JP6863406B2 - Liquid crystal compounds, liquid crystal compositions and liquid crystal display devices with halogenated alkyl - Google Patents

Description

The present invention relates to liquid crystal compounds, liquid crystal compositions and liquid crystal display devices. More specifically, the present invention relates to a liquid crystal compound having a halogenated alkyl, a liquid crystal composition containing the compound and having a nematic phase, and a liquid crystal display device containing the composition.

Liquid crystal display elements are widely used in displays such as personal computers and televisions. This device utilizes physical properties such as optical anisotropy and dielectric anisotropy of a liquid crystal compound. The operation modes of the liquid crystal display element include PC (phase change), TN (twisted nematic), STN (super twisted nematic), BTN (bistable twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), and IPS. There are modes such as (in-plane switching), VA (vertical alignment), FFS (fringe field switching), and PSA (polymer sustained alignment).

In such a liquid crystal display element, a liquid crystal composition having appropriate physical characteristics is used. In order to further improve the characteristics of the device, it is preferable that the liquid crystal compound contained in this composition has the physical characteristics shown in the following (1) to (8). (1) High stability to heat and light, (2) High transparency, (3) Low lower limit temperature of liquid crystal phase, (4) Small viscosity (η), (5) Appropriate optical anisotropy (Δn), (6) Large dielectric anisotropy (Δε), (7) Appropriate elastic constant (K), (8) Excellent compatibility with other liquid crystal compounds.

The effects of the physical properties of the liquid crystal compound on the characteristics of the device are as follows. A compound having high stability to heat and light, as in (1), increases the voltage holding ratio of the device. This prolongs the life of the device. A compound having a high transparency point as in (2) widens the usable temperature range of the device. As in (3), a compound having a low lower limit temperature of the liquid crystal phase such as a nematic phase or a smectic phase, particularly a low lower limit temperature of the nematic phase also expands the usable temperature range of the device. As in (4), a compound having a low viscosity shortens the response time of the device.

Depending on the design of the device, a compound having an appropriate optical anisotropy, that is, a large optical anisotropy or a small optical anisotropy, as in (5) is required. When the response time is shortened by reducing the cell gap of the device, a compound having a large optical anisotropy is suitable. A compound having a large dielectric anisotropy as in (6) lowers the threshold voltage of the device. This reduces the power consumption of the element. On the other hand, a compound having a small dielectric anisotropy shortens the response time of the device by lowering the viscosity of the composition. This compound extends the usable temperature range of the device by raising the upper temperature limit of the nematic phase.

Regarding (7), the compound having a large elastic constant shortens the response time of the device. Compounds with a small elastic constant lower the threshold voltage of the device. Therefore, an appropriate elastic constant is required according to the characteristics to be improved. A compound having excellent compatibility with other liquid crystal compounds as in (8) is preferable. This is because liquid crystal compounds having different physical characteristics are mixed to adjust the physical characteristics of the composition.

So far, various liquid crystal compounds having a large dielectric anisotropy have been synthesized. Various liquid crystal compounds having large optical anisotropy have also been synthesized. This is because new compounds are expected to have excellent physical properties that conventional compounds do not have. This is because it is expected that by adding a novel compound to the liquid crystal composition, an appropriate balance can be obtained between at least two physical properties in the composition. Under such circumstances, a compound having an excellent balance with the above-mentioned physical properties (1) to (8) is desired.

In paragraph 0260, Example 33 of Patent Document 1, the following compounds are described using the symbols F4-HHCF2OB (F, F) -F.

Further, Patent Documents 2 to 4 disclose the following compounds and analogs.

Japanese Unexamined Patent Publication No. 10-204016 Chinese Patent Application Publication No. 1040999105 Chinese Patent Application Publication No. 104130781 Chinese Patent Application Publication No. 1042633382

The first challenge is high stability to heat and light, high transparency (or high upper limit temperature of nematic phase), lower lower limit temperature of liquid crystal phase, low viscosity, proper optical anisotropy, large dielectric anisotropy. It is an object of the present invention to provide a liquid crystal compound satisfying at least one of physical characteristics such as an appropriate elastic constant and excellent compatibility with other liquid crystal compounds. It is to provide a compound which does not have a smectic phase and has a large elastic constant ratio as compared with similar compounds. The second challenge is that it contains this compound and has high stability to heat and light, high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, proper optical anisotropy, large dielectric anisotropy. It is an object of the present invention to provide a liquid crystal composition satisfying at least one of physical characteristics such as a large specific resistance and an appropriate elastic constant. The challenge is to provide a liquid crystal composition having an appropriate balance with respect to at least two physical characteristics. A third challenge is to provide a liquid crystal display device that includes this composition and has a wide temperature range in which the device can be used, a short response time, a large voltage retention, a low threshold voltage, a large contrast ratio, and a long life. That is.

式（１）において、
Ｒ^１Ｘは、１つまたは２つの水素が、ハロゲンで置き換えられた炭素数１から１０のアルキルであり；
環Ａ^１、環Ａ^２、環Ａ^３、環Ａ^４、および環Ａ^５は独立して、１，４−フェニレン、少なくとも１つの水素がハロゲンで置き換えられた１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、ピリジン−２，５−ジイル、またはピリミジン−２，５−ジイルであり、環Ａ^１、環Ａ^２、環Ａ^４、および環Ａ^５は１，４−シクロヘキシレンであってもよく；
Ｚ^１、Ｚ^２、Ｚ^３、およびＺ^４は独立して、単結合、−ＣＯＯ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−、−（ＣＨ_２）_４−、または−ＣＨ_２ＣＨ＝ＣＨＣＨ_２−であり；
Ｘ^１は、水素、ハロゲン、−ＣＦ_３、または−ＯＣＦ_３であり；
Ｌ^１およびＬ^２は独立して、水素、フッ素、または塩素であり；
ａ、ｂ、ｃ、およびｄは独立して、０または１であり、ａ、ｂ、ｃ、およびｄの和は１または２である。 The present invention relates to a compound represented by the formula (1), a liquid crystal composition containing this compound, and a liquid crystal display device containing this composition.

In equation (1)
R ¹ X is an alkyl with 1 to 10 carbon atoms in which one or two hydrogens have been replaced with halogen;
Ring A ¹ , Ring A ² , Ring A ³ , Ring A ⁴ , and Ring A ⁵ are independently 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with halogen, tetrahydropyran- It is 2,5-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl, and ring A ¹ , ring A ² , ring A ⁴ , and ring A ⁵ are 1,4-cyclohexylene. May;
Z ¹ , Z ² , Z ³ , and Z ⁴ are independently single-bonded, -COO-, -OCH _2- , -CF ₂ O-, -CH ₂ CH _2- , -CF ₂ CF ₂ -,- CF = CF -, - C≡C - , - (CH 2) 4 -, or _{-CH 2} CH = CHCH 2 - and is;
X ¹ is hydrogen, halogen, -CF ₃ , or -OCF ₃ ;
L ¹ and L ² are independently hydrogen, fluorine, or chlorine;
a, b, c, and d are independently 0 or 1, and the sum of a, b, c, and d is 1 or 2.

The first advantages are high stability to heat and light, high transparency (or high upper limit temperature of nematic phase), lower lower limit temperature of liquid crystal phase, low viscosity, proper optical anisotropy, large dielectric anisotropy. It is an object of the present invention to provide a liquid crystal compound satisfying at least one of physical characteristics such as an appropriate elastic constant and excellent compatibility with other liquid crystal compounds. It is to provide a compound which does not have a smectic phase and has a large elastic constant ratio as compared with a similar compound (see Comparative Examples 1 and 2). The second advantage is that it contains this compound and has high stability to heat and light, high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, suitable optical anisotropy, large dielectric anisotropy. It is an object of the present invention to provide a liquid crystal composition satisfying at least one of physical characteristics such as a large specific resistance and an appropriate elastic constant. This advantage is to provide a liquid crystal composition having an appropriate balance with respect to at least two physical characteristics. A third advantage is to provide a liquid crystal display device that includes this composition and has a wide temperature range in which the device can be used, a short response time, a large voltage retention, a low threshold voltage, a large contrast ratio, and a long life. That is.

The usage of terms in this specification is as follows. The terms "liquid crystal compound", "liquid crystal composition", and "liquid crystal display element" may be abbreviated as "compound", "composition", and "element", respectively. The "liquid crystal compound" is a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and a compound having no liquid crystal phase but adjusting the physical characteristics of the composition such as upper limit temperature, lower limit temperature, viscosity, and dielectric anisotropy. It is a general term for compounds added for the purpose. This compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-like. "Liquid crystal display element" is a general term for a liquid crystal display panel and a liquid crystal display module. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. The proportion (content) of the liquid crystal compound is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition. Additives such as polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, defoamers are required for this composition. Added accordingly. The ratio of the additive (addition amount) is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition, similarly to the ratio of the liquid crystal compound. Parts per million (ppm) by weight may also be used. The proportion of polymerization initiator or polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.

The "transparency point" is the transition temperature of the liquid crystal phase-isotropic phase in the liquid crystal compound. The "lower limit temperature of the liquid crystal phase" is the transition temperature of the solid-liquid crystal phase (smetic phase, nematic phase, etc.) in the liquid crystal compound. The "upper limit temperature of the nematic phase" is the transition temperature of the nematic phase-isotropic phase in the mixture or the liquid crystal composition of the liquid crystal compound and the mother liquid crystal, and may be abbreviated as the "upper limit temperature". The "lower limit temperature of the nematic phase" may be abbreviated as the "lower limit temperature". The expression "increase the dielectric anisotropy" means that when the composition has a positive dielectric anisotropy, its value increases positively, and the composition has a negative dielectric anisotropy. When it is a thing, it means that its value increases negatively.

The compound represented by the formula (1) may be abbreviated as the compound (1). At least one compound selected from the group of compounds represented by the formula (1) may be abbreviated as the compound (1). "Compound (1)" means one compound represented by the 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 equations (1) to (15), symbols such as ^{A 1} , B ¹ , and C ¹ enclosed in hexagons correspond to rings such as ring ^{A 1} , ring B ¹ , and ring C ^{1, respectively.} The hexagon represents a six-membered ring such as cyclohexane or benzene. The hexagon may represent a fused ring such as naphthalene or a crosslinked ring such as adamantane.

In the chemical formulas of the component compounds, with symbols of terminal groups R ¹ to a plurality of compounds. In these compounds, two groups represented by any two of R ¹ may be may be the same or different. For example, there are cases where ^{R 1 of} compound (1-1) ^{is ethyl and R 1} of compound (1-2) is ethyl. ^{In some cases, R 1 of} compound (1-1) ^{is ethyl and R 1} of compound (1-2) is propyl. This rule also applies to symbols such as ^{R 11} and Z ^11. In the compound (8), when i is 2, two rings ^{D 1} are present. The two groups represented by two rings D ¹ in the compound may be the same or different. When i is greater than 2, also apply to any two rings D ^1. This rule also applies to other symbols.

