085011000009.tif186129 In equations (5) through (13), R 13 and R 14 R is independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and this R 13 and R 14 In this, at least one -CH2- may be replaced with -O-, and at least one hydrogen may be replaced with fluorine; R 15 R is hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. 15 In this, at least one -CH2- may be replaced with -O-, and at least one hydrogen may be replaced with fluorine; Ring C 1 , ring C 2 , ring C 3 , and ring C 4 These are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene (where at least one hydrogen atom may be replaced by fluorine), tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl; Ring C 5 and ring C 6 These are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl; Z 14 , Z 15 , Z 16 , and Z 17 These are independently single bonds, -COO-, -CH2O-, -OCF2-, -(CH2)2-, or -OCF2-(CH2)2-; L 11 and L 12 These are independently fluorine or chlorine; S 11 is hydrogen or methyl; X is -O-, -S-, -CH2-, -CHF-, -CF2-, -CH2CH2-, -CHFCH2-, -CH2CHF-, -CF2CH2-, -CH2CF2-, -CF2CHF-, -CHFCF2-, -CF2CF2-, -CH=CH-, -CF=CH-, -CH=CF-, or -CF=CF-; j, k, m, n, p, q, r, and s are independently 0 or 1, the sum of k, m, n, and p is 1 or 2, the sum of q, r, and s is 0, 1, 2, or 3, and t is 1, 2, or 3.

[0029] [9] The liquid crystal composition according to item [6] or [7], further containing at least one compound selected from the group of compounds represented by formulas (21) to (23). TIFF2026085011000010.tif61107 In formulas (2l) to (23), R 16 is alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, and in this R 16 at least one -CH2- may be replaced by -O-, and at least one hydrogen may be replaced by fluorine; X 11 is fluorine, chlorine, -CF3, -CHF2, -CH2F, -OCF3, -OCHF2, -OCF_{2}CHF_{2}, or -OCF_{2}CHFCF_{3}; Ring D 1 Ring D 2 and Ring D 3 are independently 1,4 - cyclohexylene, 1,4 - phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran - 2,5 - diyl, 1,3 - dioxane - 2,5 - diyl, or pyrimidine - 2,5 - diyl; Z 18 Z 19 and Z 20 are independently a single bond, -COO-, -CH2O-, -CF2O-, -OCF2-, -(CH2)2-, -CH=CH-, -C≡C-, or -(CH2)4-; L13 and L 14 is independently hydrogen or fluorine.

[0030]

[10] The liquid crystal composition according to item [6] or [7], further containing at least one compound selected from the group of compounds represented by formula (24). TIFF2026085011000011.tif2168 In formula (24), R 17 is alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, and in this R 17 , at least one -CH2- may be replaced by -O-, and at least one hydrogen may be replaced by fluorine; X 12 is -C≡N or -C≡C-C≡N; ring E 1 is 1,4 - cyclohexylene, 1,4 - phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran - 2,5 - diyl, 1,3 - dioxane - 2,5 - diyl, or pyrimidine - 2,5 - diyl; Z 21 is a single bond, -COO-, -CH2O-, -CF2O-, -OCF2-, -(CH2)2-, or -C≡C-; L 15 and L 16 are independently hydrogen or fluorine; i is 1, 2, 3, or 4.

[0031] [1] A liquid crystal display element comprising the liquid crystal composition according to any one of items [6] to

[10] .

[0032] The present invention also includes the following items. (a) The above composition further containing at least one of an optically active compound or a polymerizable compound. (b) The above composition further containing at least one of an antioxidant or an ultraviolet absorber.

[0033] The present invention also includes the following: (c) the composition described above, further comprising at least one additive selected from the group consisting of polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dyes, and defoamers; and (d) the composition described above, wherein the upper limit temperature of the nematic phase is 70°C or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25°C) is 0.08 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25°C) is -2 or lower.

[0034] The present invention also includes the following: (e) an element containing the above composition and having modes PC, TN, STN, ECB, OCB, IPS, VA, FFS, FPA, or PSA; (f) an AM element containing the above composition; (g) a transmissive element containing the above composition; (h) the use of the above composition as a composition having a nematic phase; (i) the use of the above composition as an optically active composition by adding an optically active compound to the above composition.

[0035] The embodiments of compound (1), the synthesis of compound (1), the liquid crystal composition, and the liquid crystal display element will be described in order.

[0036] 1. Embodiment of compound (1) The present invention's compound (1) will now be described. Preferred examples of terminal groups, ring structures, and bonding groups in compound (1), and the effects of these groups on the physical properties, also apply to the subcategories of compound (1).

[0037] TIFF2026085011000012.tif2287

[0038] This compound is extremely stable physically and chemically under the conditions under which the device is normally used, and has good compatibility with other liquid crystalline compounds. Compositions containing this compound are stable under the conditions under which the device is normally used. This compound possesses the general physical properties and appropriate optical anisotropy required for the components of a composition.

[0039] In equation (1), R 1 and R2 These are independently alkyl groups having 1 to 20 carbon atoms, in which at least one -CH2- may be replaced with -O- or -S-, and at least one -(CH2)2- may be replaced with -CH=CH-, and in these groups, at least one hydrogen may be replaced with a halogen, provided that R 2 It is not methoxy.

[0040] R 1 or R 2 Preferred examples include alkyl, alkoxy, alkenyl, and alkenyloxy. 1 Further preferred examples are alkyl and alkenyl. 2 Further preferred examples are alkyl, alkoxy, and alkenyl. 1 or R 2 This may be an alkoxyalkyl, an alkyl in which at least one hydrogen is replaced by a halogen, an alkoxy in which at least one hydrogen is replaced by a halogen, or an alkenyl in which at least one hydrogen is replaced by a halogen.

[0041] Examples of alkyl groups include -CH3, -C2H5, -C3H7, -C4H9, and -C5H 11 , -C6H 13 -C7H 15 -C8H 17、 -C9H 19 , -C 10 H 21 , -C 11 H 23 , -C 12 H 25 , -C 13 H 27 , -C 14 H 29 , and -C 15 H 31 That is the case.

[0042] Examples of alkoxys include -OC2H5, -OC3H7, -OC4H9, and -OC5H. 11 -OC6H 13 -OC7H 15 -OC8H17、 -OC9H 19 -OC 10 H 21 -OC 11 H 23 -OC 12 H 25 -OC 13 H 27 , and -OC 14 H 29 That is the case.

[0043] Examples of alkoxyalkyls include -CH2OCH3, -CH2OC2H5, -CH2OC3H7, -(CH2)2-OCH3, -(CH2)2-OC2H5, -(CH2)2-OC3H7, -(CH2)3-OCH3, -(CH2)4-OCH3, and -(CH2)5-OCH3.

[0044] Examples of alkenyls are -CH=CH2, -CH=CHCH3, -CH2CH=CH2, -CH=CHC2H5, -CH2CH=CHCH3, -(CH2)2-CH=CH2, -CH=CHC3H7, -CH2CH=CHC2H5, -(CH2)2-CH=CHCH3, and -(CH2)3-CH=CH2.

[0045] Examples of alkenyloxys are -OCH2CH=CH2, -OCH2CH=CHCH3, and -OCH2CH=CHC2H5.

[0046] Examples of alkyl groups in which at least one hydrogen atom is replaced by a halogen include -CH2F, -CHF2, -CF3, -(CH2)2-F, -CF2CH3, -CF2CH2F, -CF2CHF2, -CH2CF3, -CF2CF3, -(CH2)3-F, -CF2CH2CH3, -CH2CHFCH3, -CH2CF2CH3, -(CF2)3-F, -CF2CHFCF3, -CHFCF2CF3, -(CH2)4-F, -CF2(CH2)2CH3, -(CF2)4-F, -(CH2)5-F, - (CF2)5-F, -CH2Cl, -CHCl2, -CCl3, -(CH2)2-Cl, -CCl2CH3, -CCl2CH2Cl, -CCl2CHCl2, -CH2CCl3, -CCl2CCl3, -(CH2)3-Cl, -CCl2CH2C H3, -(CCl2)3-Cl, -CCl2CHClCCl3, -CHClCCl2CCl3, -(CH2)4-Cl, -(CCl2)4-Cl, -CCl2(CH2)2CH3, -(CH2)5-Cl, and -(CCl2)5-Cl.

[0047] Examples of alkoxys in which at least one hydrogen atom is replaced by a halogen include -O-(CH2)2-F, -OCF2CH2F, -OCF2CHF2, -OCH2CF3, -O-(CH2)3-F, -O-(CF2)3-F, -OCF2CHFCF3, -OCHFCF2CF3, -O(CH2)4-F, -O-(CF2)4-F, -O-(CH2)5-F, -O-(CF2)5-F, -OCH2CHFCH2CH3, - OCH2Cl, -OCHCl2, -OCCl3, -O-(CH2)2-Cl, -OCCl2CH2Cl, -OCCl2CHCl2, -OCH2CCl3, -O-(CH2)3-Cl, -O-(CCl2)3 -Cl, -OCCl2CHClCCl3, -OCHClCCl2CCl3, -O(CH2)4-Cl, -O-(CCl2)4-Cl, -O-(CH2)5-Cl, and -O-(CCl2)5-Cl.

[0048] Examples of alkenyls in which at least one hydrogen atom is replaced by a halogen include -CH=CHF, -CH=CF2, -CF=CHF, -CH=CHCH2F, -CH=CHCF3, -(CH2)2-CH=CF2, -CH2CH=CHCF3, -CH=CHCF2CF3, -CH=CHCl, -CH=CCl2, -CCl=CHCl, -CH=CHCH2Cl, -CH=CHCCl3, -(CH2)2-CH=CCl2, -CH2CH=CHCCl3, and -CH=CHCCl2CCl3.

[0049] R 2 If the compound is methoxy, it is undesirable because its compatibility with other liquid crystalline compounds becomes significantly poor.

[0050] In equation (1), ring A 1 These are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,3-cyclohexadiene-1,4-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, 2,6,7-trioxabicyclo[2.2.2]octane-1,4-diyl, naphthalene-2,6-diyl, or pyridine-2,5-diyl, where at least one hydrogen on these rings may be replaced by a halogen.

[0051] Ring A 1 Preferred examples include 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine, tetrahydropyran-2,5-diyl, and 5,5,6,6-tetrafluoro-1,3-cyclohexadiene-1,4-diyl. Even more preferred examples are 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine, and tetrahydropyran-2,5-diyl. 1,4-cyclohexylene exists in cis and trans configurations. From the viewpoint of a high upper temperature limit, the trans configuration is preferred.

[0052] Preferred examples of 1,4-phenylene in which at least one hydrogen atom is replaced by a halogen are the groups represented by formulas (A-1) to (A-17). To have a large negative dielectric anisotropy, the groups represented by formulas (A-1), (A-5), (A-6), (A-7), (A-8), (A-9), (A-10), or (A-11) are more preferred. TIFF2026085011000013.tif99165

[0053] In equation (1), Z 1 These are independently single-bonded or C1-C4 alkylenes, in which at least one -CH2- may be replaced with -O- or -COO-, and at least one -(CH2)2- may be replaced with -CH=CH- or -C≡C-, and in these groups, at least one hydrogen may be replaced with a halogen.

[0054] Z 1 Preferred examples are single bonds, -(CH2)2-, -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -(CH2)4-, -(CH2)2CF2O-, -(CH2)2OCF2-, -CF2O(CH2)2-, -OCF2(CH2)2-, -CH=CH-(CH2)2-, and -(CH2)2-CH=CH-. More preferred examples are single bonds, -(CH2)2-, -CH=CH-, -COO-, -OCO-, -CF2O-, -OCF2-, -CH2O-, and -OCH2-. Still preferred examples are single bonds, -(CH2)2-, -CH2O-, and -OCH2-.

[0055] In formula (1), a is 0, 1, 2, or 3. Compounds with a of 2 or less are preferred, considering compatibility with other liquid crystalline compounds. When a is 1 or 0, the viscosity is low. When a is 2, there is a good balance between viscosity and the upper temperature limit. When a is 3, the upper temperature limit is high.

[0056] Compound (1) exhibits high properties due to its benzothiophene skeleton, in which F is substituted at positions 7 and 5, oxygen is substituted at position 6, and a ring or alkyl group is substituted at position 2. The effects of this invention cannot be fully obtained with skeletons in different substitution positions of these groups, or with skeletons that have increased or decreased substituents. Due to the effects of this structure, it has a high transparency point, a low lower limit temperature of the liquid crystal phase, low viscosity, appropriate optical anisotropy, large positive or negative dielectric anisotropy, appropriate elastic constants, and excellent compatibility with other liquid crystalline compounds.

[0057] As described above, by appropriately selecting the types of terminal groups, ring structures, and bonding groups, compounds with the desired physical properties can be obtained. Since there is no significant difference in the physical properties of the compounds, compound (1) is 2 H (deuterium), 13 It may contain isotopes such as 13C in amounts greater than their natural abundance.

[0058] By appropriately selecting the terminal groups, rings, and bonding groups of compound (1), it is possible to arbitrarily adjust physical properties such as optical anisotropy and dielectric anisotropy. Terminal group R 1 and R 2 , bonding group Z 1 The effect of the type on the physical properties of compound (1) is explained below.

[0059] In compound (1), R 1 or R 2 When it is linear, the temperature range of the liquid crystal phase is wide and the viscosity is low. 1 or R 2 When it is a branched chain, it has good compatibility with other liquid crystalline compounds. 1 or R 2 Compounds in which the optically active group is are useful as chiral dopants. By adding this compound to the composition, the formation of reverse twisted domains in the device can be prevented. 1 or R 2 Compounds that do not have an optically active group are useful as components of the composition. 1 or R 2When the compound is an alkenyl, the preferred stereochemistry depends on the position of the double bond. Alkenyl compounds with a preferred stereochemistry have a high upper temperature limit or a wide temperature range for the liquid crystal phase. A detailed explanation can be found in Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327.

[0060] Ring A 1 However, when it is 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl, the optical anisotropy is high. Ring A 1 However, when it is 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, dihydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl, the optical anisotropy is small.

[0061] Multiple rings A 1 When is 1,4-cyclohexylene, the upper temperature limit is high, the optical anisotropy is low, and the viscosity is low; when at least two are 1,4-phenylene, the optical anisotropy is high, the temperature range of the liquid crystal phase is wide, and the upper temperature limit is high. Ring A 1 When at least one of the elements is 1,4-phenylene, the optical anisotropy is relatively large, and the orientational order parameter is large.

[0062] Z 1 When the bond is a single bond, -CH2O-, -CF2O-, -OCF2-, -(CH2)2-, -CH=CH-, -CF=CF-, or -(CH2)4-, the viscosity is low. 1 However, the viscosity is lower when it is a single bond, -OCF2-, -CF2O-, -(CH2)2-, or -CH=CH-. 1 When -CH=CH-, the temperature range of the liquid crystal phase is wide, and the ratio of elastic constants K is high. 33 / K 11 (K 33: Bending elastic constant, K 11 The spray elastic constant is large. 1 When -C≡C-, the optical anisotropy is large.

[0063] When compound (1) has one or two rings, it has good compatibility with other liquid crystalline compounds and low viscosity. When compound (1) has three or four rings, it has a high upper temperature limit. When compound (1) has four rings, it has a wide temperature range for the liquid crystal phase. As described above, by appropriately selecting the types of terminal groups, rings, and bonding groups, and the number of rings, a compound with the desired physical properties can be obtained. Therefore, compound (1) is useful as a component of compositions used in devices having modes such as PC, TN, STN, ECB, OCB, IPS, and VA.

[0064] Preferred examples of compound (1) are compounds (1-1) to (1-4) described in section 3. More preferred examples are compounds (1-1-1) and (1-4-1) described in section 5. Compound (1) is suitable for devices having modes such as VA, IPS, and PSA.

[0065] 2. Synthesis of compound (1) This section describes the synthesis method of compound (1). Compound (1) can be synthesized by appropriately combining methods of organic synthesis. Methods for introducing the required terminal groups, rings, and bonding groups into the starting materials are described in textbooks such as "Organic Syntheses" (John Wiley & Sons, Inc.), "Organic Reactions" (John Wiley & Sons, Inc.), "Comprehensive Organic Synthesis" (Pergamon Press), and "New Experimental Chemistry Course" (Maruzen).

[0066] 2-1. Formation of the binding group Z bonding group Z 1Regarding the method for generating MSG, we first present the scheme. Next, we explain the reactions described in the scheme in (1) to (11). In this scheme, MSG 1 (or MSG) 2 ) is a monovalent organic group having at least one ring. Multiple MSGs used in the scheme 1 (or MSG) 2 The monovalent organic group represented by ) may be the same or different. Compounds (1A) through (1J) correspond to compound (1).

[0067] TIFF2026085011000014.tif238163

[0068] TIFF2026085011000015.tif82161

[0069] (1) Formation of single bonds Compound (1A) is synthesized by reacting arylboric acid (31), synthesized by known methods, with a halide (32) in the presence of a carbonate and a catalyst such as tetrakis(triphenylphosphine)palladium. Compound (1A) can also be synthesized by reacting a halide (33), synthesized by known methods, with n-butyllithium, then with zinc chloride, and then reacting the resulting mixture with the halide (32) in the presence of a catalyst such as dichlorobis(triphenylphosphine)palladium.

[0070] (2) Generation of COO- n-butyllithium is reacted with the halide (33) followed by carbon dioxide to obtain a carboxylic acid (34). Compound (1B) is synthesized by dehydrating compound (35), which is synthesized by a known method, and carboxylic acid (34) in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine).

[0071] (3) Formation of -CF2O- Compound (1B) is treated with a sulfurizing agent such as Lawson's reagent to obtain thionoester (36). Thionoester (36) is fluorinated with a pyridine hydrogen fluoride complex and NBS (N-bromosuccinimide) to synthesize compound (1C). See M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1C) can also be synthesized by fluorinating thionoester (36) with DAST ((diethylamino)sulfate trifluoride). See WH Bunnelle et al., J. Org. Chem. 1990, 55, 768. This bonding group can also be generated by the method described in Peer. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480.

[0072] (4) Formation of -CH=CH- After treating the halide (32) with n-butyllithium, it is reacted with DMF (N,N-dimethylformamide) to obtain the aldehyde (38). The phosphonium salt (37), synthesized by known methods, is treated with a base such as potassium t-butoxide to generate a phosphorus ylide. This phosphorus ylide is reacted with the aldehyde (38) to synthesize compound (1D). Depending on the reaction conditions, the cis isomer may be formed, so if necessary, the cis isomer is converted to the trans isomer by known methods.

[0073] (5) Formation of (CH2)2- Compound (1E) is synthesized by hydrogenating compound (1D) in the presence of a catalyst such as palladium-carbon.

[0074] (6) Formation of (CH2)4- Using phosphonium salt (39) instead of phosphonium salt (37), a compound having -(CH2)2-CH=CH- is obtained according to method (4). Compound (1F) is synthesized by catalytic hydrogenation of this compound.

[0075] (7) - CH2CH = CHCH2- Compound (1G) is synthesized according to method (4), using phosphonium salt (40) instead of phosphonium salt (37) and aldehyde (41) instead of aldehyde (38). Depending on the reaction conditions, the trans isomer may be formed, so if necessary, the trans isomer is converted to the cis isomer by a known method.

[0076] (8) Generation of -C≡C- In the presence of a dichloropalladium-copper halide catalyst, the halide (33) is reacted with 2-methyl-3-butyne-2-ol, and then deprotected under basic conditions to obtain compound (42). In the presence of a dichloropalladium-copper halide catalyst, compound (42) is reacted with the halide (32) to synthesize compound (1H).

[0077] (9) -CF=CF- generation After treating the halide (33) with n-butyllithium, it is reacted with tetrafluoroethylene to obtain compound (43). After treating the halide (32) with n-butyllithium, it is reacted with compound (43) to synthesize compound (1I).

[0078] (10) Formation of OCH2- Aldehyde (38) is reduced with a reducing agent such as sodium borohydride to obtain compound (44). Compound (44) is brominated with hydrobromic acid or the like to obtain bromide (45). In the presence of a base such as potassium carbonate, bromide (45) is reacted with compound (46) to synthesize compound (1J).

[0079] (11)-(CF2)2- generation According to the method described in J. Am. Chem. Soc., 2001, 123, 5414, a diketone (-COCO-) is fluorinated with sulfur tetrafluoride in the presence of a hydrogen fluoride catalyst to obtain a compound having -(CF2)2-.

[0080] Examples of methods for synthesizing compound (1) are as follows. In these compounds, R 1 , R 2 , ring A 1, Z 1 The definitions of , and a are the same as in item 1 above. Compound (b-1), synthesized by a known method, is lithiated with sec-BuLi and reacted with S and bromoacetaldehyde diethyl acetal to obtain (b-2). This is reacted with polyphosphate in toluene or chlorobenzene to obtain (b-3). (b-3) is lithiated with LDA to obtain (b-4), and various reagents are reacted to obtain various intermediates. These are used to derive compound (1) by a known method. TIFF2026085011000016.tif54164

[0081] 3. Liquid crystal composition 3-1.Component compounds The liquid crystal composition of the present invention will now be described. This composition contains at least one compound (1) as component (a). This composition may contain two or more compounds (1). The composition may consist only of compound (1). It is preferable for the composition to contain at least one compound (1) in an amount ranging from 1% to 99% by weight in order to exhibit good physical properties. In a composition with negative dielectric anisotropy, the preferred content of compound (1) is in the range of 5% to 60% by weight. In a composition with positive dielectric anisotropy, the preferred content of compound (1) is 30% by weight or less.

[0082] TIFF2026085011000017.tif48119

[0083] This composition preferably further contains a liquid crystalline compound selected from the compounds (b) to (e) shown in Table 1. When preparing this composition, it is preferable to select the compounds (b) to (e) considering the positive / negative and magnitude of the dielectric anisotropy. This composition may also contain liquid crystalline compounds different from compounds (1) to (13) and (21) to (24). This composition may not contain such liquid crystalline compounds.

[0084] Component (b) is a compound in which two terminal groups are alkyl or the like. Preferred examples of component (b) include compounds (2-1) to (2-11), compounds (3-1) to (3-21), and compounds (4-1) to (4-7). In these compounds, R 11 and R 12 R is independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and this R 11 or R 12 In this, at least one -CH2- may be replaced with -O-, and at least one hydrogen may be replaced with fluorine, provided that it does not contain -CF3, -CHF2, -CH2F, -OCF3, -OCHF2, -OCF2CHF2, or -OCF2CHFCF3.