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'B'" is that when the number of'A's is 1, the position of the'A'is arbitrary and the number of'A's is 2. When more than one, it means that their positions can be selected without limitation. This rule also applies to the expression "at least one'A' has been replaced by a'B'". The expression "at least one'A' may be replaced by'B','C',or'D'" is any'if any'A' is replaced by a'B'. If A'is replaced by'C', and any'A' is replaced by'D', then more than one'A'is'B','C', and / or'D' It means to include the case where it is replaced by at least two. For example, " _{alkyl in which at least one -CH 2-} may be replaced with -O- or -CH = CH-" includes alkyl, alkoxy, alkoxyalkyl, alkoxy, alkoxyalkenyl, alkenyloxyalkyl. It is not preferable that two consecutive −CH ₂₋ are replaced with −O− to become −O−O−. In alkyl such, -CH ₂ methyl moiety _(-CH 2 -H) - by is replaced by -O- is not preferred also be the -O-H.

Halogen means fluorine, chlorine, bromine and iodine. Preferred halogens are fluorine and chlorine. A more preferred halogen is fluorine. The alkyl of the liquid crystal compound is linear or branched and does not contain cyclic alkyl. Linear alkyl is generally preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. The configuration for 1,4-cyclohexylene is preferably trans over cis in order to raise the upper temperature limit. 2-Fluoro-1,4-phenylene means 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 generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl.

The present invention includes the following items and the like.

式（１）において、
Ｒ^１Ｘは、１つまたは２つの水素が、ハロゲンで置き換えられた炭素数１から１０のアルキルであり；
環Ａ^１、環Ａ^２、環Ａ^３、環Ａ^４、および環Ａ^５は独立して、１，４−フェニレン、少なくとも１つの水素がハロゲンで置き換えられた１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、ピリジン−２，５−ジイル、またはピリミジン−２，５−ジイルであり、環Ａ^１、環Ａ^２、環Ａ^４、および環Ａ^５は１，４−シクロヘキシレンであってもよく；
Ｚ^１、Ｚ^２、Ｚ^３、およびＺ^４は独立して、単結合、−ＣＯＯ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−、−（ＣＨ_２）_４−、または−ＣＨ_２ＣＨ＝ＣＨＣＨ_２−であり；
Ｘ^１は、水素、ハロゲン、−ＣＦ_３、または−ＯＣＦ_３であり；
Ｌ^１およびＬ^２は独立して、水素、フッ素、または塩素であり；
ａ、ｂ、ｃ、およびｄは独立して、０または１であり、ａ、ｂ、ｃ、およびｄの和は１または２である。 Item 1. A compound represented by the formula (1).

In equation (1)
R ¹ X is an alkyl with 1 to 10 carbon atoms in which one or two hydrogens have been replaced with halogen;
Ring A ¹ , Ring A ² , Ring A ³ , Ring A ⁴ , and Ring A ⁵ are independently 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with halogen, tetrahydropyran- It is 2,5-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl, and ring A ¹ , ring A ² , ring A ⁴ , and ring A ⁵ are 1,4-cyclohexylene. May;
Z ¹ , Z ² , Z ³ , and Z ⁴ are independently single-bonded, -COO-, -OCH _2- , -CF ₂ O-, -CH ₂ CH _2- , -CF ₂ CF ₂ -,- CF = CF -, - C≡C - , - (CH 2) 4 -, or _{-CH 2} CH = CHCH 2 - and is;
X ¹ is hydrogen, halogen, -CF ₃ , or -OCF ₃ ;
L ¹ and L ² are independently hydrogen, fluorine, or chlorine;
a, b, c, and d are independently 0 or 1, and the sum of a, b, c, and d is 1 or 2.

Item 2. In the formula (1) described in Item 1,
R ¹ X is an alkyl with 1 to 10 carbon atoms in which one or two hydrogens have been replaced with fluorine or chlorine;
Ring A ¹ , Ring A ² , Ring A ³ , Ring A ⁴ , and Ring A ⁵ are independently 1,4-phenylene, a 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine. , Ring A ¹ , Ring A ² , Ring A ⁴ and Ring A ⁵ may be 1,4-cyclohexylene;
Z ¹ , Z ² , Z ³ , and Z ⁴ are independently single-bonded, -COO-, -OCH _2- , -CF ₂ O-, -CH ₂ CH _2- , -CF ₂ CF ₂ -,- CF = CF -, - C≡C - , - (CH 2) 4 -, or _{-CH 2} CH = CHCH 2 - and is;
X ¹ is fluorine, chlorine, -CF ₃ , or -OCF ₃ ;
L ¹ and L ² are independently hydrogen, fluorine, or chlorine;
a, b, c, and d are independently 0 or 1, and the sum of a, b, c, and d is 1 or 2.

式（１−１）から式（１−５）において、
Ｒ^１Ｘは、１つまたは２つの水素がフッ素または塩素で置き換えられた炭素数１から１０のアルキルであり；
環Ａ^１、環Ａ^２、環Ａ^３、環Ａ^４、および環Ａ^５は独立して、１，４−フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレン、またはテトラヒドロピラン−２，５−ジイルであり、環Ａ^１、環Ａ^２、環Ａ^４、および環Ａ^５は１，４−シクロヘキシレンであってもよく；
Ｚ^１、Ｚ^２、Ｚ^３、およびＺ^４は独立して、単結合、−ＣＯＯ−、−ＯＣＨ_２−、−Ｃ
Ｆ_２Ｏ−、または−ＣＨ_２ＣＨ_２−であり；
Ｘ^１は、フッ素、塩素、−ＣＦ_３、または−ＯＣＦ_３であり；
Ｌ^１およびＬ^２は独立して、水素、フッ素、または塩素である。 Item 3. Item 1 or 2 represented by any one of the formula (1-1), the formula (1-2), the formula (1-3), the formula (1-4), and the formula (1-5). The compound described.

In equations (1-1) to (1-5),
R ¹ X is an alkyl with 1 to 10 carbon atoms in which one or two hydrogens have been replaced with fluorine or chlorine;
Ring A ¹ , Ring A ² , Ring A ³ , Ring A ⁴ , and Ring A ⁵ are independently 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine, or It is tetrahydropyran-2,5-diyl, and ring A ¹ , ring A ² , ring A ⁴ and ring A ⁵ may be 1,4-cyclohexylene;
Z ¹ , Z ² , Z ³ , and Z ⁴ are independently single-bonded, -COO-, -OCH _2- , -C.
F ₂ O- or -CH ₂ CH _2- ;
X ¹ is fluorine, chlorine, -CF ₃ , or -OCF ₃ ;
L ¹ and L ² are independently hydrogen, fluorine, or chlorine.

式（１−１）、式（１−３）、および式（１−４）において、
Ｒ^１Ｘは、１つまたは２つの水素がフッ素で置き換えられた炭素数１から１０のアルキルであり；
環Ａ^１、環Ａ^２、環Ａ^３、および環Ａ^４は独立して、１，４−フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレン、またはテトラヒドロピラン−２，５−ジイルであり、環Ａ^１および環Ａ^２は１，４−シクロヘキシレンであってもよく；
Ｚ^１、Ｚ^２、およびＺ^３は独立して、単結合、−ＣＯＯ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、または−ＣＨ_２ＣＨ_２−であり；
Ｘ^１は、フッ素、−ＣＦ_３、または−ＯＣＦ_３であり；
Ｌ^１およびＬ^２は独立して、水素またはフッ素である。 Item 4. Item 6. The compound according to any one of Items 1 to 3, represented by any one of Formula (1-1), Formula (1-3), and Formula (1-4).

In equations (1-1), (1-3), and (1-4),
R ¹ X is an alkyl with 1 to 10 carbon atoms in which one or two hydrogens have been replaced with fluorine;
Ring A ¹ , Ring A ² , Ring A ³ , and Ring A ⁴ are independently 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine, or tetrahydropyran-2. , 5-diyl, ring A ¹ and ring A ² may be 1,4-cyclohexylene;
Z ¹ , Z ² , and Z ³ are independently single-bonded, -COO-, -OCH _2- , -CF ₂ O-, or -CH ₂ CH _2- ;
X ¹ is fluorine, -CF ₃ , or -OCF ₃ ;
L ¹ and L ² are independently hydrogen or fluorine.

式（１−ａ）から（１−ｈ）において、Ｒ^１Ｘは、１つの水素がフッ素で置き換えられた炭素数１から１０のアルキルであり；Ｘ^１は、フッ素、−ＣＦ_３、または−ＯＣＦ_３であり；Ｌ^１およびＬ^２は独立して、水素またはフッ素である。 Item 5. Item 6. The compound according to any one of Items 1 to 3, represented by any one of the formulas (1-a) to (1-h).

In formulas (1-a) through (1-h), R ¹ X is an alkyl having 1 to 10 carbon atoms in which one hydrogen is replaced with fluorine; X ¹ is fluorine, -CF ₃ , or-. OCF ₃ ; L ¹ and L ² are independently hydrogen or fluorine.

Item 6. In the formulas (1-a) to (1-h) described in Item 5, R ¹ X is − (CH ₂ ) _{h − CH 2} F, and h is an integer from 0 to 9. The compound described.

式（１−ｉ）から（１−ｐ）において、Ｒ^１Ｘは、１つの水素がフッ素で置き換えられた炭素数１から１０のアルキルであり；Ｘ^１は、フッ素、−ＣＦ_３、または−ＯＣＦ_３であり；Ｌ^１およびＬ^２は独立して、水素またはフッ素である。 Item 7. Item 6. The compound according to any one of Items 1 to 3, represented by any one of the formulas (1-i) to (1-p).

In formulas (1-i) to (1-p), R ¹ X is an alkyl having 1 to 10 carbon atoms in which one hydrogen is replaced with fluorine; X ¹ is fluorine, -CF ₃ , or-. OCF ₃ ; L ¹ and L ² are independently hydrogen or fluorine.

Item 8. In the formulas (1-i) to (1-p) described in Item 7, R ¹ X is − (CH ₂ ) _h.
Item 7. The compound according to Item 7, wherein the compound is −CH _{2 F and h is an integer from 1 to 9.}

Item 9. A liquid crystal composition containing at least one compound according to any one of Items 1 to 8.

式（２）から（４）において、
Ｒ^１１およびＲ^１２は独立して、炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、少なくとも１つの水素はフッ素で置き換えられてもよく；
環Ｂ^１、環Ｂ^２、環Ｂ^３、および環Ｂ^４は独立して、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，５−ジフルオロ−１，４−フェニレン、またはピリミジン−２，５−ジイルであり；
Ｚ^１１、Ｚ^１２、およびＺ^１３は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、または−ＣＯＯ−である。 Item 10. Item 9. The liquid crystal composition according to Item 9, further comprising at least one compound selected from the group of compounds represented by the formulas (2) to (4).

In equations (2) to (4)
R ¹¹ and R ¹² are independently alkyls with 1 to 10 carbons or alkenyl with 2 to 10 carbons, even if at least one -CH ₂ − is replaced with -O- in the alkyl and alkenyl. Well, at least one hydrogen may be replaced by fluorine;
Ring B ¹ , Ring B ² , Ring B ³ and Ring B ⁴ are independent, 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 are independently single-bonded, −CH ₂ CH _2- , −CH = CH−, −C≡C−, or −COO−.