[0085] TIFF2026085011000018.tif218163

[0086] Component (b) has a small dielectric anisotropy. Component (b) is close to neutral. Compound (2) has the effect of lowering viscosity or adjusting optical anisotropy. Compounds (3) and (4) have the effect of extending the temperature range of the nematic phase or adjusting optical anisotropy by raising the upper temperature limit.

[0087] As the content of component (b) increases, the viscosity of the composition decreases, but the dielectric anisotropy decreases. Therefore, a higher content is preferable as long as the required threshold voltage of the device is met. When preparing compositions for modes such as IPS and VA, the content of component (b) is preferably 30% by weight or more, and more preferably 40% by weight or more, based on the weight of the liquid crystal composition.

[0088] Component (c) is compounds (5) to (13). These compounds have phenylene with two halogens substituted at the lateral position, such as 2,3-difluoro-1,4-phenylene. Preferred examples of component (c) include compounds (5-1) to (5-10), compounds (6-1) to (6-23), compounds (7-1) and (7-2), compounds (8-1) to (8-3), compounds (9-1) to (9-3), compounds (10-1) to (10-11), compounds (11-1) to (11-13), compounds (12-1) to (12-3), and compound (13-1). In these compounds, R 13 and R 14 R is independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and this R 13 or R 14 In this, at least one -CH2- may be replaced with -O-, and at least one hydrogen may be replaced with fluorine, R 15 R is hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. 15 In this, at least one -CH2- may be replaced with -O-, and at least one hydrogen may be replaced with fluorine.

[0089] TIFF2026085011000019.tif244154

[0090] TIFF2026085011000020.tif249157

[0091] Component (c) has a large negative dielectric anisotropy. Component (c) is used when preparing compositions for modes such as IPS, VA, and PSA. As the content of component (c) increases, the dielectric anisotropy of the composition becomes larger in the negative, but the viscosity also increases. Therefore, as long as the required threshold voltage of the device is met, a smaller content is preferable. Considering that the dielectric anisotropy is about -5, a content of 40% by weight or more is preferable for sufficient voltage driving.

[0092] Of the components (c), compound (5) is a bicyclic compound, and therefore has the effect of lowering viscosity, adjusting optical anisotropy, or increasing dielectric anisotropy. Compounds (6) and (7) are tricyclic compounds, and compound (8) is a tetracyclic compound, and therefore have the effect of raising the upper temperature limit, increasing optical anisotropy, or increasing dielectric anisotropy. Compounds (9) to (13) have the effect of increasing dielectric anisotropy.

[0093] When preparing compositions for modes such as IPS, VA, and PSA, the content of component (c) is suitable in the range of 1% to 99% by weight, based on the weight of the liquid crystal composition. When component (c) is added to a composition with positive dielectric anisotropy, the content of component (c) is preferably 30% by weight or less. By adding component (c), it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.

[0094] Component (d) is compounds (21) to (23), which have a halogen or fluorine-containing group at their right end. Preferred examples of component (d) include compounds (21-1) to (21-16), compounds (22-1) to (22-116), and compounds (23-1) to (23-59). In these compounds, R 16 This R is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. 16 In this, at least one -CH2- may be replaced with -O-, and at least one hydrogen may be replaced with fluorine. 11 These are fluorine, chlorine, -CF3, -CHF2, -CH2F, -OCF3, -OCHF2, -OCF2CHF2, or -OCF2CHFCF3.

[0095] TIFF2026085011000021.tif98124

[0096] TIFF2026085011000022.tif234160

[0097] TIFF2026085011000023.tif245158

[0098] TIFF2026085011000024.tif244159

[0099] TIFF2026085011000025.tif4670

[0100] TIFF2026085011000026.tif237159

[0101] TIFF2026085011000027.tif172158

[0102] Component (d) has positive dielectric anisotropy and excellent stability against heat and light, and is therefore used when preparing compositions for modes such as IPS, FFS, and OCB. The content of component (d) is suitable in the range of 1% to 99% by weight, preferably in the range of 10% to 97% by weight, and more preferably in the range of 40% to 95% by weight, based on the weight of the liquid crystal composition. When component (d) is added to a composition with negative dielectric anisotropy, the content of component (d) is preferably 30% by weight or less. By adding component (d), it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.

[0103] Component (e) is compound (24) whose right-terminal group is -C≡N or -C≡CC≡N. Preferred examples of component (e) include compounds (24-1) to (24-64). In these compounds, R 17 This R is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. 17 In this, at least one -CH2- may be replaced with -O-, and at least one hydrogen may be replaced with fluorine. 12 -C≡N or -C≡CC≡N.

[0104] TIFF2026085011000028.tif239150

[0105] TIFF2026085011000029.tif141163

[0106] Component (e) has a positive dielectric anisotropy and a large value, so it is used when preparing compositions for modes such as TN. By adding component (e), the dielectric anisotropy of the composition can be increased. Component (e) has the effect of broadening the temperature range of the liquid crystal phase, adjusting viscosity, or adjusting optical anisotropy. Component (e) is also useful for adjusting the voltage-transmittance curve of the device.

[0107] When preparing compositions for modes such as TN, the content of component (e) is suitable in the range of 1% to 99% by weight, preferably in the range of 10% to 97% by weight, and more preferably in the range of 40% to 95% by weight, based on the weight of the liquid crystal composition. When component (e) is added to a composition with negative dielectric anisotropy, the content of component (e) is preferably 30% by weight or less. By adding component (e), it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.

[0108] By combining a compound appropriately selected from the above components (b) to (e) with compound (1), a liquid crystal composition can be prepared that satisfies at least one of the following physical properties: high stability against heat and light, a high upper temperature limit, a low lower temperature limit, low viscosity, appropriate optical anisotropy (i.e., large or small optical anisotropy), large positive or negative dielectric anisotropy, large resistivity, and appropriate elastic constants (i.e., large or small elastic constants). Devices containing such compositions have a wide temperature range over which the device can be used, a short response time, a large voltage retention rate, a low threshold voltage, a large contrast ratio, a low flicker rate, and a long lifetime.

[0109] When an element is used for a long period of time, flicker may occur on the display screen. The flicker rate (%) can be expressed as (|Brightness when a positive voltage is applied - Brightness when a negative voltage is applied| / Average Brightness) × 100. Elements with a flicker rate in the range of 0% to 1% are less likely to produce flicker on the display screen even when used for a long period of time. This flicker is related to image burn-in and is presumed to be caused by the potential difference between the positive and negative frames when driven by AC. Compositions containing compound (1) are also useful in reducing the occurrence of flicker.

[0110] 3-2. Additives Liquid crystal compositions are prepared by known methods. For example, component compounds are mixed and then dissolved by heating. Depending on the application, additives may be added to the composition. Examples of additives include polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dyes, and defoamers. Such additives are well known to those skilled in the art and are described in the literature.

[0111] In liquid crystal display elements with PSA (polymer-sustained alignment) mode, the composition contains a polymer. A polymerizable compound is added to the composition for the purpose of generating a polymer. By applying a voltage between the electrodes and irradiating with ultraviolet light, the polymerizable compound is polymerized, thereby generating a polymer in the composition. This method achieves appropriate pre-tilt, resulting in a shortened response time and the fabrication of an element with improved image burn-in.

[0112] Preferred examples of polymerizable compounds include acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes), and vinyl ketones. More preferred examples are compounds having at least one acryloyloxy compound and compounds having at least one methacryloyloxy compound. Further preferred examples include compounds having both acryloyloxy and methacryloyloxy compounds.

[0113] Further preferred examples are compounds (M-1) to (M-18). In these compounds, R 25 From R 31 R is independently hydrogen or methyl; 32 , R 33 , and R 34 L is independently hydrogen or an alkyl group having 1 to 5 carbon atoms; v, w, and x are independently 0 or 1; and u and y are independently integers from 1 to 10. 21 From L 26 L is independently hydrogen or fluorine; 27 and L 28 These are independently hydrogen, fluorine, or methyl.

[0114] TIFF2026085011000030.tif252163

[0115] Polymerizable compounds can be rapidly polymerized by adding polymerization initiators. By optimizing the reaction conditions, the amount of residual polymerizable compound can be reduced. Examples of photoradical polymerization initiators include TPO, 1173, and 4265 from BASF's Darocur series (Darocur is a registered trademark), and 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850, and 2959 from IRGACURE (IRGACURE is a registered trademark) series.

[0116] Examples of additional photoradical polymerization initiators include 4-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(4-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michlar's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, benzyldimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,4-diethylxanthone / p-dimethylaminobenzoate methyl mixture, and benzophenone / methyltriethanolamine mixture.

[0117] Polymerization can be carried out by adding a photoradical polymerization initiator to a liquid crystal composition and then irradiating it with ultraviolet light while applying an electric field. However, unreacted polymerization initiators or decomposition products of polymerization initiators may cause display defects such as image burn-in on the device, so to prevent this, photopolymerization may be carried out without adding a polymerization initiator. The preferred wavelength of the irradiated light is in the range of 150 nm to 500 nm. A more preferred wavelength is in the range of 250 nm to 450 nm, and the most preferred wavelength is in the range of 300 nm to 400 nm.

[0118] When storing polymerizable compounds, polymerization inhibitors may be added to prevent polymerization. Polymerizable compounds are usually added to compositions without removing the polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, and phenothiazine.

[0119] Optically active compounds have the effect of preventing reverse twisting by inducing a helical structure in liquid crystal molecules and giving them the necessary twist angle. The helical pitch can be adjusted by adding optically active compounds. Two or more optically active compounds may be added to adjust the temperature dependence of the helical pitch. Preferred examples of optically active compounds include the following compounds (Op-1) to (Op-18). In compound (Op-18), ring F is 1,4-cyclohexylene or 1,4-phenylene, and R 35 These are alkyl groups with 1 to 10 carbon atoms. * indicates a chiral carbon.

[0120] TIFF2026085011000031.tif229161

[0121] Antioxidants are effective in maintaining a high voltage retention rate. Preferred examples of antioxidants include the following compounds (AO-1) and (AO-2): Irganox 415, Irganox 565, Irganox 1010, Irganox 1035, Irganox 3114, and Irganox 1098 (trade names; BASF; IRGANOX is a registered trademark). UV absorbers are effective in preventing a decrease in the upper temperature limit. Preferred examples of UV absorbers include benzophenone derivatives, benzoate derivatives, and triazole derivatives, with specific examples being the following compounds (AO-3) and (AO-4); Tinuvin 329, Tinuvin P, Tinuvin 326, Tinuvin 234, Tinuvin 213, Tinuvin 400, Tinuvin 328, and Tinuvin 99-2 (trade name; BASF; TINUVIN and Tinuvin are registered trademarks); and 1,4-diazabicyclo[2.2.2]octane (DABCO).

[0122] Light stabilizers such as sterically hindered amines are preferred for maintaining a high voltage retention rate. Preferred examples of light stabilizers include the following compounds: (AO-5), (AO-6), (AO-7), (AO-8), and (AO-9); Tinuvin 144, Tinuvin 765, Tinuvin 770DF, Tinuvin 780 (trade names: BASF); LA-52, LA-57, LA-77Y, and LA-77G (trade names: ADEKA). This is possible. Thermal stabilizers are also effective in maintaining a high voltage retention rate, and a preferred example is Irgafos 168 (trade name; BASF; Irgafos is a registered trademark). Dichroic dyes such as azo dyes and anthraquinone dyes are added to the composition to suit GH (guest host) mode elements. Defoaming agents are effective in preventing foaming. Preferred examples of defoaming agents are dimethyl silicone oil and methylphenyl silicone oil.