式（５）から（７）において、
Ｒ^１３は炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、少なくとも１つの水素はフッ素で置き換えられてもよく；
Ｘ^１１は、フッ素、塩素、−ＯＣＦ₃、−ＯＣＨＦ₂、−ＣＦ₃、−ＣＨＦ₂、−ＣＨ₂Ｆ、−ＯＣＦ₂ＣＨＦ₂、または−ＯＣＦ₂ＣＨＦＣＦ₃であり；
環Ｃ^１、環Ｃ^２、および環Ｃ^３は独立して、１，４−シクロヘキシレン、少なくとも１つの水素がフッ素で置き換えられてもよい１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはピリミジン−２，５−ジイルであり；
Ｚ^１４、Ｚ^１５、およびＺ^１６は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２Ｏ−、または−（ＣＨ_２）_４−であり；
Ｌ^１１およびＬ^１２は独立して、水素またはフッ素である。 Item 11. Item 9. The liquid crystal composition according to Item 9 or 10, further containing at least one compound selected from the group of compounds represented by the formulas (5) to (7).

In equations (5) to (7)
R ¹³ is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one -CH ₂ − may be replaced by -O-, and at least one hydrogen is contained in the alkyl and alkenyl. May be replaced with fluorine;
X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ , or -OCF ₂ CHFCF ₃ ;
Ring C ¹ , Ring C ² , and Ring C ³ are independently 1,4-cyclohexylene, 1,4-phenylene, where 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 ¹⁴ , Z ¹⁵ and Z ¹⁶ are independently single-bonded, -CH ₂ CH _2- , -CH = CH-, -C≡C-, -COO-, -CF ₂ O-, -OCF _2- , _-CH 2 O-, or - _{(CH 2) 4} - a and;
L ¹¹ and L ¹² are independently hydrogen or fluorine.

式（８）において、
Ｒ^１４は炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、少なくとも１つの水素はフッ素で置き換えられてもよく；
Ｘ^１２は−Ｃ≡Ｎまたは−Ｃ≡Ｃ−Ｃ≡Ｎであり；
環Ｄ^１は、１，４−シクロヘキシレン、少なくとも１つの水素がフッ素で置き換えられてもよい１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはピリミジン−２，５−ジイルであり、環Ｄ^１が複数有る場合は、同じであっても、異なっていてもよく；
Ｚ^１７は、単結合、−ＣＨ_２ＣＨ_２−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−ＣＨ_２Ｏ−であり、Ｚ^１７が複数有る場合は、同じであっても、異なっていてもよく；
Ｌ^１３およびＬ^１４は独立して、水素またはフッ素であり；
ｉは、１、２、３、または４である。 Item 12. Item 6. The liquid crystal composition according to any one of Items 9 to 11, further containing at least one compound selected from the group of compounds represented by the formula (8).

In equation (8)
R ¹⁴ is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one −CH ₂ − may be replaced by −O − and at least one hydrogen is present. May be replaced with fluorine;
X ¹² is -C ≡ N or -C ≡ C-C ≡ N;
Ring D 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 a pyrimidine-2,5-diyl, if ring D ¹ has a plurality may be the same or different;
Z ¹⁷ represents a single _{bond, -CH 2 CH 2 -, -} C≡C -, - COO -, - CF 2 O -, - OCF 2 -, or _-CH 2 is ^{O-, if Z 17} has a plurality May be the same or different;
L ¹³ and L ¹⁴ are independently hydrogen or fluorine;
i is 1, 2, 3, or 4.

式（９）から（１５）において、
Ｒ^１５およびＲ^１６は独立して、炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、少なくとも１つの水素はフッ素で置き換えられてもよく；
Ｒ^１７は、水素、フッ素、炭素数１から１０のアルキル、または炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、少なくとも１つの水素はフッ素で置き換えられてもよく；
環Ｅ^１、環Ｅ^２、環Ｅ^３、および環Ｅ^４は独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、少なくとも１つの水素がフッ素で置き換えられてもよい１，４−フェニレン，テトラヒドロピラン−２，５−ジイル、またはデカヒドロナフタレン−２，６−ジイルであり、環Ｅ^１、環Ｅ^２、環Ｅ^３、および環Ｅ^４が複数有る場合は、同じであっても、異なっていてもよく；
環Ｅ^５および環Ｅ^６は独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン，テトラヒドロピラン−２，５−ジイル、またはデカヒドロナフタレン−２，６−ジイルであり；
Ｚ^１８、Ｚ^１９、Ｚ^２０、およびＺ^２１は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＯＯ−、−ＣＨ_２Ｏ−、−ＯＣＦ_２−、または−ＯＣＦ_２ＣＨ_２ＣＨ_２−であり、Ｚ^１８、Ｚ^１９、Ｚ^２０、およびＺ^２１が複数有る場合は、同じであっても、異なっていてもよく；
Ｌ^１５およびＬ^１６は独立して、フッ素または塩素であり；
Ｓ^１１は、水素またはメチルであり；
Ｘは、−ＣＨＦ−または−ＣＦ_２−であり；
ｊ、ｋ、ｍ、ｎ、ｐ、ｑ、ｒ、およびｓは独立して、０または１であり、ｋ、ｍ、ｎ、およびｐの和は、１または２であり、ｑ、ｒ、およびｓの和は、０、１、２、または３であり、ｔは、１、２、または３である。 Item 13. Item 6. The liquid crystal composition according to any one of Items 9 to 12, further containing at least one compound selected from the group of compounds represented by the formulas (9) to (15).

In equations (9) to (15)
R ¹⁵ and R ¹⁶ are independently alkyls with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, even if at least one -CH ₂ − is replaced with -O- in the alkyl and alkenyl. Well, at least one hydrogen may be replaced by fluorine;
R ¹⁷ is hydrogen, fluorine, an alkyl having 1 to 10 carbon atoms, or an alkenyl having 2 to 10 carbon atoms, in which at least one −CH ₂ − may be replaced by −O−. , At least one hydrogen may be replaced by fluorine;
Ring E ¹ , Ring E ² , Ring E ³ , and Ring E ⁴ may independently replace 1,4-cyclohexylene, 1,4-cyclohexenylene, and at least one hydrogen with fluorine 1, is 4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6-diyl, ring ^{E 1,} ring ^{E 2,} wherein ring ^{E 3,} and ring ^{E 4} have multiple, identical May be present or different;
Ring ^{E 5} and ring ^{E 6} are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene, 2,6 -Jeil;
^{Z 18, Z 19, Z 20} , and ^{Z 21} are independently a single _{bond, -CH 2 CH 2 -, -} COO -, - CH 2 O -, - OCF 2 -, or -OCF ₂ CH ₂ CH ₂ -And if there are multiple Z ¹⁸ , Z ¹⁹ , Z ²⁰ , and Z ²¹ , they may be the same or different;
L ¹⁵ and L ¹⁶ are independently fluorine or chlorine;
S ¹¹ is hydrogen or methyl;
X is -CHF- or -CF _2- ;
j, k, m, n, p, q, r, and s are independently 0 or 1, and the sum of k, m, n, and p is 1 or 2, q, r, and The sum of s is 0, 1, 2, or 3, and t is 1, 2, or 3.

Item 14. At least one additive selected from the group of polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, and defoamers. Item 8. The liquid crystal composition according to any one of Items 9 to 13, which is further contained.

Item 15. A liquid crystal display device containing the liquid crystal composition according to any one of Items 9 to 14.

The present invention also includes the following sections. (A) One selected from the group of polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, and defoamers. The composition described above further comprising two, or at least three additives. (B) 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 0.07 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C.). ) Is 2 or more, the above liquid crystal composition. (C) The above-mentioned liquid crystal display element in which the operation mode of the liquid crystal display element is TN mode, ECB mode, OCB mode, IPS mode, or FPA mode, and the drive method of the liquid crystal display element is the active matrix (AM) method. ..

The aspect of compound (1), the method for synthesizing compound (1), the liquid crystal composition, and the liquid crystal display element will be described in order.

1. 1. Embodiments compounds of the present invention compounds (1) (1) has an alkyl halogenated and CF 2 _O bonding group. This CF ₂ O binding group is located between the two phenylenes (see Compound BXB). On the other hand, the compound of Patent Document 1 has a CF ₂ O bonding group between cyclohexylene and phenylene (see Compound HXB). The compound (1) has a feature that it has a large optical anisotropy as compared with the compound described in Patent Document 1.

The first feature of compound (1) is that it does not have a smectic phase. Compound (1) has a nematic phase even when similar compounds have a smectic phase (see Comparative Examples 1 and 2). The second feature is that it has a large elastic constant ratio (K ₃₃ / K ₁₁ ). Compound (1) has a larger elastic constant ratio than similar compounds (see Comparative Example 2). When this elastic constant ratio is large, the voltage-transmittance curve of the device becomes steep. This means that a small voltage difference causes a large change in transmittance.

For the smectic phase, refer to JP-A-2007-308707. Paragraph 0007 states, "Recent commercial mixtures need to operate over a wide temperature range, so crystallization and formation of smectic phases at low temperatures must be eliminated. Usefulness of liquid crystals in the development of nematic mixtures. One of the most important prerequisites for sex is good solubility. For this reason, compounds that tend to form high melting temperatures or smectic phases are not suitable. " That is, it is preferable that the smectic phase does not exist.

A preferred example of compound (1) will be described. ^{Terminal groups R 1} X and X ¹ , ring A ¹ , ring A ² , ring A ³ , ring A ⁴ , and ring A ⁵ , binding groups Z ¹ , Z ² , Z ³ , and Z ⁴ , in compound (1). and preferred examples of the substituents L ¹ and L ^2, are applied to the sub-formulas of compound (1). In compound (1), the physical properties can be arbitrarily adjusted by appropriately combining these groups. Because large difference is not in the physical properties of the compound, the compound (1) is, ^{2 H} (deuterium), isotopes such as ^{13 C} may contain more than the amount of natural abundance. The definition of the symbol of compound (1) is as described in Item 1.

In formula (1), R ¹ X is an alkyl having 1 to 10 carbon atoms in which one or two hydrogens are replaced with halogen.

R ¹ X is monohaloalkyl or dihaloalkyl. Preferred halogens are fluorine or chlorine. A preferred monohaloalkyl is an alkyl in which one hydrogen is replaced by fluorine or chlorine. Examples of monofluoroalkyl are -CHF- (CH ₂ ) _e- CH ₃ ,-(CH ₂ ) _f- CHF- (CH ₂ ) _g- CH ₃ ,-(CH ₂ ) _h- CH ₂ F. Here, e is an integer from 0 to 8, the sum of f and g is an integer from 0 to 8, and h is an integer from 0 to 9. In these groups, fluorine may be replaced by chlorine.

The preferred dihaloalkyl is an alkyl in which two hydrogens are replaced with fluorine or chlorine. Examples of difluoroalkyl are -CF _2- (CH ₂ ) _e- CH ₃ ,-(CH ₂ ) _f- CF _2- (CH ₂ ) _g- CH ₃ ,-(CH ₂ ) _h- CHF ₂ , -CHF. -(CH ₂ ) _f- CHF- (CH ₂ ) _g- H and the like can be mentioned. Here, e is an integer from 0 to 8, the sum of f and g is an integer from 0 to 8, and h is an integer from 0 to 9. In these groups, fluorine may be replaced by chlorine.