[0123] TIFF2026085011000032.tif95162

[0124] In compound (AO-1), R 40 These are alkyl groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, and -COOR groups. 41 , or -(CH2)2-COOR 41 And here R 41 is an alkyl group having 1 to 20 carbon atoms. In compounds (AO-2) and (AO-5), R 42 R is an alkyl group having 1 to 20 carbon atoms. In compound (AO-5), R 43 is hydrogen, methyl or O · (Oxygen radical) and ring G 1 is 1,4-cyclohexylene or 1,4-phenylene; in compounds (AO-7) and (AO-8), ring G 2z is 1,4-cyclohexylene, 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine; in compounds (AO-5), (AO-7), and (AO-8), z is 1, 2, or 3.

[0125] 4. Liquid crystal display element The liquid crystal composition has operating modes such as PC, TN, STN, OCB, and PSA, and can be used in liquid crystal display elements driven by an active matrix system. This composition also has operating modes such as PC, TN, STN, OCB, VA, and IPS, and can be used in liquid crystal display elements driven by a passive matrix system. These elements can be applied to reflective, transmissive, or semi-transmissive types.

[0126] This composition is also suitable for NCAP (nematic curvilinear aligned phase) elements, where the composition is microencapsulated. This composition can also be used for polymer-dispersed liquid crystal displays (PDLCDs) and polymer-network liquid crystal displays (PNLCDs). In these compositions, a large amount of polymerizable compound is added. On the other hand, when the proportion of polymerizable compound is 10% by weight or less based on the weight of the liquid crystal composition, a PSA mode liquid crystal display element is fabricated. A preferred proportion is in the range of 0.1% to 2% by weight. A more preferred proportion is in the range of 0.2% to 1.0% by weight. PSA mode elements can be driven by drive methods such as active-matrix and passive-matrix. Such elements can be applied to reflective, transmissive, and semi-transmissive types. [Examples]

[0127] 1. Examples of Compound (1) The present invention will be described in more detail by reference to examples. Since the examples are typical, the present invention is not limited by them. Compound (1) was synthesized by the following procedure. The synthesized compound was identified by methods such as NMR analysis. The physical properties of the compound and composition, and the characteristics of the device, were measured by the following methods.

[0128] NMR analysis: Bruker BioSpin DRX-500, AVANCE III HD 400, and AVANCE III 400 were used for the measurements. 1 For 1H-NMR measurements, the sample was dissolved in a deuterated solvent such as CDCl3, and measurements were performed at room temperature, 500 MHz or 400 MHz, and with 16 integration cycles. Tetramethylsilane was used as an internal standard. 19 In the F-NMR measurements, CFCl3 was used as an internal standard, and the measurement was performed 24 times. In the description of nuclear magnetic resonance spectra, s means singlet, d means doublet, t means triplet, q means quartet, quin means quintet, sext means sextet, m means multiplet, and br means broad.

[0129] Gas chromatographic analysis: A Shimadzu GC-2010 gas chromatograph was used for the measurements. The column used was an Agilent Technologies Inc. capillary column DB-1 (length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm). Helium (1 mL / min) was used as the carrier gas. The temperature of the sample vaporization chamber and the detector (FID) were set to 300°C. The sample was dissolved in acetone to prepare a 1% by weight solution, and 1 μL of the resulting solution was injected into the sample vaporization chamber. A Shimadzu GCSolution system was used as the recorder.

[0130] Gas chromatograph-mass spectrometry (hereinafter sometimes referred to as GC-MS): A Shimadzu QP-2010Ultra gas chromatograph-mass spectrometer was used for the measurement. The column used was an Agilent Technologies Inc. capillary column DB-1 (length 60m, inner diameter 0.25mm, film thickness 0.25μm). Helium (1mL / min) was used as the carrier gas. The temperature of the sample vaporization chamber was set to 300°C, the temperature of the ion source to 200°C, the ionization voltage to 70eV, and the emission current to 150μA. The sample was dissolved in acetone to prepare a 0.1% by weight solution, and 1 μL of the resulting solution was injected into the sample vaporization chamber. A Shimadzu GCMSsolution system was used as the recorder.

[0131] HPLC analysis: A Shimadzu Prominence (LC-20AD; SPD-20A) was used for the measurements. The column used was a YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle size 5 μm) manufactured by YMC Corporation. The eluent was a mixture of acetonitrile and water as appropriate. UV detectors, RI detectors, and CORONA detectors were used as appropriate detectors. When using a UV detector, the detection wavelength was set to 254 nm. The sample was dissolved in acetonitrile to prepare a 0.1 wt% solution, and 1 μL of this solution was introduced into the sample chamber. A Shimadzu C-R7Aplus was used as the recorder.

[0132] Ultraviolet-Vis spectroscopic analysis: A Shimadzu PharmaSpec UV-1700 was used for the measurements. The detection wavelength was set from 190 nm to 700 nm. The sample was dissolved in acetonitrile to prepare a 0.01 mmol / L solution, which was then placed in a quartz cell (optical path length 1 cm) for measurement.

[0133] Measurement Samples: When measuring phase structure and transition temperatures (transparency point, melting point, polymerization initiation temperature, etc.), the compound itself was used as the sample. When measuring physical properties such as the upper temperature limit of the nematic phase, viscosity, optical anisotropy, and dielectric anisotropy, a mixture of the compound and the mother liquid crystal was used as the sample.

[0134] When a sample containing a compound mixed with a mother liquid crystal was used, the measurement was performed as follows: A sample was prepared by mixing 15% by weight of the compound with 85% by weight of the mother liquid crystal. From the measured values ​​of this sample, an extrapolated value was calculated according to the following equation, and this value is recorded: <Extrapolated value> = (100 × <Measured value of sample> - <Weight % of mother liquid crystal> × <Measured value of mother liquid crystal>) / <Weight % of compound>

[0135] If crystals (or smectic phase) precipitate at 25°C in this ratio, the ratio of compound to matrix liquid crystal was changed in the following order: 10% by weight:90% by weight, 5% by weight:95% by weight, and 1% by weight:99% by weight. The physical properties of the sample were measured at the ratio in which crystals (or smectic phase) no longer precipitated at 25°C. Unless otherwise specified, the ratio of compound to matrix liquid crystal is 15% by weight:85% by weight.

[0136] When the dielectric anisotropy of the compound was zero or positive, the following mother liquid crystal (A) was used. The proportion of each component is expressed in weight percent.

[0137] TIFF2026085011000033.tif5183

[0138] When the dielectric anisotropy of the compound was zero or negative, the following mother liquid crystal (B) was used. The proportion of each component is expressed in weight percent.

[0139] TIFF2026085011000034.tif8292

[0140] Mother liquid crystal (C): Mother liquid crystal (C) containing the following fluorine-based compounds was also used. The proportion of the components of mother liquid crystal (C) is expressed in weight percent.

[0141] TIFF2026085011000035.tif14571

[0142] The ratio of compound to matrix liquid crystal (C) was set to 20% by weight:80% by weight. When crystals (or smectic phase) precipitated at 25°C with this ratio, the ratio of compound to matrix liquid crystal (C) was changed in the following order: 15% by weight:85% by weight, 10% by weight:90% by weight, 5% by weight:95% by weight, and 1% by weight:99% by weight. The physical properties of the sample were measured at the ratio in which crystals (or smectic phase) no longer precipitated at 25°C. Unless otherwise specified, the ratio of compound to matrix liquid crystal (C) is 20% by weight:80% by weight.

[0143] Measurement Method: The physical properties were measured using the following methods. Many of these are described in the JEITA standard (JEITA-ED-2521B), which is deliberated and established by the Japan Electronics and Information Technology Industries Association (JEITA). Modified versions of these methods were also used. Thin-film transistors (TFTs) were not attached to the TN elements used for measurement.

[0144] (1) Phase structure: The sample was placed on the hot plate of a melting point measuring device equipped with a polarizing microscope (Mettler FP-52 hot stage). The phase state and its changes were observed with a polarizing microscope while the sample was heated at a rate of 3°C / min, and the type of phase was identified.

[0145] (2) Transition temperature (°C): Measurement was performed using a PerkinElmer scanning calorimeter, Diamond A DSC system or a high-sensitivity differential scanning calorimeter, X-DSC7000, manufactured by SII Nanotechnology, was used. The sample was heated and cooled at a rate of 3°C / min, and the transition temperature was determined by extrapolating the starting point of the endothermic or exothermic peak associated with the phase change of the sample. The melting point and polymerization initiation temperature of the compound were also measured using this instrument. The temperature at which a compound transitions from solid to liquid crystal phases such as the smectic phase and nematic phase is sometimes abbreviated as the "lower limit temperature of the liquid crystal phase." The temperature at which a compound transitions from the liquid crystal phase to liquid is sometimes abbreviated as the "transparency point."

[0146] Crystals were represented by C. If the crystal could be distinguished into two types, they were represented as C1 or C2. Smectic phases were represented by S, and nematic phases by N. When phases could be distinguished, such as smectic A, smectic B, smectic C, and smectic F, they were represented by S. A S B S C , and S F This was expressed as follows. Liquid (isotropic) was represented as I. The transition temperature was expressed as, for example, "C 50.0 N 100.0 I". This indicates that the transition temperature from crystal to nematic phase is 50.0°C, and the transition temperature from nematic phase to liquid is 100.0°C.

[0147] (3) Compatibility of compounds: Samples were prepared by mixing the mother liquid crystal and the compound so that the compound was present in proportions of 20% by weight, 15% by weight, 10% by weight, 5% by weight, 3% by weight, or 1% by weight. The samples were placed in glass bottles and stored in a freezer at -10°C or -20°C for a certain period of time. The nematic phase of the sample was observed to see if it was maintained or if crystals (or smectic phase) precipitated. The conditions under which the nematic phase was maintained were used as a measure of compatibility. The proportion of the compound and the freezer temperature may be changed as needed.

[0148] (4) Upper limit temperature of the nematic phase (T NI (or NI; °C): The sample was placed on a hot plate of a melting point analyzer equipped with a polarizing microscope and heated at a rate of 1 °C / min. The temperature at which a portion of the sample changed from the nematic phase to an isotropic liquid was measured. When the sample is a mixture of compound (1) and the mother liquid crystal, T NI The symbol is used to indicate the sample. When the sample is a mixture of compound (1) and a compound selected from compounds (2) to (15), the symbol NI is used. The upper limit temperature of the nematic phase is sometimes abbreviated as "upper limit temperature".

[0149] (5) Lower limit temperature of the nematic phase (T C;℃): Samples having a nematic phase were placed in glass bottles and stored in freezers at 0℃, -10℃, -20℃, -30℃, and -40℃ for 10 days, after which the liquid crystal phase was observed. For example, when the sample remained in the nematic phase at -20℃ and changed to a crystalline or smectic phase at -30℃, T C This was written as <-20℃. The lower limit temperature of the nematic phase is sometimes abbreviated as "lower limit temperature".