In formula (1), ring A ¹ , ring A ² , ring A ³ , ring A ⁴ and ring A ⁵ are independently 1,4-phenylene, at least one hydrogen replaced with halogen 1,4. -Phenylene, tetrahydropyran-2,5-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl, ring A ¹ , ring A ² , ring A ⁴ , and ring A ⁵ are 1, It may be 4-cyclohexylene.

Preferred rings A ¹ to A ⁵ are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro. -1,4-phenylene, 2,3,5-trifluoro-1,4-phenylene, tetrahydropyran-2,5-diyl, or pyrimidine-2,5-diyl. More preferred rings A ¹ to A ⁵ are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, or tetrahydropyran-. 2,5-Zyle. Particularly preferred rings A ¹ to A ⁵ are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,6-difluoro-1,4-phenylene.

When at least one of the rings ^{A 5} from ring ^{A 1} is a 1,4-cyclohexylene, high clearing point, a small viscosity. When at least one of these is 1,4-phenylene, or when at least one hydrogen is 1,4-phenylene replaced by fluorine, the optical anisotropy is high and the orientation parameter. ) Is relatively large. When at least one of these is 1,4-phenylene in which at least one hydrogen is replaced with fluorine, the dielectric anisotropy is large.

In equation (1), Z ¹ , Z ² , Z ³ , and Z ⁴ are independently single-bonded, -COO-, -OCH _2- , -CF ₂ O-, -CH ₂ CH _2- , -CF. _{2 CF 2 -, - CF =} CF -, - C≡C -, - (CH 2) 4 -, or _{-CH 2} CH = CHCH 2 - a.

Preferred Z ¹ to Z ⁴ are single bonds, -COO-, -OCH _2- , -CF ₂ O-, or -CH ₂ CH _2- . More preferred Z ¹ to Z ⁴ are single bonds, -COO-, -OCH _2- , or -CF ₂ O-. Particularly preferred Z ¹ to Z ⁴ are single bonds or −CF ₂ O−. The most preferred Z ¹ to Z ⁴ are single bonds.

When Z ¹ , Z ² , Z ³ , or Z ⁴ is a single bond, the chemical stability is high and the viscosity is low. When Z ¹ , Z ² , Z ³ , or Z ⁴ is −CF ₂ O−, the viscosity is low, the dielectric anisotropy is high, and the upper limit temperature is high.

In formula (1), X ¹ is hydrogen, halogen, -CF ₃ , or -OCF ₃ . Preferred X ¹ is fluorine, chlorine, -CF ₃ , or -OCF ₃ . More preferred X ¹ is fluorine, -CF ₃ , or -OCF ₃ . Particularly preferred X ¹ is fluorine or -OCF ₃ . The most preferred X ¹ is fluorine. The most preferred X ¹ is −OCF ₃ . When X ¹ is fluorine, the viscosity is low. When X ¹ is −CF ₃ , the dielectric anisotropy is large. When X ¹ is −OCF ₃ , the compatibility with other liquid crystal compounds is excellent.

In formula (1), L ¹ and L ² are independently hydrogen, fluorine, or chlorine. Preferred L ¹ and L ² are combinations of hydrogen and fluorine. Preferred L ¹ and L ² are a combination of fluorine and fluorine. When L ¹ and L ² are a combination of hydrogen and fluorine, the dielectric anisotropy is large. When L ¹ and L ² are a combination of fluorine and fluorine, the dielectric anisotropy is particularly large.

In formula (1), a, b, c, and d are independently 0 or 1, and the sum of a, b, c, and d is 1 or 2. When the sum of a, b, c, and d is 1, compound (1) has three rings. This compound is preferred from the standpoint of low viscosity. When the sum of a, b, c, and d is 2, compound (1) has four rings. This compound is preferred from the standpoint of high transparency.

Examples of the preferable compound (1) are the compounds (1-1) to (1-5) described in Item 3. Examples of the more preferable compound (1) are the compound (1-1), the compound (1-3), and the compound (1-4) described in Item 4. Examples of the most preferable compound (1) are the compounds (1-a) to (1-h) described in Item 5. Examples of the most preferable compound (1) are also the compounds (1-i) to (1-p) described in Item 7.

Compound (1-1) is preferred from the standpoint of high stability to heat and light and low viscosity. Compound (1-3) is preferable from the viewpoint of high transparency and excellent compatibility. Compound (1-4) is preferable from the viewpoint of high transparency and large optical anisotropy.

2. Synthesis of Compound (1) A method for synthesizing compound (1) will be described. Compound (1) can be synthesized by appropriately combining the methods of synthetic organic chemistry. Houben-Wyle, Methoden der Organische Chemie, Georg-Thieme Verlag, Stuttgart, Organic Syntheses, John Wily & Sons, Inc.), Organic Reactions (John Wily & Sons Inc.), Comprehensive Organic Synthesis (Pergamon Press), New Experimental Chemistry Course (Maruzen), etc. Has been done.

2-1. From generation bonding group Z ¹ of the bonding group Z on how to generate Z ^4, illustrating a first scheme. Next, the reaction will be described. In this scheme, MSG ¹ (or MSG ² ) is a monovalent organic group with at least one ring. The monovalent organic groups represented by the plurality of MSG ¹ (or MSG ² ) used in the scheme may be the same or different. Compounds (1A) to (1I) correspond to compound (1). In the production of esters, a method for synthesizing a compound having -COO- was shown. Compounds having −OCO− can also be synthesized by this synthetic method. The same is true for other asymmetric binding groups.

(1) Generation of single bond

Arylboric acid (11) and compound (12) synthesized by a known method are reacted in an aqueous carbonate solution in the presence of a tetrakis (triphenylphosphine) palladium catalyst or the like to synthesize compound (1A). This compound (1A) is prepared by reacting compound (13) synthesized by a known method with n-butyllithium and then zinc chloride, and in the presence of a catalyst such as dichlorobis (triphenylphosphine) palladium, compound (12). ) Is also reacted.

(2) Generation of -COO-

Compound (13) is reacted with n-butyllithium followed by carbon dioxide to give carboxylic acid (14). Compound (14) and phenol (15) synthesized by a known method are dehydrated and condensed in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (N, N-dimethyl-4-aminopyridine). Compound (1B) is synthesized.

(3) Generation of _{-CH 2 O-}

Compound (16) is reduced with a reducing agent such as sodium borohydride to obtain compound (17). This is halogenated with hydrobromic acid to obtain compound (18). Compound (18) is reacted with compound (19) in the presence of a base such as potassium carbonate to synthesize compound (1C).

化合物（１Ｂ）をローソン試薬のような硫黄化剤で処理して化合物（２０）を得る。化合物（２０）をフッ化水素ピリジン錯体とＮＢＳ（Ｎ−ブロモスクシンイミド）でフッ素化し、−ＣＦ_２Ｏ−を有する化合物（１Ｄ）を合成する。M. Kuroboshi et al., Chem. Lett., 1992，827.を参照。化合物（１Ｄ）は化合物（１Ｂ）を（ジエチルアミノ）サルファートリフルオリド（ＤＡＳＴ）でフッ素化しても合成される。W. H. Bunnelle et al.,
J. Org. Chem. 1990, 55, 768.を参照。Peer. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480.に記載の方法によってこれらの結合基を生成させることも可能である。 (4) Generation of _{-CF 2 O-}

Compound (1B) is treated with a sulfurizing agent such as Lawesson's reagent to give compound (20). Compound (20) is fluorinated with a hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize compound (1D) having _{-CF 2 O-.} See M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1D) is also synthesized by fluorinating compound (1B) with (diethylamino) sulfatrifluoride (DAST). WH Bunnelle et al.,
See J. Org. Chem. 1990, 55, 768. It is also possible to generate these linking groups by the method described in Peer. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480.

(5) -CH ₂ CH _2- generation

A base such as potassium t-butoxide is allowed to act on the phosphonium salt (21) synthesized by a known method to prepare phosphorus irid. The compound (1E) is synthesized by hydrogenating the olefin obtained by reacting this with an aldehyde (16) in the presence of a catalyst such as palladium carbon.

(6)-(CF ₂ ) _2- Generation
Diketone (-COCO-) was fluorinated with sulfur tetrafluoride in the presence of a hydrogen fluoride catalyst according to the method described in J. Am. Chem. Soc., 2001, 123, 5414.-(CF ₂ ). Obtain a compound having _{2 −.}

(7) Generation of -CF = CF-

After treating compound (13) with n-butyllithium, it is reacted with tetrafluoroethylene to obtain compound (22). After treating compound (12) with n-butyllithium, it is reacted with compound (22) to synthesize compound (1F).

(8) Generation of -C≡C-

Compound (13) is reacted with 2-methyl-3-butin-2-ol in the presence of a catalyst of dichloropalladium and copper halide, and then deprotected under basic conditions to obtain compound (23). .. Compound (23) is reacted with compound (12) in the presence of a catalyst of dichloropalladium and copper halide to synthesize compound (1G).

ホスホニウム塩（２１）の代わりにホスホニウム塩（２４）を用い、項（５）の方法に従って−（ＣＨ_２）_２−ＣＨ＝ＣＨ−を有する化合物を得る。これをパラジウム炭素のような触媒の存在下で水素化することにより、化合物（１Ｈ）を合成する。 (9)-(CH ₂ ) _4- generation

A phosphonium salt (24) is used instead of the phosphonium salt (21) to obtain a compound having _{− (CH 2} ) _{2-CH = CH − according to the method of item (5).} Compound (1H) is synthesized by hydrogenating this in the presence of a catalyst such as palladium carbon.

(10) Generation of _{−CH 2} CH = CHCH _2-

A base such as potassium t-butoxide is allowed to act on a phosphonium salt (25) synthesized by a known method to prepare phosphorus iris. Compound (1I) is synthesized by reacting this with aldehyde (26).

2-2. Describing the synthesis relating to ring ^{A 5} from ring ^{A 1} in the product compound (1) of the ring ^{A 5} from ring ^{A 1.} 1,4-Cyclohexylene, pyrimidine-2,5-diyl, pyridine-2,5-diyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, 3-fluoro-1,4-phenylene, 3, For rings such as 5-difluoro-1,4-phenylene and 2,3-difluoro-1,4-phenylene, starting materials are commercially available or synthetic methods are well known.

2-3. Method for generating about the left terminal group R ^{1 X} in the product compound of R 1 ^X (1), first shows a scheme, will now be described reaction. In this scheme, MSG ² is a monovalent organic group with at least one ring. The organic groups represented by a plurality of MSG ² used in the scheme may be the same or different. Compounds (1J) and (1K) correspond to compound (1). The structural unit of the alkyl halide is synthesized by the following method. Even if the halogen is substituted at an arbitrary position of the alkyl, it can be synthesized in the same manner.

The alkyl halide halide (31) is reacted with triphenylphosphine to give the phosphonium salt (32). Phosphoride generated by treating compound (32) with a base such as potassium t-butoxide is reacted with aldehyde (16). Compound (1J) is synthesized by hydrogenating the obtained olefin (33) in the presence of a catalyst such as palladium carbon.

Compound (1K) can also be synthesized by halogenating compound (34) synthesized by a known method with (diethylamino) sulfatrifluoride (DAST) or triphenylphosphine and carbon tetrahalogenate.

3. 3. Liquid crystal composition 3-1. Ingredients Compounds The liquid crystal composition of the present invention will be described. This composition contains at least one compound (1) as component A. The composition may include two or more compounds (1). The component of the composition may be only compound (1). The composition preferably contains at least one of the compound (1) in the range of 1% by weight to 99% by weight in order to exhibit excellent physical properties. In the composition having a positive dielectric anisotropy, the preferable content of the compound (1) is in the range of 5% by weight to 60% by weight. In the composition having a negative dielectric anisotropy, the preferable content of the compound (1) is 30% by weight or less. The composition may include compound (1) and a liquid crystal compound not described herein.

This composition preferably contains compound (1) as component A and further contains a liquid crystal compound selected from the components B, C, D, and E shown below. Component B is compounds (2) to (4). Component C is compounds (5) to (7). Component D is compound (8). Component E is compounds (9) to (15). This composition may contain other liquid crystal compounds different from the compounds (2) to (15). When preparing this composition, it is preferable to select the components B, C, D, and E in consideration of the positive and negative values and the magnitude of the dielectric anisotropy. A composition with properly selected ingredients will have high stability to heat and light, high upper and lower temperature, low lower limit, low viscosity, good optical anisotropy (ie, large or small optical anisotropy). Has a large modulus anisotropy, a large specific resistance, and a suitable elastic constant (ie, a large elastic constant or a small elastic constant).

Component B is a compound having two terminal groups such as alkyl. Preferred examples of component B include compounds (2-1) to (2-11), compounds (3-1) to (3-19), and compounds (4-1) to (4-7). it can. In these compounds, R ¹¹ and R ¹² are independently alkyls with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, in which at least one -CH ₂ − is -O-. It may be replaced with, and at least one hydrogen may be replaced with fluorine.

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

As the content of component B is increased, the viscosity of the composition decreases, but the dielectric anisotropy decreases. Therefore, as long as the required value of the threshold voltage of the element is satisfied, it is preferable that the content is large. When preparing a composition for modes such as IPS and VA, the content of component B is preferably 30% by weight or more, more preferably 40% by weight or more, based on the weight of the liquid crystal composition.

Component C is a compound having a halogen or fluorine-containing group at the right end. Preferred examples of the component C include compounds (5-1) to (5-16), compounds (6-1) to (6-113), and compounds (7-1) to (7-57). .. In these compounds, R ¹³ is alkenyl having 2 to 10 carbon alkyl or C 1 to 10 carbon atoms, in the alkyl and alkenyl, at least one -CH 2 _- may be replaced by -O-; X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ , or -OCF ₂ CHFCF ₃ .

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

Component D is compound (8) whose right terminal group is -C≡N or -C≡C-C≡N. Preferred examples of the component D include compounds (8-1) to (8-64). In these compounds, R ¹⁴ is an alkyl with 1 to 10 carbons or an alkenyl with 2 to 10 carbons, in which at least one -CH ₂ − may be replaced with -O-. At least one hydrogen may be replaced by fluorine; X ¹² is -C ≡ N or -C ≡ C-C ≡ N.

Component D has a positive dielectric anisotropy and a large value, and is therefore used when preparing a composition for a mode such as a TN mode. By adding this component D, the dielectric anisotropy of the composition can be increased. Component D has the effect of widening the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. Component D is also useful for adjusting the voltage-transmittance curve of the device.

When preparing a composition for a mode such as TN mode, the content of component D is preferably in the range of 1% by weight to 99% by weight, preferably 10% by weight, based on the weight of the liquid crystal composition. It is in the range of 97% by weight, more preferably 40% by weight to 95% by weight. When the component D is added to a composition having a negative dielectric anisotropy, the content of the component D is preferably 30% by weight or less. By adding the component D, it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.

Component E is compounds (9) to (15). These compounds have phenylene in which the lateral position is replaced by two halogens, such as 2,3-difluoro-1,4-phenylene. Preferred examples of component E are compounds (9-1) to (9-8), compounds (10-1) to (10-17), compounds (11-1), compounds (12-1) to (12-). 3), compounds (13-1) to (13-11), compounds (14-1) to (14-3), and compounds (15-1) to (15-3) can be mentioned. In these compounds, R ¹⁵ and R ¹⁶ are independently alkyls with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, in which at least one -CH ₂ − is -O-. It may be replaced by, at least one hydrogen may be replaced by fluorine; R ¹⁷ is hydrogen, fluorine, alkenyl alkyl, or from 2 to 10 carbon atoms having 1 to 10 carbon atoms, the alkyl and In alkenyl, at least one -CH _2- may be replaced by -O- and at least one hydrogen may be replaced by fluorine.

Component E has a large negative dielectric anisotropy. Component E is used when preparing a composition for modes such as IPS, VA, and PSA modes. As the content of the component E is increased, the dielectric anisotropy of the composition becomes negatively large, but the viscosity becomes large. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the content is preferably small. Considering that the dielectric anisotropy is about −5, the content is preferably 40% by weight or more in order to drive the voltage sufficiently.

Since the compound (9) of the component E is a bicyclic compound, it has an effect of lowering the viscosity, adjusting the optical anisotropy, or increasing the dielectric anisotropy. Since the compounds (10) and (11) are tricyclic compounds, they have the effects of increasing the upper limit temperature, increasing the optical anisotropy, or increasing the dielectric anisotropy. Compounds (12) to (15) have the effect of increasing the dielectric anisotropy.

When preparing a composition for a mode such as IPS, VA, PSA mode, the content of the component E is preferably 40% by weight or more, more preferably 50% by weight, based on the weight of the liquid crystal composition. It ranges from% to 95% by weight. When the component E is added to the composition having a positive dielectric anisotropy, the content of the component E is preferably 30% by weight or less. By adding the component E, it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.

By properly combining the components B, C, D, and E described above, high stability to heat and light, high upper limit temperature, lower lower limit temperature, small viscosity, appropriate optical anisotropy, large dielectric anisotropy A liquid crystal composition can be prepared that satisfies at least one of physical characteristics such as physical characteristics, large resistivity, and appropriate elastic constant. If necessary, liquid crystal compounds different from the components B, C, D, and E may be added.

3-2. Additives The liquid crystal composition is prepared by a known method. For example, the constituent compounds are mixed and dissolved by heating. Additives may be added to this composition depending on the application. Examples of additives are polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dyes, defoamers and the like. Such additives are well known to those of skill in the art and are described in the literature.

In a liquid crystal display device having a PSA (polymer sustained alignment) mode, the composition contains a polymer. The polymerizable compound is added for the purpose of forming a polymer in the composition. A polymer is produced in the composition by irradiating ultraviolet rays with a voltage applied between the electrodes to polymerize the polymerizable compound. By this method, an appropriate pre-tilt is achieved, so that the response time is shortened and the device with improved image burn-in is produced.

Preferred examples of polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxylane, oxetane), and vinyl ketones. More preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. More preferred examples also include compounds having both acryloyloxy and methacryloyloxy.

More preferred examples are compounds (M-1) to (M-17). In these compounds, R ²⁵ to R ³¹ are independently hydrogen or methyl; s, v, and x are independently 0 or 1, and t and u are independently 1 to 10. It is an integer. L ²¹ to L ²⁶ are independently hydrogen or fluorine, and ^{if there are multiple L 25} and L ²⁶ respectively, they may be the same or different; L ²⁷ and L ²⁸ are independent, Hydrogen, fluorine, or methyl.

The polymerizable compound can be rapidly polymerized by adding a polymerization initiator. By optimizing the reaction temperature, the amount of residual polymerizable compound can be reduced. Examples of photoradical polymerization initiators are TPO, 1173, and 4265 from BASF's DaroCure series and 184,369,500,651,784,819,907,1300,1700,1800,1850 from the Irgacure series. , And 2959.

Additional examples of photoradical polymerization initiators include 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-Phenylaclysine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyl Dimethylketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2,4-diethylxanthone / p-dimethylaminomethyl benzoate mixture, benzophenone / methyltriethanolamine mixture Is.

Polymerization can be carried out by adding a photoradical polymerization initiator to the liquid crystal composition and then irradiating the liquid crystal composition with ultraviolet rays in a state where an electric field is applied. However, unreacted polymerization initiators or decomposition products of the polymerization initiators may cause display defects such as image burn-in on the device. In order to prevent this, photopolymerization may be carried out without adding a polymerization initiator. The preferred wavelength of the emitted light is in the range of 150 nm to 500 nm. More preferred wavelengths are in the range of 250 nm to 450 nm, and most preferred wavelengths are in the range of 300 nm to 400 nm.

When storing the polymerizable compound, a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine and the like.

The optically active compound has the effect of preventing reverse twisting by inducing a helical structure in the liquid crystal molecule to give a necessary twist angle. The spiral pitch can be adjusted by adding an optically active compound. Two or more optically active compounds may be added for the purpose of adjusting the temperature dependence of the spiral pitch. Preferred examples of the optically active compound include the following compounds (Op-1) to (Op-18). In compound (Op-18), ring J is 1,4-cyclohexylene or 1,4-phenylene, and R ²⁸ is an alkyl having 1 to 10 carbon atoms.

Antioxidants are effective in maintaining a large voltage retention. 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 name: BASF). be able to. The ultraviolet absorber is effective for preventing a decrease in the upper limit temperature. Preferred examples of the UV absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like, and specific examples thereof include 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); and 1,4-diazabicyclo [2.2.2] octane (DABCO) can be mentioned.

Light stabilizers such as amines with steric hindrance are preferred for maintaining high voltage retention. Preferred examples of the light stabilizer include the following compounds (AO-5) and (AO-6); TINUVIN 144, TINUVIN 765, and TINUVIN 770DF (trade name: BASF). A heat stabilizer is also effective for maintaining a large voltage holding ratio, and a preferable example thereof is IRGAFOS 168 (trade name; BASF). Dichroic dyes such as azo dyes, anthraquinone dyes and the like are added to the composition to accommodate devices in GH (guest host) mode. Defoamers are effective in preventing foaming. Preferred examples of the defoaming agent are dimethyl silicone oil, methyl phenyl silicone oil and the like.

In compound (AO-1), R ⁴⁰ is an alkyl having 1 to 20 carbons, an alkoxy having 1 to 20 carbons, -COOR ⁴¹ , or -CH ₂ CH ₂ COOR ⁴¹ , where R ⁴¹ has 1 carbon. To 20 alkyl. In compounds (AO-2) and (AO-5), R ⁴² is an alkyl having 1 to 20 carbon atoms. In compound (AO-5), R ⁴³ is hydrogen, methyl or O ^· (oxygen radical); ring G is 1,4-cyclohexylene or 1,4-phenylene; z is 1, 2, or It is 3.

4. Liquid crystal display element The liquid crystal composition has an operation mode such as PC, TN, STN, OCB, and PSA mode, and can be used for a liquid crystal display element driven by an active matrix. This composition has an operation mode such as PC, TN, STN, OCB, VA, and IPS mode, and can also be used for a liquid crystal display element driven by a passive matrix method. These elements can be applied to any type of reflective type, transmissive type, and semitransparent type.