[0150] (6) Viscosity (bulk viscosity; η; measured at 20°C; mPa·s): An E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used for the measurement.

[0151] (7) Optical anisotropy (refractive index anisotropy; measured at 25°C; Δn): The measurement was performed using light with a wavelength of 589 nm and an Abbe refractometer with a polarizer attached to the eyepiece. After rubbing the surface of the main prism in one direction, the sample was dropped onto the main prism. The refractive index (n∥) was measured when the direction of polarization was parallel to the direction of rubbing. The refractive index (n⊥) was measured when the direction of polarization was perpendicular to the direction of rubbing. The value of optical anisotropy (Δn) was calculated from the equation Δn = n∥ - n⊥.

[0152] (8) Resistivity (ρ; measured at 25℃; Ωcm): 1.0 mL of the sample was injected into a container equipped with electrodes. A DC voltage (10V) was applied to this container, and the DC current was measured after 10 seconds. The resistivity was calculated from the following equation: (Resistivity) = {(Voltage) × (Capacitance of the container)} / {(DC current) × (Permittivity of vacuum)}.

[0153] (9) Voltage retention rate (VHR-1; measured at 25°C; %): The TN element used for the measurement had a polyimide orientation film, and the distance between the two glass substrates (cell gap) was 5 μm. After placing the sample inside the element, it was sealed with an adhesive that hardens with ultraviolet light. The element was charged by applying a pulse voltage (5V for 60 microseconds). The decaying voltage was measured with a high-speed voltmeter for 16.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit period was determined. Area B was the area when there was no decay. The voltage retention rate was expressed as the percentage of area A to area B.

[0154] (10) Voltage retention rate (VHR-2; measured at 80°C; %): The voltage retention rate was measured using the method described above, except that it was measured at 80°C instead of 25°C. The obtained results are indicated by the symbol VHR-2.

[0155] (11) Flicker rate (measured at 25°C; %): A Yokogawa Electric Corporation 3298F multimedia display tester was used for the measurement. The light source was an LED. The sample was placed in a normally black mode FFS element with a 3.5 μm gap between two glass substrates and an antiparallel rubbing direction. This element was sealed using an adhesive that hardens with ultraviolet light. A voltage was applied to this element, and the voltage at which the amount of light transmitted through the element was maximized was measured. While applying this voltage to the element, the sensor was brought close to the element, and the displayed flicker rate was read.

[0156] The measurement methods for physical properties may differ between samples with positive dielectric anisotropy and those with negative dielectric anisotropy. The measurement methods for samples with positive dielectric anisotropy are described in Measurements (12a) to (16a). The methods for samples with negative dielectric anisotropy are described in Measurements (12b) to (16b).

[0157] (12a) Viscosity (rotational viscosity; γ1; measured at 25℃; mPa·s; sample with positive dielectric anisotropy): The measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). The sample was placed in a TN element with a twist angle of 0 degrees and a cell gap of 5 μm between the two glass substrates. A voltage was applied to this element in increments of 0.5 V from 16 V to 19.5 V. After a 0.2 second period of no application, the application was repeated under the condition of only one square wave (square pulse; 0.2 seconds) followed by no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. The value of rotational viscosity was obtained from these measurements and equation (8) on page 40 of the paper by M. Imai et al. The dielectric anisotropy value required for this calculation was determined using the element whose rotational viscosity was measured, and the method described below.

[0158] (12b) Viscosity (rotational viscosity; γ1; measured at 25℃; mPa·s; sample with negative dielectric anisotropy): Measurements are from M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 The method described in (1995) was followed. The sample was placed in a VA element with a 20 μm gap between two glass substrates. The element was then subjected to stepwise voltages from 39 V to 50 V in 1 V increments. After a 0.2 second period of no voltage, the application was repeated under the condition of a single square wave (square pulse; 0.2 seconds) followed by no voltage (2 seconds). The peak current and peak time of the transient current generated by this application were measured. The rotational viscosity value was obtained from these measurements and equation (8) on page 40 of the paper by M. Imai et al. The dielectric anisotropy necessary for this calculation was measured in the dielectric anisotropy section below.

[0159] (13a) Dielectric Anisotropy (Δε; measured at 25°C; sample with positive dielectric anisotropy): A sample was placed in a TN element with a cell gap of 9 μm between two glass substrates and a twist angle of 80 degrees. A sine wave (10V, 1kHz) was applied to this element, and the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecules was measured after 2 seconds. A sine wave (0.5V, 1kHz) was applied to this element, and the dielectric constant (ε⊥) in the short axis direction of the liquid crystal molecules was measured after 2 seconds. The value of dielectric anisotropy was calculated from the equation Δε = ε∥ - ε⊥.

[0160] (13b) Dielectric anisotropy (Δε; measured at 25°C; sample with negative dielectric anisotropy): The value of dielectric anisotropy was calculated from the equation Δε = ε∥ - ε⊥. The dielectric constants (ε∥ and ε⊥) were measured as follows. 1) Measurement of dielectric constant (ε∥): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a well-cleaned glass substrate. After rotating the glass substrate with a spinner, it was heated at 150°C for 1 hour. The sample was placed in a VA element with a cell gap of 4 μm between two glass substrates, and this element was sealed with an adhesive that hardens with ultraviolet light. A sine wave (0.5 V, 1 kHz) was applied to this element, and the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecules was measured after 2 seconds. 2) Measurement of dielectric constant (ε⊥): A polyimide solution was applied to a well-cleaned glass substrate. After firing this glass substrate, the resulting alignment film was subjected to a rubbing treatment. The sample was placed in a TN element with a cell gap of 9 μm between two glass substrates and a twist angle of 80 degrees. A sine wave (0.5V, 1kHz) was applied to this element, and the dielectric constant (ε⊥) in the short axis direction of the liquid crystal molecules was measured after 2 seconds.

[0161] (14a) Elastic constant (K; measured at 25℃; pN; sample with positive dielectric anisotropy): An HP4284A LCR meter manufactured by Yokogawa-Hewlett-Packard Corporation was used for the measurement. The sample was placed in a horizontally aligned element with a cell gap of 20 μm between two glass substrates. A charge from 0V to 20V was applied to this element, and the capacitance (C) and applied voltage (V) were measured. These measured values ​​were fitted using equations (2.98) and (2.101) found on page 75 of the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), and K was derived from equation (2.99). 11 and K 33 We obtained the value of K. Next, we apply the equation (3.18) on page 171 to the K we just found. 11 and K 33 Using the value of K 22 The elastic constant K was calculated in this way. 11 , K 22 , and K 33 It was expressed as the average value.

[0162] (14b) Elastic constant (K 11 and K 33 ;Measured at 25℃;pN;Sample with negative dielectric anisotropy): An EC-1 type elastic constant measuring instrument manufactured by Toyo Technica Co., Ltd. was used for the measurement. The sample was placed in a vertically aligned element with a cell gap of 20 μm between two glass substrates. A charge from 20 V to 0 V was applied to this element, and the capacitance (C) and applied voltage (V) were measured. These values ​​were fitted using equations (2.98) and (2.101) found on page 75 of the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), and the value of the elastic constant was obtained from equation (2.100).

[0163] (15a) Threshold voltage (Vth; measured at 25°C; V; sample with positive dielectric anisotropy): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. The sample was placed in a normally white mode TN element with a cell gap of 0.45 / Δn (μm) between two glass substrates and a twist angle of 80 degrees. The voltage (32Hz, square wave) applied to this element was increased stepwise from 0V to 10V in increments of 0.02V. At this time, light was shone perpendicularly onto the element, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was created where the maximum light amount represented 100% transmittance, and the minimum light amount represented 0% transmittance. The threshold voltage was expressed as the voltage at which the transmittance reached 90%.

[0164] (15b) Threshold voltage (Vth; measured at 25°C; V; sample with negative dielectric anisotropy): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The sample was placed in a normally black mode VA element with a 4 μm gap between two glass substrates (cell gap) and an antiparallel rubbing direction, and this element was sealed using an adhesive that hardens with ultraviolet light. The voltage applied to this element (60 Hz, square wave) was increased stepwise from 0 V to 20 V in increments of 0.02 V. At this time, light was irradiated onto the element from a direction perpendicular to it, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was created where the maximum light amount was 100% transmittance and the minimum light amount was 0% transmittance. The threshold voltage was expressed as the voltage at which the transmittance became 10%.

[0165] (16a) Response time (τ; measured at 25℃; ms; sample with positive dielectric anisotropy): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The low-pass filter was set to 5kHz. The sample was placed in a normally white mode TN element with a cell gap of 5.0 μm between two glass substrates and a twist angle of 80 degrees. A square wave (60Hz, 5V, 0.5 sec) was applied to this element. At this time, light was shone onto the element from a direction perpendicular to it, and the amount of light transmitted through the element was measured. When the amount of light was at its maximum, the transmittance was considered to be 100%, and when the amount of light was at its minimum, the transmittance was considered to be 0%. The rise time (τr; milliseconds) is the time required for the transmittance to change from 90% to 10%. The fall time (τf; milliseconds) is the time required for the transmittance to change from 10% to 90%. The response time was expressed as the sum of the rise time and fall time, which were calculated in this way.

[0166] (16b) Response time (τ; measured at 25°C; ms; sample with negative dielectric anisotropy): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The low-pass filter was set to 5 kHz. The sample was placed in a normally black mode PVA element with a cell gap of 3.2 μm between two glass substrates and an antiparallel rubbing direction. This element was sealed using an adhesive that hardens with ultraviolet light. A voltage slightly exceeding the threshold voltage was applied to this element for 1 minute, and then a voltage of 5.6 V was applied while measuring 23.5 mW / cm². 2 The element was irradiated with ultraviolet light for 8 minutes. A square wave (60Hz, 10V, 0.5 seconds) was applied to the element. During this time, light was shone perpendicularly to the element, and the amount of light transmitted through the element was measured. The maximum light intensity was considered to represent a transmittance of 100%, and the minimum light intensity was considered to represent a transmittance of 0%. The response time was expressed as the time required for the transmittance to change from 90% to 10% (fall time; milliseconds).

[0167] [Synthesis Example 1] Synthesis of compound (No. 42)

[0168] TIFF2026085011000036.tif58166

[0169] Step 1: Synthesis of compound (S-2) Under a nitrogen atmosphere, compound (S-1) (50 g) and THF (1000 ml) were placed in a reactor and cooled to -60°C. n-butyllithium (1.6 M; n-hexane, cyclohexane solution; 220 ml) was added dropwise, and the mixture was stirred for another 2 hours. Sulfur powder (10.6 g) was then added, and the mixture was stirred for 2 hours while returning to 25°C. Bromoacetaldehyde diethyl acetal (65.4 g) was added, and the mixture was refluxed for 2 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene) to obtain (S-2) (84 g). (S-1) was commercially available from Combi-Blocks (Order Number: QJ-5097), etc., and this was used.

[0170] Step 2: Synthesis of compound (S-3) Under a nitrogen atmosphere, compound (S-2) (75 g), polyphosphate (100 g), and toluene (1000 ml) were added to a reactor and heated under reflux for 3 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane = 2:3) to obtain (S-3) (42.0 g).

[0171] Step 3: Synthesis of compound (S-4) Under a nitrogen atmosphere, compound (S-3) (42 g) and THF (500 ml) were placed in a reactor and cooled to -60°C. LDA (1 M; n-hexane, THF solution; 196 ml) was added dropwise thereto, and the mixture was further stirred for 2 hours. Subsequently, iodine (54.7 g) was added, and the mixture was stirred for 2 hours while returning to 25°C. The reaction mixture was poured into water and extracted with toluene. The organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane = 2:3) to obtain (S-4) (60.0 g). Incidentally, (S-5) is sold by Combi-Blocks (Order Number: FA-1772) etc., and this was used.

[0172] Step 4: Synthesis of compound (No. 42) Under a nitrogen atmosphere, (S-4) (3 g), (S-5) (2.8 g) and toluene (80 ml) were placed in a reactor, and then water (50 m), ethanol (50 ml), Pd(PPh3)4 (0.3 g), TBAB (0.28 g) and potassium carbonate (2. The mixture was heated under reflux for 6 hours. After completion of the reaction, the mixture was extracted with toluene, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a light brown solid. This solid was made into a solution and purified by silica gel column chromatography (volume ratio, heptane:toluene = 3:2) and recrystallization (ethanol) to obtain (No. 42) as colorless crystals (3.9 g).

[0173] 1 H-NMR (δ ppm; CDCl3): 7.70 (t, 1H), 7.64 (d, 1H), 7.53 (d, 2H), 7.44 (d, 1H), 7.42 (d, 1H), 7.31 (d, 1H), 7.28 (d, 2H), 4.27 (q, 2H), 2.64 (t, 2H), 1.69 (sex, 2H), 1.44 (t, 3H), 0.98 (t, 3H).

[0174] The physical properties of compound (No. 42) were as follows. Transition temperature: C 36.1 S 257.4 I. T NI= 223.4 °C; Δn = 0.366; Δε = 9.5; η = 61.7 mPa·s.

[0175] [Synthesis Example 2] Synthesis of Compound (No. 43)

[0176] TIFF2026085011000037.tif33165

[0177] Under a nitrogen atmosphere, (S-4) (3 g), (S-6) (2.8 g) and toluene (80 ml) were placed in a reactor, and then water (50 m), ethanol (50 ml), Pd(PPh3)4 (0.3 g), TBAB (0.28 g) and potassium carbonate (2.4 g) were added, and the mixture was heated under reflux for 6 hours. After completion of the reaction, the mixture was extracted with toluene, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale brown solid. This solid was dissolved and purified by silica gel column chromatography (volume ratio, heptane:toluene = 3:2) and recrystallization (ethanol) to obtain (No. 43) as colorless crystals (4.0 g). Incidentally, (S-6) is sold by Aquila Pharmatech (Order Number: AN11274) etc. and this was used.

[0178] 1 1H-NMR (δ ppm; CDCl3): 7.58 (d, J = 1H), 7.55 (d, J = 1H), 7.28 (d, J = 1H), 7.24 (d, J = 1H), 7.19 (d, J = 1H), 6.23 (t, J = 1H), 4.27 (q, J = 2H), 2.42 (br, J = 2H), 2.35 (d, J = 1H), 1.94 (d, J = 1H), 1.9 - 1.8 (m, J = 1H), 1.61 (sex, J = 1H), 1.42 (t, J = 3H), 1.41 - 1.25 (m, J = 5H), 0.93 (t, J = 3H).

[0179] The physical properties of Compound (No. 43) were as follows. Transition temperature: C 67.1 S 241.8 I. T NI = 228.7 °C; Δn = 0.320; Δε = 7.5; η = 43.5 mPa·s.

[0180] [Synthesis Example 3] Synthesis of compound (No. 52)

[0181] TIFF2026085011000038.tif32158

[0182] Under a nitrogen atmosphere, (S-4) (3g), (S-7) (2.8g), and toluene (80ml) were added to a reactor. Then, water (50ml), ethanol (50ml), Pd(PPh3)4 (0.3g), TBAB (0.28g), and potassium carbonate (2.4g) were added, and the mixture was heated under reflux for 6 hours. After the reaction was complete, the mixture was extracted with toluene, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a light brown solid. This solid was dissolved and subjected to silica gel column chromatography (volume ratio, heptane:toluene = 3:2) and recrystallization (ethanol) to obtain (No. 51) as colorless crystals (4.1g). (S-7) was purchased from A2B Chem (Order Number: AX54239), etc., and this was used.

[0183] 1 H-NMR(δppm;CDCl3):7.54(d,1H),7.53(d,1H),7.28(d,1H),7.04(d,1H),7.02(d,1H) ,4.26(q,2H),2.49(t,1H),1.89(t,4H),1.50-1.18(m,10H),1.05(q,2H),0.91(t,3H).

[0184] The physical properties of compound (No. 51) were as follows: Transition temperature: C 86.8 S 206.7 N 237.7 I. T NI =220.7℃;Δn=0.253;Δε=6.8;η=57.8mPa·s.

[0185] [Synthesis Example 4] Synthesis of compound (No. 44)

[0186] TIFF2026085011000039.tif34164

[0187] Under a nitrogen atmosphere, (S-4) (3g), (S-8) (2.8g), and toluene (80ml) were added to a reactor. Then, water (50ml), ethanol (50ml), Pd(PPh3)4 (0.3g), TBAB (0.28g), and potassium carbonate (2.4g) were added, and the mixture was heated under reflux for 6 hours. After the reaction was complete, the mixture was extracted with toluene, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a light brown solid. This solid was dissolved and subjected to silica gel column chromatography (volume ratio, heptane:toluene = 3:2) and recrystallization (ethanol) to obtain (No. 44) as colorless crystals (3.9g). (S-8) was purchased from Aldrich (Order Number: AOBH99101C23), etc., and this was used.

[0188] 1 H-NMR(δppm;CDCl3):7.70(t,1H),7.64(d,1H),7.53(d,2H),7.44(d,1H),7.42(d, 1H),7.31(d,1H),7.28(d,2H),4.27(q,2H),2.71(q,2H),1.44(t,3H),1.29(t,3H).

[0189] The physical properties of compound (No. 44) were as follows: Transition temperature: C 96.0 S 247.9 I. T NI =220.4℃;Δn=0.356;Δε=9.5;η=82.7mPa·s.

[0190] [Synthesis Example 5] Synthesis of compound (No. 56)

[0191] TIFF2026085011000040.tif33165

[0192] Under a nitrogen atmosphere, (S-4) (3 g), (S-9) (2.8 g) and toluene (80 ml) were placed in a reactor, and then water (50 m), ethanol (50 ml), Pd(PPh3)4 (0.3 g), TBAB (0.28 g) and potassium carbonate (2.4 g) were added, and the mixture was heated under reflux for 6 hours. After completion of the reaction, the mixture was extracted with toluene, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale brown solid. This solid was dissolved and subjected to silica gel column chromatography (volume ratio: heptane:toluene = 3:2) and recrystallization (ethanol) to obtain (No.56) as colorless crystals (4.1 g). Incidentally, (S-9) was sold by Aldrich (Order Number: AMBH303C4B5C) etc. and this was used.

[0193] 1 1H-NMR (δ ppm; CDCl3): 7.70 (t, 1H), 7.64 (d, 1H), 7.53 (d, 2H), 7.44 (d, 1H), 7.42 (d, 1H), 7.31 (d, 1H), 7.28 (d, 2H), 4.27 (q, 2H), 2.66 (t, 2H), 1.64 (quint, 2H), 1.44 (t, 3H), 1.39 (sex, 2H), 0.95 (t, 3H).

[0194] The physical properties of compound (No.56) were as follows. Transition temperature: C 86​​​​​​​​​​​​​​​​Under a nitrogen atmosphere, (S-4) (3g), (S-10) (2.8g), and toluene (80ml) were added to a reactor, followed by water (50ml), ethanol (50ml), Pd(PPh3)4 (0.3g), TBAB (0.28g), and potassium carbonate (2.4g), and the mixture was heated under reflux for 6 hours. After the reaction was complete, the mixture was extracted with toluene, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a light brown solid. This solid was then dissolved and subjected to silica gel column chromatography (volume ratio, heptane:toluene = 3:2) and recrystallization (ethanol) to obtain (No. 45) as colorless crystals (4.0g). (S-9) was purchased from Alfa Chemistry (Order Number: ACM163129144), etc., and was used.

[0198] 1 H-NMR(δppm;CDCl3):7.70(t,1H),7.64(d,1H),7.53(d,2H),7.44(d,1H),7.42(d,1H),7.31(d,1H),7.28(d, 2H),4.27(q,2H),2.66(t,2H),1.64(quint,2H),1.44(t,3H),1.36(quint,2H),1.35(sex,2H),0.91(t,3H).

[0199] The physical properties of compound (No. 45) were as follows: Transition temperature: C 78.6°C S 253.6°C I. T NI =219.4℃;Δn=0.336;Δε=7.5;η=39.7mPa·s.

[0200] [Synthesis Example 7] Synthesis of compound (No. 51)

[0201] TIFF2026085011000042.tif34164

[0202] Under a nitrogen atmosphere, (S-4) (3g), (S-11) (2.8g), and toluene (80ml) were added to a reactor. Then, water (50ml), ethanol (50ml), Pd(PPh3)4 (0.3g), TBAB (0.28g), and potassium carbonate (2.4g) were added, and the mixture was heated under reflux for 6 hours. After the reaction was complete, the mixture was extracted with toluene, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a light brown solid. This solid was dissolved and subjected to silica gel column chromatography (volume ratio, heptane:toluene = 3:2) and recrystallization (ethanol) to obtain (No. 51) as a colorless crystal (4.1g). (S-9) was purchased from A2B Chem (Order Number: BR63513), etc., and this was used.

[0203] 1 H-NMR(δppm;CDCl3):7.10(d,1H),7.53(d,2H),7.36(d,1H),7.30(d,2H),7.2 8(d,2H),4.29(q,2H),2.65(t,2H),1.69(sex,2H),1.45(t,3H),0.98(t,3H).

[0204] The physical properties of compound (No. 51) were as follows: Transition temperature: C 83.0 S 229.2 I. T NI =201.4℃;Δn=0.346;Δε=12.5;η=36.9mPa·s.

[0205] [Synthesis Example 8] Synthesis of compound (No. 8)

[0206] TIFF2026085011000043.tif30164

[0207] Under a nitrogen atmosphere, (S-4) (3g), (S-12) (2.3g), and toluene (80ml) were added to a reactor. Then, water (50ml), ethanol (50ml), Pd(PPh3)4 (0.3g), TBAB (0.28g), and potassium carbonate (2.4g) were added, and the mixture was heated under reflux for 6 hours. After the reaction was complete, the mixture was extracted with toluene, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a light brown solid. This solid was dissolved and subjected to silica gel column chromatography (volume ratio, heptane:toluene = 3:2) and recrystallization (ethanol) to obtain (No. 8) as colorless crystals (2.8g). (S-12) was purchased from TCI (Order Number: P1827), etc., and this was used.

[0208] 1 H-NMR(δppm;CDCl3):7.57(d,2H),7.37(d,1H),7.25(d,1H),7.23(d,2H),4.24(q,2H),2.61(t,2H),1.65(sex,2H),1.42(t,3H),0.96(t,3H).

[0209] The physical properties of compound (No. 8) were as follows: Transition temperature: C 56.1 S 128.6 I. T NI =81.4℃;Δn=0.246;Δε=12.5;η=25.9mPa·s.