This composition is also suitable for NCAP (nematic curvilinear aligned phase) devices, where the composition is microencapsulated. This composition can also be used in a polymer-dispersed liquid crystal display device (PDLCD) and a polymer network liquid crystal display device (PNLCD). In these compositions, a large amount of polymerizable compound is added. On the other hand, when the amount of the polymerizable compound added is 10% by weight or less based on the weight of the liquid crystal composition, a liquid crystal display element in PSA mode is produced. The preferred proportion is in the range of 0.1% by weight to 2% by weight. A more preferable ratio is in the range of 0.2% by weight to 1.0% by weight. The PSA mode element can be driven by a drive method such as an active matrix or a passive matrix. Such an element can be applied to any type of reflective type, transmissive type, and semitransparent type.

The present invention will be described in more detail by way of examples (including synthetic examples and usage examples). The present invention is not limited by these examples. The present invention includes a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes compositions prepared by mixing at least two of the compositions of Examples.

1. 1. Example of compound (1) Compound (1) was synthesized by the following procedure. The synthesized compound was identified by a method such as NMR analysis. The physical characteristics of the compound or composition and the characteristics of the device were measured by the following methods.

NMR analysis: A DRX-500 manufactured by Bruker Biospin was used for the measurement. ^{1 In the 1} H-NMR measurement, the sample _{was dissolved in a deuterated solvent such as CDCl 3} , and the measurement was performed under the conditions of room temperature, 500 MHz, and 16 times of integration. Tetramethylsilane was used as an internal standard. ^{19 In the} F-NMR measurement, CFCl ₃ was used as an internal standard, and the number of integrations was 24. In the description of the nuclear magnetic resonance spectrum, s means singlet, d means doublet, t means triplet, q means quartet, quin means quintet, sex means sextet, m means multiplet, and br means broad.

Gas chromatograph analysis: A GC-2010 type gas chromatograph manufactured by Shimadzu Corporation was used for the measurement. As the column, a capillary column DB-1 (length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc. was used. Helium (1 ml / min) was used as the carrier gas. The temperature of the sample vaporization chamber was set to 300 ° C., and the temperature of the detector (FID) portion was set to 300 ° C. The sample was dissolved in acetone to prepare a 1% by weight solution, and 1 μl of the obtained solution was injected into the sample vaporization chamber. A GC Solution system manufactured by Shimadzu Corporation was used as the recorder.

HPLC analysis: Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used for the measurement. As the column, YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle diameter 5 μm) manufactured by YMC was used. The eluate used was an appropriate mixture of acetonitrile and water. As the detector, a UV detector, an RI detector, a CORONA detector and the like were appropriately used. When a UV detector was used, the detection wavelength was 254 nm. The sample was prepared to dissolve in acetonitrile to form a 0.1% by weight solution, and 1 μL of this solution was introduced into the sample chamber. As a recorder, C-R7Aplus manufactured by Shimadzu Corporation was used.

Ultraviolet-visible spectroscopic analysis: A PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used for the measurement. The detection wavelength was 190 nm to 700 nm. The sample was prepared by dissolving it in acetonitrile to form a solution of 0.01 mmol / L, and placed in a quartz cell (optical path length 1 cm) for measurement.

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

When a sample in which the compound was mixed with the mother liquid crystal was used, the extrapolation value was calculated by the following formula, and this value was described. <Extrapolation value> = (100 x <measured value of sample>-<weight% of mother liquid crystal> x <measured value of mother liquid crystal>) / <weight% of compound>.

Mother liquid crystal (A): When the dielectric anisotropy of the compound was zero or positive, the following mother liquid crystal (A) was used. The ratio of each component was expressed in% by weight.

The ratio of the compound to the mother liquid crystal (A) was 15% by weight: 85% by weight. When crystals (or smectic phase) are precipitated at this ratio at 25 ° C., the ratio of the compound to the mother liquid crystal (A) is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99. The sample was measured at a rate at which crystals (or smectic phase) did not precipitate at 25 ° C. by changing in the order of% by weight. Unless otherwise specified, the ratio of the compound to the mother liquid crystal (A) was 15% by weight: 85% by weight.

Measurement method: The physical properties were measured by the following method. Many of these are described in the JEITA standard (JEITA ED-2521B), which is deliberated and enacted by the Japan Electronics and Information Technology Industries Association (JEITA). A modified method was also used. A thin film transistor (TFT) was not attached to the TN element used for the measurement.

(1) Phase structure: A sample was placed on a hot plate (FP-52 type hot stage manufactured by Mettler) of a melting point measuring device equipped with a polarizing microscope. While heating this sample at a rate of 3 ° C./min, the phase state and its change were observed with a polarizing microscope to identify the type of phase.

(2) Transition temperature (° C.): For measurement, a scanning calorimeter manufactured by PerkinElmer, Diamond.
A DSC system or X-DSC7000, a high-sensitivity differential scanning calorimeter manufactured by SII Nanotechnology, was used. The temperature of the sample was raised and lowered at a rate of 3 ° C./min, and the start point of the endothermic peak or exothermic peak accompanying the phase change of the sample was determined by extrapolation to determine the transition temperature. The melting point of the compound and the polymerization initiation temperature were also measured using this device. The temperature at which a compound transitions from a solid to a liquid crystal phase such as a smectic phase or a nematic phase may be abbreviated as "lower limit temperature of the liquid crystal phase". The temperature at which a compound transitions from the liquid crystal phase to a liquid may be abbreviated as "transparency point".

The crystal was represented as C. When the types of crystals can be distinguished, they are represented _{as C 1} or C _2. The smectic phase was represented as S and the nematic phase was represented as N. Among the smectic phase, a smectic A phase, a smectic B phase, if can be distinguished in the smectic C phase, or a smectic F phase, respectively _{S A,} S B, expressed as _{S C} or _{S F,.} The liquid (isotropic) was represented as I. The transition temperature is expressed as, for example, "C 50.0 N 100.0 I". This indicates that the transition temperature from the crystal to the nematic phase is 50.0 ° C. and the transition temperature from the nematic phase to the liquid is 100.0 ° C.

(3) Low temperature compatibility: A sample in which the mother liquid crystal and the compound are mixed so that the ratio of the compound is 20% by weight, 15% by weight, 10% by weight, 5% by weight, 3% by weight, and 1% by weight. Prepared and placed in a glass bottle. After storing this glass bottle in a freezer at −10 ° C. or −20 ° C. for a certain period of time, it was observed whether crystals or smectic phases were precipitated.

(4) Upper limit temperature of nematic phase ( _TNI or NI; ° C.): A sample was placed on a hot plate of a melting point measuring device equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature when a part of the sample changed from the nematic phase to the isotropic liquid was measured. When the sample was a mixture of compound (1) and the mother liquid crystal, it was indicated by the _{TNI symbol.} When the sample is a mixture of compound (1) and compounds such as components B, C and D, it is indicated by the symbol NI. The upper limit temperature of the nematic phase may be abbreviated as "upper limit temperature".

(5) Minimum Temperature of a Nematic Phase _{(T C;} ° C.): A sample having a nematic phase was put in a glass bottle, 0 ℃, -10 ℃, -20 ℃, -30 ℃, and -40 ℃ for 10 days in a freezer After storage, the liquid crystal phase was observed. _{For example, TC} was described as <-20 ° C. when the sample remained in the nematic phase at −20 ° C. and changed to a crystalline or smectic phase at −30 ° C. The lower limit temperature of the nematic phase may be abbreviated as "lower limit temperature".

(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.

(7) Viscosity (rotational viscosity; γ1; measured at 25 ° C.; mPa · s): The measurement was carried out according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). I obeyed. The sample was placed in a TN device having a twist angle of 0 ° and a distance (cell gap) between the two glass substrates of 5 μm. A stepwise application was applied to this device in 0.5 V increments in the range of 16 V to 19.5 V. After no application for 0.2 seconds, application was repeated under the conditions of only one square wave (square pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. The values of rotational viscosity were obtained from these measured values and the paper by M. Imai et al., Calculation formula (8) on page 40. The value of the dielectric anisotropy required for this calculation was obtained by the method described below using the element whose rotational viscosity was measured.

(8) Optical anisotropy (refractive index anisotropy; measured at 25 ° C.; Δn): The measurement was carried out using light having a wavelength of 589 nm and using an Abbe refractometer with a polarizing plate 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 ⊥.

(9) Dielectric constant anisotropy (Δε; measured at 25 ° C.): The sample was placed in a TN element having a distance (cell gap) between two glass substrates of 9 μm and a twist angle of 80 degrees. A sine wave (10 V, 1 kHz) was applied to this device, and after 2 seconds, the permittivity (ε ‖) of the liquid crystal molecule in the long axis direction was measured. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the permittivity (ε⊥) of the liquid crystal molecule in the minor axis direction was measured. The value of permittivity anisotropy was calculated from the equation Δε ＝ ε‖−ε⊥.

(10) Elastic constant (K; measured at 25 ° C.; pN): An HP4284A type LCR meter manufactured by Yokogawa Hewlett-Packard Co., Ltd. was used for the measurement. The sample was placed in a horizontally oriented element in which the distance (cell gap) between the two glass substrates was 20 μm. A charge of 0 to 20 volts was applied to this device, and the capacitance and applied voltage were measured. Use the measured capacitance (C) and applied voltage (V) values in "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), equations (2.98) and 2.101 on page 75. The fitting was performed, and the values of _{K 11} and K ₃₃ were obtained from the formula (2.99). _{Next, K 22} was calculated using the values of _{K 11} and K ₃₃ obtained earlier in the formula (3.18) on page 171. The elastic constant K is represented by the average value of _{K 11} , K ₂₂ , and K _{33 thus obtained.}

(11) Threshold voltage (Vth; measured at 25 ° C.; V): An LCD5100 type 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 white mode TN element in which the distance (cell gap) between the two glass substrates was 0.45 / Δn (μm) and the twist angle was 80 degrees. The voltage (32 Hz, square wave) applied to this device was gradually increased by 0.02 V from 0 V to 10 V. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the amount of light was maximum and the transmittance was 0% when the amount of light was minimum. The threshold voltage is expressed as the voltage when the transmittance reaches 90%.

(12) Voltage retention rate (VHR-1; measured at 25 ° C.;%): The TN element used for the measurement had a polyimide alignment film, and the distance (cell gap) between the two glass substrates was 5 μm. .. This device was sealed with an adhesive that cures with UV light after the sample is placed. A pulse voltage (60 microseconds at 5 V) was applied to this device at 25 ° C. to charge it. 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 attenuation. The voltage holding ratio is expressed as a percentage of the area A with respect to the area B.

(13) Voltage retention rate (VHR-2; measured at 80 ° C.;%): The voltage retention rate was measured by the above method except that the voltage retention rate was measured at 80 ° C. instead of 25 ° C. The results obtained are indicated by the symbol VHR-2.

(14) Specific resistance (ρ; measured at 25 ° C.; Ωcm): 1.0 mL of the sample was injected into a container equipped with an electrode. A DC voltage (10 V) was applied to this container, and the DC current after 10 seconds was measured. The specific resistance was calculated from the following formula. (Specific resistance) = {(voltage) x (electrical capacity of container)} / {(DC current) x (vacuum permittivity)}.

(15) Response time (τ; measured at 25 ° C.; ms): An LCD5100 type 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 white mode TN element in which the distance (cell gap) between the two glass substrates was 5.0 μm and the twist angle was 80 degrees. A square wave (60 Hz, 5 V, 0.5 seconds) was applied to this device. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. It was considered that the transmittance was 100% when the amount of light was maximum, and the transmittance was 0% when the amount of light was minimum. The rise time (τr: rise time; millisecond) was the time required for the transmittance to change from 90% to 10%. The fall time (τf: fall time; millisecond) was 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 the fall time obtained in this way.

Ingredients: Solmix® A-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (1.1%), obtained from Japan Alcohol Trading Co., Ltd. .. Tetrahydrofuran may be abbreviated as THF. Tetrabutylammonium bromide may be abbreviated as TBAB. N, N-dimethylformamide may be abbreviated as DMF. 2-Propanol may be abbreviated as IPA. 1,2-Dimethoxyethane may be abbreviated as DME. Hexamethyldisilazane potassium may be abbreviated as KHMDS.

[Synthesis Example 1]
Synthesis of compound (1-4-059)

First step: Synthesis of (S-3) Compound (S-1) (10.0 g, 54.1 mmol), compound (S-2) (9.9 g, 56.8 mmol), potassium carbonate (14.9 g, 108.1 mmol), tetrakis (triphenylphosphine) palladium (0.6 g, 0.5 mmol), tetrabutylammonium bromide (4.4 g, 13.5 mmol), water (100 mL), ethanol (200 mL) and toluene (200 mL). ) Was refluxed under a nitrogen stream for 12 hours. The reaction mixture was washed with saturated aqueous sodium chloride solution (200 mL) and water (200 mL) in that order. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (toluene) and recrystallization (toluene: heptane = 1: 1) to obtain compound (S-3) (9.6 g, 40.5 mmol) as colorless acicular crystals.

Second step: Synthesis of (S-4) Compound (S-3) (6.6 g, 28.1 mmol), p-toluenesulfonic acid monohydrate (0.1 g, 0.6 mmol) and ethylene glycol (1. A mixture of 9 g) was added to toluene (100 mL) under a nitrogen stream. The water was refluxed for 3 hours while being removed by azeotrope. After returning to room temperature, the mixture was washed in the order of saturated aqueous sodium hydrogen carbonate solution (100 mL), water (100 mL), and saturated aqueous sodium chloride solution (100 mL). The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (toluene) and recrystallization (toluene: heptane = 1: 1) to give compound (S-4) (5.6 g, 20.1 mmol) as colorless needle-like crystals.

Third step: Synthesis of (S-6) Compound (S-4) (4.0 g, 14.4 mmol), compound (S-5) (5.3 g, 15.1 mmol), potassium carbonate (4.0 g, A mixture of 28.7 mmol), PEPPSI-IPr (0.10 g, 0.15 mmol), water (10 mL), ethanol (50 mL) and toluene (50 mL) was refluxed under a nitrogen stream for 3 hours. The reaction mixture was washed with saturated aqueous sodium chloride solution (100 mL) and water (100 mL) in that order. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by recrystallization (toluene: heptane = 1: 1) to obtain compound (S-6) (5.3 g, 9.6 mmol) as colorless acicular crystals.

Fourth step: Synthesis of (S-7) Compound (S-6) (5.3 g, 9.6 mmol), tetrabutylammonium bromide (0.6 g, 1.9 mmol), formic acid (6.4 g) and toluene The mixture (50 mL) was stirred at 90 ° C. for 3 hours under a nitrogen stream. The reaction mixture was washed in the order of saturated aqueous sodium hydrogen carbonate solution (100 mL), water (100 mL) and saturated aqueous sodium chloride solution (100 mL). The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by recrystallization (toluene: heptane = 1: 1) to obtain compound (S-7) (4.6 g, 9.1 mmol) as colorless acicular crystals.

Fifth step: Synthesis of (S-9) Compound (S-8) (4.5 g, 10.9 mmol) was suspended in tetrahydrofuran (50 mL) under a nitrogen stream and cooled to −40 ° C. Potassium t-butoxide (1.2 g, 10.9 mmol) was added, and the mixture was stirred for 1 hour. A solution of compound (S-7) (4.6 g, 9.1 mmol) in tetrahydrofuran (20 mL) was added dropwise, the temperature was gradually returned to room temperature, and the mixture was stirred overnight. The reaction mixture was poured into saturated aqueous ammonium chloride solution (100 mL) and extracted with toluene (200 mL 3 times). The combined organic layers were washed with water (100 mL) and saturated aqueous sodium chloride solution (100 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (toluene) to give compound (S-9) (3.4 g, 6.0 mmol) as a colorless solid.

6th step: Synthesis of (1-4-059) Compound (S-9) (3.4 g, 6.0 mmol), 5% palladium carbon-1% sulfur poisoning (0.1 g), toluene (20 mL) The mixture of ethanol (20 mL) was stirred at room temperature under a hydrogen atmosphere. The catalyst was filtered off and then concentrated under reduced pressure. Compound (1-4-059) (0.4 g, 0.6 mmol) by purifying the residue by silica gel chromatography (heptane: ethyl acetate = 20: 1) and recrystallization (heptane: ethanol = 1: 1). Was obtained as colorless acicular crystals.

^{1 1} H-NMR (CDCl ₃ ; δppm): 7.54 (d, J = 8.2Hz, 2H), 7.48 (d, J = 4.4Hz, 2H), 7.42 (d, J = 12) 0.0Hz, 1H), 7.29 (d, J = 7.6Hz, 2H), 7.00 (t, J = 10.1Hz, 2H), 7.00 (t, J = 6.6Hz, 2H) , 4.51 (td, J = 6.0, 47.3Hz, 2H), 2.53 (t, J = 7.6Hz, 2H), 1.80-1.68 (m, 4H), 1. 52-1.46 (m, 2H). ¹⁹ F-NMR (δppm; CDCl ₃ ): -62.24 (t, J = 25.9Hz, 2F), -111.20 (dt, J = 10.7, 26.7Hz, 2F), -117. 32 (d, J = 12.2Hz, 1F), -132.97 (dd, J = 7.6, 19.9Hz, 2F), -163.65 (tt, J = 6.1,20.6Hz, 1F), -218.69 (tt, J = 25.2, 47.3Hz, 1F).

Phase transition temperature: C 48.6 N 105.8 I. Upper limit temperature (NI) = 88.4 ° C.; Dielectric constant anisotropy (Δε) = 30.77; Optical anisotropy (Δn) = 0.1837; Viscosity (η) = 83.3 mPa · s.

[Synthesis Example 2]
Synthesis of compound (1-4-010)

First step: Synthesis of (T-3) An isopropylmagnesium chloride-lithium chloride complex (1.3 M, 300 mL, 390 mmol) was dissolved in tetrahydrofuran (100 mL) under a nitrogen stream and cooled to −40 ° C. A solution of 4-iodobromobenzene (100 g, 354 mmol) in tetrahydrofuran (100 mL) was added dropwise, and the mixture was stirred for 1 hour. A solution of compound (T-2) (58 g, 371 mmol) in tetrahydrofuran (100 mL) was added dropwise, the temperature was returned to room temperature, and the mixture was further stirred for 8 hours. The reaction mixture was poured into saturated aqueous ammonium chloride solution (500 mL) and extracted with ethyl acetate (200 mL, 3 times). The combined organic layer was washed with saturated aqueous sodium chloride solution (500 mL) and water (500 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to make compound (T-3) a colorless solid (107 g, 341 mmol). Obtained.

Second step: Synthesis of (T-4) Compound (T-3) (48.0 g, 153 mmol), p-toluenesulfonic acid monohydrate (1.4 g, 7.6 mmol) and ethylene glycol (2.7 mL) Was added to toluene (300 mL) under a nitrogen stream. The water was refluxed for 2 hours while being removed by azeotrope. The reaction mixture was cooled to room temperature and then washed in the order of water (500 mL), saturated aqueous sodium hydrogen carbonate solution (500 mL), and water (500 mL). The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (toluene) to give compound (T-4) as a colorless solid (32.0 g, 108 mmol).

Third step: Synthesis of (T-6) Compound (T-4) (11.0 g, 37.3 mmol), compound (T-5) (16.4 g, 41.0 mmol), tripotassium phosphate (23. 7 g, 111.8 mmol), a mixture of 1,1'-bis (diphenylphosphino) ferrocene-palladium (II) dichloride-dichloromethane complex (0.3 g, 0.37 mmol) and dioxane (300 mL) for 5 hours under a nitrogen stream. It was refluxed. The reaction mixture was cooled to room temperature, filtered through Celite, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (toluene) to obtain a solid. To this solid isopropyl alcohol (500 mL) solution was added 5% palladium-carbon (0.6 g) and hydrogenated. The catalyst was filtered off and concentrated under reduced pressure. The residue was purified by silica gel chromatography (toluene) and recrystallization (toluene: heptane = 1: 1) to obtain compound (T-6) (11.3 g, 23.0 mmol) as colorless acicular crystals.

Step 4: Synthesis of (T-7) Compound (T-6) (11.3 g, 23.0 mmol), tetrabutylammonium bromide (1.5 g, 4.6 mmol), formic acid (34 mL) and toluene (50 mL) ) Was stirred under a nitrogen stream for 2 hours. The reaction mixture was washed with water (200 mL), saturated aqueous sodium hydrogen carbonate solution (200 mL), and water (200 mL) in that order. This solution was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give compound (T-7) (10.1 g, 22.6 mmol) as a colorless solid.

Fifth step: Synthesis of (T-9) Compound (T-8) (10.8 g, 29.4 mmol) was suspended in tetrahydrofuran (100 mL) under a nitrogen stream and cooled to −40 ° C. Potassium t-butoxide (3.3 g, 29.4 mmol) was added, and the mixture was stirred for 1 hour. A solution of compound (T-7) (10.1 g, 22.6 mmol) in tetrahydrofuran (25 mL) was added dropwise, the temperature was gradually returned to room temperature, and the mixture was stirred overnight. The reaction mixture was poured into saturated aqueous ammonium chloride solution (200 mL) and extracted with toluene (200 mL 3 times). The combined organic layers were washed with saturated aqueous sodium chloride solution (200 mL) and water (200 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
The residue was purified by silica gel chromatography (toluene: heptane = 1: 1) to give compound (T-9) (9.7 g, 20.4 mmol) as a colorless solid.