[0210] [Synthesis Example 9] Synthesis of compound (No. 46)

[0211] TIFF2026085011000044.tif57164

[0212] Step 1: Synthesis of compound (S-13) Under a nitrogen atmosphere, compound (S-1-1) (50 g) and THF (1000 ml) were placed in a reactor and cooled to -60°C. n-butyllithium (1.6 M; n-hexane, cyclohexane solution; 222 ml) was added dropwise, and the mixture was stirred for another 2 hours. Sulfur powder (11.0 g) was then added, and the mixture was stirred for 2 hours while returning to 25°C. Bromoacetaldehyde diethyl acetal (66.4 g) was added, and the mixture was refluxed for 2 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene) to obtain (S-13) (84 g). (S-1-1) was commercially available from Combi-Blocks (Order Number: OR-3820), etc., and this was used.

[0213] Step 2: Synthesis of compound (S-14) Under a nitrogen atmosphere, compound (S-13) (84 g), polyphosphate (100 g), and toluene (1000 ml) were added to a reactor and heated under reflux for 3 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane = 2:3) to obtain (S-14) (41.0 g).

[0214] Step 3: Synthesis of compound (S-15) Under a nitrogen atmosphere, compound (S-14) (41 g) and THF (500 ml) were placed in a reactor and cooled to -60°C. LDA (1 M; n-hexane, THF solution; 196 ml) was added dropwise, and the mixture was stirred for a further 2 hours. Subsequently, iodine (55.0 g) was added, and the mixture was stirred for 2 hours while returning to 25°C. The reaction mixture was poured into water and extracted with toluene. The organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane = 2:3) to obtain (S-15) (59.0 g).

[0215] Step 4: Synthesis of compound (No. 46) Under a nitrogen atmosphere, (S-15) (3g), (S-5) (2.8g), and toluene (80ml) were added to a reactor, followed by water (50ml), ethanol (50ml), Pd(PPh3)4 (0.3g), TBAB (0.28g), and potassium carbonate (2.4g), and the mixture was heated under reflux for 6 hours. After the reaction was complete, the mixture was extracted with toluene, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a light brown solid. This solid was dissolved and subjected to silica gel column chromatography (volume ratio, heptane:toluene = 3:2) and recrystallization (ethanol) to obtain (No. 46) as colorless crystals (3.8g).

[0216] 1 H-NMR(δppm;CDCl3):7.69(t,1H),7.64(d,1H),7.53(d,2H),7.44(d,1H),7.42(d,1 H),7.31(d,1H),7.28(d,2H),4.04(s,3H),2.62(t,2H),1.67(sex,2H),0.98(t,3H).

[0217] The physical properties of compound (No. 46) were as follows: Transition temperature: C 96.05 S 252.8 I. T NI =214.4℃;Δn=0.376;Δε=10.5;η=64.7mPa·s.

[0218] [Synthesis Example 10] Synthesis of compound (No. 47) TIFF2026085011000045.tif45166

[0219] Step 1: Synthesis of compound (S-16) Under a nitrogen atmosphere, compound (No. 46) (10 g) and dichloromethane (200 ml) were placed in a reactor and cooled to below 10°C. Boron tribromide (1 M; dichloromethane solution; 26 ml) was added dropwise, and the mixture was stirred for a further 2 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate = 9:1) to obtain (S-16) (8.5 g).

[0220] Step 2: Synthesis of compound (No. 47) Under a nitrogen atmosphere, compound (S-16) (3g), iodopropane (1.5g), potassium carbonate (K2CO3; 2g), and DMF (100ml) were added to a reactor and stirred at 60°C for 2 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:heptane = 1:3) to obtain (No. 47) (2.8g).

[0221] 1 H-NMR(δppm;CDCl3):7.69(t,1H),7.64(d,1H),7.53(d,2H),7.44(d,1H),7.42(d,1H),7.31(d,1H ),7.28(d,2H),4.16(t,2H),2.64(t,2H),1.82(sex,2H),1.69(sex,2H),1.09(t,3H),0.98(t,3H).

[0222] The physical properties of compound (No. 46) were as follows: Transition temperature: C 81.53 S 246.7 I. T NI =214.4℃;Δn=0.376;Δε=10.5;η=64.7mPa·s.

[0223] [Synthesis Example 11] Synthesis of compound (No. 57) TIFF2026085011000046.tif26165

[0224] Under a nitrogen atmosphere, compound (S-16) (3g), allyl bromide (1.4g), potassium carbonate (K2CO3; 2g), and DMF (100ml) were added to a reactor and stirred at 60°C for 2 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:heptane = 1:3) to obtain (No. 57) (2.7g).

[0225] 1 H-NMR(δppm;CDCl3):7.70(t,1H),7.64(d,1H),7.52(d,2H),7.43(d,1H),7.42(d,1H),7.31(d,1H),7.29 (d,2H),6.10(oct,1H),5.40(d,1H),5.29(d,1H),4.70(d,2H),2.64(t,2H),1.70(sex,2H),0.99(t,3H).

[0226] The physical properties of compound (No. 57) were as follows: Transition temperature: C 60.56 S T NI =214.4℃;Δn=0.376;Δε=10.5;η=64.7mPa·s.

[0227] [Synthesis Example 12] Synthesis of compound (No. 60)

[0228] TIFF2026085011000047.tif56165

[0229] Step 1: Synthesis of compound (S-17) Under a nitrogen atmosphere, compound (S-20) (5g) and THF (100ml) were placed in a reactor and cooled to -60°C. n-butyllithium (1.6M; n-hexane, cyclohexane solution; 24ml) was added dropwise, and the mixture was stirred for another 2 hours. Sulfur powder (12g) was then added, and the mixture was stirred for 2 hours while returning to 25°C. Bromoacetaldehyde diethyl acetal (7.4g) was added, and the mixture was refluxed for 2 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene) to obtain (S-17) (8.2g). (S-16) was purchased from Combi-Blocks (Order Number: QC-7388), etc., and this was used.

[0230] Step 2: Synthesis of compound (S-18) Under a nitrogen atmosphere, compound (S-17) (8.2 g), polyphosphate (10 g), and toluene (100 ml) were placed in a reactor and heated under reflux for 3 hours. The reaction mixture was poured into water and extracted with toluene. The organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane = 2:3) to obtain (S-18) (4.2 g).

[0231] Step 3: Synthesis of compound (S-19) Under a nitrogen atmosphere, compound (S-18) (4.2 g) and THF (50 ml) were placed in a reactor and cooled to -60°C. LDA (1 M; n-hexane, THF solution; 20 ml) was added dropwise, and the mixture was stirred for a further 2 hours. Subsequently, iodine (5.7 g) was added, and the mixture was stirred for 2 hours while returning to 25°C. The reaction mixture was poured into water and extracted with toluene. The organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane = 2:3) to obtain (S-19) (6.1 g).

[0232] Step 4: Synthesis of compound (No. 60) Under a nitrogen atmosphere, (S-19) (6.1g), (S-5) (6.0g) and toluene (160ml) were added to the reactor, followed by water (100ml), ethanol (100ml), and Pd(PPh3)4( 0.5g of (a, TBAB, 0.7g, and potassium carbonate, 5.0g) were added and heated under reflux for 6 hours. After the reaction was complete, the mixture was extracted with toluene, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a light brown solid. This solid was dissolved and subjected to silica gel column chromatography (volume ratio, heptane:toluene = 3:2) and recrystallization (ethanol) to obtain (No. 60) as colorless crystals (7.1g).

[0233] 1 H-NMR(δppm;CDCl3):7.72(t,1H),7.70(d,1H),7.54(d,2H),7.48(d,1H),7.4 4(d,1H),7.42(d,1H),7.29(d,2H),2.65(t,2H),1.70(sex,2H),0.99(t,3H).

[0234] The physical properties of compound (No. 60) were as follows: Transition temperature: C 75.5 S 241.1 I. T NI =167.4℃;Δn=0.285;Δε=23.5;η=29.1mPa·s.

[0235] [Comparative Example] Compound (A) described in Patent Document 1 (International Publication No. 2016 / 132998) and compound (B) described in Patent Document 2 (International Publication No. 2017 / 064892) are used as comparative examples.

[0236] [Physical properties of the examples and comparative examples] Using the compound (No. 42) synthesized in Synthesis Example 1 as an example, the physical properties of the examples and comparative examples are summarized as follows. TIFF2026085011000048.tif72164

[0237] Compound (No. 42) exhibits superior physical properties compared to compounds (A) or (B), including a higher transparency point (NI), lower viscosity (η), and greater dielectric anisotropy (Δε). In particular, viscosity (η) and transparency point (NI) or dielectric anisotropy (Δε) are in a trade-off relationship, and it is usually difficult to achieve excellent properties in both. However, this has been achieved in the present compound compared to the comparative compounds, and it can be said that it has an extremely excellent balance of physical properties.

[0238] The following compounds can be synthesized by referring to the methods described in the synthesis examples and to the section "2. Synthesis of Compound (1)".

[0239] TIFF2026085011000049.tif233165

[0240] TIFF2026085011000050.tif234163

[0241] TIFF2026085011000051.tif213160

[0242] TIFF2026085011000052.tif217165

[0243] TIFF2026085011000053.tif197165

[0244] TIFF2026085011000054.tif167166

[0245] TIFF2026085011000055.tif25289

[0246] 2. Examples of compositions The present invention will be further described in detail by examples of compositions. Since the examples are typical, the present invention is not limited by the examples (examples of use). For example, the present invention includes, in addition to the compositions of the examples of use, a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes a mixture prepared by mixing at least two of the compositions of the examples of use. The compounds in the examples of use are represented by symbols based on the definitions in Table 3 below. In Table 3, the stereochemistry of 1,4-cyclohexylene is trans. In the examples of use, the number in parentheses after the symbol represents the chemical formula to which the compound belongs. The symbol (-) indicates a liquid crystalline compound different from compounds (1) to (13) and compounds (21) to (24). The percentage of liquid crystalline compounds is the weight percentage (W%) based on the weight of the liquid crystalline composition without additives. Finally, the physical properties of the compositions are summarized. The physical properties were measured according to the method described above, and the measured values ​​are listed as is (without extrapolation).

[0247] TIFF2026085011000056.tif231167

[0248] [Usage example 1] 3-BB(F)bt(5F,7F)-O2 (No.42) 3% 1-BB-3 (2-8) 7% 1-BB-5 (2-8) 8% 2-BTB-1 (2-10) 3% 3-HHB-1 (3-1) 8% 3-HHB-O1 (3-1) 5% 3-HHB-3 (3-1) 14% 3-HHB-F (22-1) 4% 2-HHB(F)-F (22-2) 7% 3-HHB(F)-F (22-2) 7% 5-HHB(F)-F (22-2) 7% 3-HHB(F,F)-F (22-3) 5% 3-HHEB-F (22-10) 1% 5-HHEB-F (22-10) 4% 2-HB-C (24-1) 5% 3-HB-C (24-1) 12% NI = 95.4 °C; η = 16.7 mPa·s; Δn = 0.114; Δε = 4.9.

[0249] [Example of Use 2] 3-chB(F)bt(5F,7F)-O2 (No.43) 4% V-HBB-2 (3-4) 10% 1O1-HBBH-4 (4-1) 2% 1O1-HBBH-5 (4-1) 2% 3-HHB(F,F)-F (22-3) 9% 3-H₂HB(F,F)-F (22-15) 8% 4-H₂HB(F,F)-F (22-15) 8% 5-H₂HB(F,F)-F (22-15) 8% 3-HBB(F,F)-F (22-24) 11% 5-HBB(F,F)-F (22-24) 20% 3-H₂BB(F,F)-F (22-27) 10% 5-HHBB(F,F)-F (23-6) 3% 3-HH₂BB(F,F)-F (23-15).3% 5-HHEBB-F (23-17) 2% NI = 1O5.7 °C; η = 38.5 mPa's; Δn = 0.128; Δε = 8.4.

[0250] [Example of Use 3] 3-HB(F)bt(5F,7F)-O2 (No.52) 4% V₂-HHB-1 (3-1) 5% 3-HB-CL (21-2) 6% 5-HB-CL (z1-2) 4% 3-HHB-OCF₃ (22-1) 5% 5-HHB(F)-F (22-2) 5% V-HHB(F)-F (22-2) 5% 3-H2HB-OCF3(22-13) 5% 5-H2HB(F,F)-F(22-15) 5% 5-H4HB-OCF3(22-19) 11% 5-H4HB(F,F)-F(22-21) 7% 3-H4HB(F,F)-CF3(22-21) 8% 5-H4HB(F,F)-CF3(22-21) 10% 2-H2BB(F)-F(22-26) 5% 3-H2BB(F)-F(22-26) 10% 3-HBEB(F,F)-F(22-39) 5% NI=72.6°C;η=24.8mPa·s;Δn=0.099;Δε=8.1.

[0251] [Section 4] 2-BB(F)bt(5F,7F)-O2 (No.44) 2% 3-HH-VFF (2-1) 5% 5-HH-VFF (2-1) 25% 2-BTB-1 (2-10) 10% 3-HHB-1 (3-1) 4% VFF-HHB-1 (3-1) 8% VFF2-HHB-1 (3-1) 11% 3-H2BTB-2(3-17) 5% 3-H2BTB-3(3-17) 2% 3-H2BTB-4(3-17) 4% 3-HB-C (24-1) 18% 1V2-BEB(F,F)-C(24-15) 6% NI=82.0°C;η=12.4mPa·s;Δn=0.132;Δε=6.7.

[0252] [Reference 5] 4-BB(F)bt(5F,7F)-O2 (No.56) 2% 1-BB-3 (2-8) 7% 1-BB-5 (2-8) 8% 2-BTB-1 (2-10) 3% 3-HHB-1 (3-1) 8% 3-HHB-O1 (3-1) 5% 3-HHB-3 (3-1) 14% 3-HHB-F (22-1) 4% 2-HHB(F)-F (22-2) 7% 3-HHB(F)-F (22-2) 7% 5-HHB(F)-F (22-2) 7% 3-HHB(F,F)-F (22-3) 5% ​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ NI=107.5℃; η=31.5mPa·s; Δn=0.128; Δε=8.1.

[0254] [Usage Example 7] 3-BB(F,F)bt(5F,7F)-O2 (No.51) 3% V2-HHB-1 (3-1) 2% 3-HB-CL (21-2) 6% 5-HB-CL (21-2) 4% 3-HHB-OCF3 (22-1) 5% 5-HHB(F)-F (22-2) 5% V-HHB(F)-F (22-2) 5% 3-H2HB-OCF3 (22-13) 5% 5-H2HB(F,F)-F (22-15) 5% 5-H4HB-OCF3 (22-19) 15% 5-H4HB(F,F)-F (22-21) 7% 3-H4HB(F,F)-CF3 (22-21) 8% 5-H4HB(F,F)-CF3 (22-21) 10% 2-H2BB(F)-F (22-26) 5% 3-H2BB(F)-F (22-26) 10% 3-HBEB(F,F)-F (22-39) 5% NI=67.7℃; η=24.2mPa·s; Δn=0.095; Δε=8.0.

[0255] [Usage Example 8] 3-Bbt(5F,7F)-O2 (No.8) 4% 3-HH-VFF (2-1) 5% 5-HH-VFF (2-1) 21% 2-BTB-1 (2-10) 10% 3-HHB-1 (3-1) 4% VFF-HHB-1 (3-1) 8% VFF2-HHB-1 (3-1) 11% 3-H2BTB-2 (3-17) 5% 3-H2BTB-3 (3-17) 4% 3-H2BTB-4 (3-17) 4% 3-HB-C (24-1) 18% 1V2-BEB(F,F)-C (24-15) 6% NI = 82.3°C; η = 15.8 mPa·s; Δn = 0.138; Δε = 6.8.

[0256] [Example of Use 9] 3-BB(F)bt(5F,7F)-O1 (No.46) 2% 1-BB-3 (2-8) 7% 1-BB-5 (2-8) 8% 2-BTB-1 (2-10) 3% 3-HHB-1 (3-1) 8% 3-HHB-O1 (3-1) 5% 3-HHB-3 (3-1) 14% 3-HHB-F (22-1) 4%[[ID=...]] 2-HHB(F)-F (22-2) 7% 3-HHB(F)-F (22-2) 7% 5-HHB(F)-F (22-2) 7% 3-HHB(F,F)-F (22-3) 5% 3-HHEB-F (22-10) 2% 5-HHEB-F (22-10) 4% 2-HB-C (24-1) 5% ​​​​​​​​​​​​​​​​3-HHB(F,F)-F (22-3) 9% 3-H2HB(F,F)-F (22-15) 8% 4-H2HB(F,F)-F (22-15) 8% 5-H2HB(F,F)-F (22-15) 8% 3-HBB(F,F)-F (22-24) 11% 5-HBB(F,F)-F (22-24) 20% 3-H2BB(F,F)-F (22-27) 10% 5-HHBB(F,F)-F (23-6) 3% 3-HH2BB(F,F)-F (23-15) 3% 5-HHEBB-F (23-17) 2% NI = 105.7 °C; η = 32.6 mPa·s; Δn = 0.126; Δε = 8.3.

[0258] [Example of Use 11] 3-BB(F)bt(5F,7F)-O1V (No.57) 2% V2-HHB-1 (3-1) 5% 3-HB-CL (21-2) 6% 5-HB-CL (21-2) 4% 3-HHB-OCF3 (22-1) 3% 5-HHB(F)-F (22-2) 5% V-HHB(F)-F (22-2) 5% 3-H2HB-OCF3 (22-13) 5% 5-H2HB(F,F)-F (22-15) 5% 5-H4HB-OCF3 (22-19) 15% 5-H4HB(F,F)-F (22-21) 7% 3-H4HB(F,F)-CF3 (22-21) 8% 5-H4HB(F,F)-CF3 (22-21) 10% 2-H2BB(F)-F (22-26) 5% 3-H2BB(F)-F (22-26) 10% 3-HBEB(F,F)-F (22-39) 5% NI=70.2℃;η=24.4mPa·s;Δn=0.097;Δε=8.0.

[0259] [Usage example 12] 3-BB(F)bt(5F,7F)-OCF3 (No.60) 2% 3-HH-VFF (2-1) 5% 5-HH-VFF (2-1) 25% 2-BTB-1 (2-10) 10% 3-HHB-1 (3-1) 4% VFF-HHB-1 (3-1) 8% VFF2-HHB-1 (3-1) 11% 3-H2BTB-2 (3-17) 3% 3-H2BTB-3 (3-17) 4% 3-H2BTB-4 (3-17) 4% 3-HB-C (24-1) 18% 1V2-BEB(F,F)-C (24-15) 6% NI=81.0℃;η=11.4mPa·s;Δn=0.131;Δε=6.9. [Industrial applicability]

[0260] The liquid crystalline compound of the present invention has excellent physical properties. Liquid crystal compositions containing this compound can be widely used in liquid crystal display elements for personal computers, televisions, and the like.

Claims

1. A compound represented by formula (1). In equation (1), R １ and R ２ These are independently alkyl groups having 1 to 20 carbon atoms, and in this alkyl group, at least one -CH group ２ - may be replaced with -O- or -S-, and at least one -(CH ２ ) ２ - may be replaced by -CH=CH-, and in these groups, at least one hydrogen may be replaced by a halogen, provided that R ２ It is not a mesotherapy; Ring A １ These are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,3-cyclohexadiene-1,4-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, 2,6,7-trioxabicyclo[2.2.2]octane-1,4-diyl, naphthalene-2,6-diyl, or pyridine-2,5-diyl, where at least one hydrogen on these rings may be replaced by a halogen; Z １ is independently a single bond or an alkylene having 1 to 4 carbon atoms, and in this alkylene, at least one -CH ２ - may be replaced by -O- or -COO-, and at least one -(CH ２ ) ２ - may be replaced by -CH=CH- or -C≡C-, and in these groups, at least one hydrogen may be replaced by a halogen; a is 0, 1, 2, or 3.

2. In the above formula (1), R １ R is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is replaced by fluorine, ２ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 2 to 9 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is replaced by fluorine; Ring A １ These are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by a halogen, or tetrahydropyran-2,5-diyl; Z １ These are independently single bonds, -(CH ２ ) ２ -, -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -CF ２ O-, -OCF ２ -ien-CH ２ O-, -OCH ２ -, - (CH ２ ) ４ -, - (CH ２ ) ２ CF ２ O-,-(CH ２ ) ２ OCF ２ -, -CF ２ O(CH ２ ) ２ -, -OCF ２ (CH ２ ) ２ -, -CH=CH-(CH ２ ) ２ - or - (CH ２ ) ２ -CH=CH-; The compound according to claim 1, wherein a is 0, 1, 2, or 3.

3. The compound according to claim 1, represented by any one of formulas (1-1) to (1-4). In equations (1-1) through (1-4), R １ R is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is replaced by fluorine; ２ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 2 to 9 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is replaced by fluorine; Ring A ２ , ring A ３ and ring A ４ These independently include 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by a halogen, and tetrahydropyran-2,5-diyl; Z ２ Z ４ , and Z ５ These are independently single bonds, -(CH ２ ) ２ -, -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -CF ２ O-, -OCF ２ -ien-CH ２ O-, -OCH ２ -, - (CH ２ ) ４ -, - (CH ２ ) ２ CF ２ O-,-(CH ２ ) ２ OCF ２ -, -CF ２ O(CH ２ ) ２ -, -OCF ２ (CH ２ ) ２ -, -CH=CH-(CH ２ ) ２ - or - (CH ２ ) ２ -CH = CH-.

4. In equations (1-1) to (1-4) above, R １ R is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is replaced by fluorine; ２ These are alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 9 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and alkyl groups having 1 to 10 carbon atoms in which at least one hydrogen atom is replaced by fluorine; Ring A ２ , ring A ３ , and ring A ４ These are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by a halogen, or tetrahydropyran-2,5-diyl; Z ２ Z ４ , and Z ５ These are independently single bonds, -(CH ２ ) ２ -, -CH=CH-, -CF ２ O-, -OCF ２ -ien-CH ２ O-, or -OCH ２ - The compound according to claim 3.

5. The compound according to claim 4, represented by any one of formulas (1-1-1) to (1-4-1). From equation (1-1-1) to equation (1-4-1), R １ R is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is replaced by fluorine; ２ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 2 to 9 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is replaced by fluorine; Ring A ２ Ring A ３ and Ring A ４ are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by halogen, or tetrahydropyran-2,5-diyl.

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