Step 6: Synthesis of (T-10) Compound (T-9) (9.7 g, 20.4 mmol), tetrabutylammonium bromide (1.3 g, 4.1 mmol), formic acid (29 mL) and toluene (50 mL) ) Was stirred under a nitrogen stream for 4 hours. The reaction mixture was washed with water (200 mL), saturated aqueous sodium hydrogen carbonate solution (200 mL), and water (200 mL) in that order. The solution was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was dissolved in isopropyl alcohol (100 mL) under a nitrogen stream and cooled to 0 ° C. An aqueous sodium hydroxide solution (2 mol / L, 50 mL) was added dropwise. The mixture was further stirred for 3 hours. The reaction mixture was poured into water (500 mL) and extracted with toluene (200 mL 3 times). The combined organic layers were washed with saturated aqueous sodium chloride solution (200 mL) and water (200 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by recrystallization (toluene: heptane = 1: 2) to obtain compound (T-10) (6.8 g, 14.8 mmol) as colorless acicular crystals.

7th step: Synthesis of (T-12) Compound (T-11) (2.0 g, 4.7 mmol) was suspended in tetrahydrofuran (30 mL) under a nitrogen stream and cooled to −40 ° C. Potassium t-butoxide (0.5 g, 4.7 mmol) was added, and the mixture was stirred for 1 hour. A solution of compound (T-10) (1.8 g, 3.9 mmol) in tetrahydrofuran (20 mL) was added dropwise, the temperature was gradually returned to room temperature, and the mixture was stirred overnight. The reaction mixture was poured into saturated aqueous ammonium chloride solution (100 mL) and extracted with toluene (3 times at 100 mL). The combined organic layers were washed with saturated aqueous sodium chloride solution (100 mL) and water (100 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (heptane: ethyl acetate = 20: 1) to give compound (T-12) (1.8 g, 3.5 mmol) as a colorless solid.

Eighth step: Synthesis of (1-4-010) Compound (T-12) (1.4 g, 2.8 mmol) and tosyl hydrazide (6.3 g, 33.9 mmol) are added to dimethoxyethane (30 mL) and refluxed. It was. A solution of sodium acetate (3.0 g, 35.8 mmol) in water (6 mL) was added dropwise thereto, and the mixture was refluxed for another 4 hours. The reaction mixture was poured into water (80 mL) and extracted with toluene (3 times at 100 mL). The combined organic layers were washed with saturated aqueous sodium chloride solution (100 mL) and water (100 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Compound (1-4-010) (0.7 g, 1.3 mmol) by purifying the residue by silica gel chromatography (heptane: ethyl acetate = 20: 1) and recrystallization (heptane: ethanol = 1: 1). Was obtained as colorless acicular crystals.

^{1 1} H-NMR (CDCl ₃ ; δppm): 7.73 (d, J = 8.4Hz, 2H), 7.68 (d, J = 8.4Hz, 2H), 7.54 (d, J = 8) .2Hz, 2H), 7.32 (d, J = 8.2Hz, 2H), 6.97 (dd, J = 6.1, 7.8Hz, 2H), 4.46 (td, J = 6. 3,47.3Hz, 2H), 2.53 (tt, J = 3.2, 12.1Hz, 1H), 1.95-1.88 (m, 4H), 1.76-1.68 (m) , 2H), 1.53-1.25 (m, 9H), 1.12-1.04 (m, 2H). ¹⁹ F-NMR ( _{δppm; CDCl 3} ): -66.62 (s, 2F), -133.17 (dd, J = 8.0, 20.3Hz, 2F), -164.31 (tt, J = 6.0, 21.2Hz, 1F), -218.45 (tt, J = 25.2, 47.3Hz, 1F).

Phase transition temperature: C 63.6 N 177.4 I. Upper limit temperature (NI) = 148.4 ° C.; Dielectric constant anisotropy (Δε) = 16.57; Optical anisotropy (Δn) = 0.157; Viscosity (η) =
57.9 mPa · s.

It is possible to synthesize the compounds shown below by referring to the methods described in Synthesis Examples 1 and 2 and the section “2. Synthesis of compound (1)”.

[Comparative Example 1]
The following compound (C-1) was selected for comparison. This is because the left end of this compound is alkyl, which is different from the compound of the present invention. This compound was synthesized according to the method described in JP-A-10-204016.

^{1 1} H-NMR (CDCl ₃ ; δppm): 7.54 (d, J = 8.2Hz, 2H), 7.48 (d, J = 4.5Hz, 2H), 7.42 (d, J = 12) .6Hz, 1H), 7.59 (d, J = 8.2Hz, 2H), 7.27 (s, 1H), 7.00 (dd, J = 6.3, 7.6Hz, 2H), 2 .67 (t, J = 7.6Hz, 2H), 1.66 (quin, J = 7.6Hz, 2H), 1.37-1.34 (m, 4H), 0.91 (t, J = 6.9Hz, 3H). ¹⁹ F-NMR ( _{δppm; CDCl 3} ): -62.18 (t, J = 26.7Hz, 2F), -111.16 (dt, J = 10.7, 26.7Hz, 2F), -117. 28--117.33 (m, 1F), -132.90 (dd, J = 7.6, 19.8Hz, 2F), -163.58 (tt, J = 6.1,21.4Hz, 1F) ). Phase transition temperature: C 61.1 SA 62.8 N 121.8 I.

Table 1 summarizes the phase transition temperatures of the compound (1-4-059) obtained in Synthesis Example 1 and the comparative compound (C-1). Comparative compound (C-1) showed a smectic phase _{(S A)} in the range of 62.8 ° C. from 61.1 ° C.. On the other hand, the compound (1-4-059) shows only a nematic phase was found to be superior smectic phase _{(S A)} with no points.

[Comparative Example 2]
The following compound (C-2) was selected for comparison. This is because the left end of this compound is alkyl, which is different from the compound of the present invention in this respect. This compound was synthesized according to the method described in JP-A-10-204016.

^{1 1} H-NMR (CDCl ₃ ; δppm): 7.73 (d, J = 8.5Hz, 2H), 7
.. 68 (d, J = 8.5Hz, 2H), 7.54 (d, J = 8.2Hz, 2H), 7.32 (d, J = 8.2Hz, 2H), 6.97 (dd, J) = 6.1, 7.9Hz, 2H), 2.53 (tt, J = 3.1, 12.1Hz, 1H), 1.91 (t, J = 14.9Hz, 4H), 1.53- 1.46 (m, 2H), 1.33-1.22 (m, 9H), 1.11-1.04 (m, 2H), 0.90 (t, J = 7.1Hz, 3H). ¹⁹ F-NMR ( _{δppm; CDCl 3} ): -66.62 (s, 2F), 133.19 (dd, J = 8.5, 21.2Hz, 2F), -164.33 (tt, J = 6.0, 21.3Hz, 1F). Phase transition temperature: C 51.4 SC 97.5 SA 97.5 N 184.3 I. Elastic constant ratio (K ₃₃ / K ₁₁ ) = 1.99 (K ₃₃ : bend elastic constant, K ₁₁ : spray elastic constant).

Table 2 summarizes the physical characteristics of the compound (1-4-010) obtained in Synthesis Example 2 and the comparative compound (C-2). Comparative compound (C-2) showed a smectic phase _{S C} and _{S A} added to the nematic phase. On the other hand, the compound (1-4-010) was found to be excellent in that it showed only the nematic phase and did not have the smectic phase. It was also found that the compound (1-4-010) was excellent in that the elastic constant ratio (K ₃₃ / K _{11) was large.}

2. Examples of Composition The composition of the present invention will be described in detail by way of examples. The present invention includes a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes a mixture of at least two of the compositions of Examples. The compounds in the use cases are represented by symbols based on the definitions in Table 3 below. In Table 3, the molecular configuration for 1,4-cyclohexylene is trance. In use cases, the number in parentheses after the symbol represents the chemical formula to which the compound belongs. The symbol (-) means other liquid crystal compounds. The proportion (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition. Finally, the physical characteristics of the composition are summarized. The physical properties were measured according to the method described above, and the measured values were described as they were (without extrapolation).

[Usage example 1]
F5-HBBXB (F, F) -F (1) 9%
2-HB-C (8-1) 5%
3-HB-C (8-1) 12%
3-HB-O2 (2-5) 12%
2-BTB-1 (2-10) 5%
3-HHB-F (6-1) 5%
3-HHB-1 (3-1) 5%
3-HHB-O1 (3-1) 5%
3-HHB-3 (3-1) 12%
3-HHEB-F (6-10) 5%
5-HHEB-F (6-10) 5%
2-HHB (F) -F (6-2) 5%
3-HHB (F) -F (6-2) 5%
5-HHB (F) -F (6-2) 5%
3-HHB (F, F) -F (6-3) 5%
NI = 106.0 ° C.; η = 22.4 mPa · s; Δn = 0.110; Δε = 5.7.

[Usage example 2]
F5-BB (F) B (F, F) XB (F, F) -F (1) 10%
3-HB-CL (5-2) 13%
3-HH-4 (2-1) 12%
3-HB-O2 (2-5) 8%
3-HHB (F, F) -F (6-3) 3%
3-HBB (F, F) -F (6-24) 25%
5-HBB (F, F) -F (6-24) 21%
5-HBB (F) B-2 (4-5) 4%
5-HBB (F) B-3 (4-5) 4%
NI = 70.3 ° C; η = 23.1 mPa · s; Δn = 0.120; Δε = 7.5.

[Usage example 3]
F5-BB (F, F) XB (F, F) -F (1) 7%
7-HB (F, F) -F (5-4) 3%
3-HB-O2 (2-5) 7%
2-HHB (F) -F (6-2) 9%
3-HHB (F) -F (6-2) 9%
5-HHB (F) -F (6-2) 9%
2-HBB (F) -F (6-23) 8%
3-HBB (F) -F (6-23) 8%
5-HBB (F) -F (6-23) 15%
2-HBB-F (6-22) 4%
3-HBB-F (6-22) 4%
5-HBB-F (6-22) 3%
3-HBB (F, F) -F (6-24) 5%
5-HBB (F, F) -F (6-24) 9%

[Usage example 4]
F3-BB (F, F) XB (F) B (F, F) -F (1) 6%
5-HB-CL (5-2) 13%
3-HH-4 (2-1) 12%
3-HH-5 (2-1) 4%
3-HHB-F (6-1) 4%
3-HHB-CL (6-1) 3%
4-HHB-CL (6-1) 3%
3-HHB (F) -F (6-2) 10%
4-HHB (F) -F (6-2) 8%
5-HHB (F) -F (6-2) 8%
7-HHB (F) -F (6-2) 8%
5-HBB (F) -F (6-23) 3%
1O1-HBBH-5 (4-1) 3%
3-HHBB (F, F) -F (7-6) 3%
4-HHBB (F, F) -F (7-6) 3%
5-HHBB (F, F) -F (7-6) 3%
3-HH2BB (F, F) -F (7-15) 3%
4-HH2BB (F, F) -F (7-15) 3%

[Usage example 5]
F5-HBBXB (F, F) -F (1) 8%
3-HHB (F, F) -F (6-3) 9%
3-H2HB (F, F) -F (6-15) 7%
4-H2HB (F, F) -F (6-15) 8%
5-H2HB (F, F) -F (6-15) 7%
3-HBB (F, F) -F (6-24) 19%
5-HBB (F, F) -F (6-24) 18%
3-H2BB (F, F) -F (6-27) 10%
5-HHBB (F, F) -F (7-6) 3%
5-HHEBB-F (7-17) 2%
3-HH2BB (F, F) -F (7-15) 3%
1O1-HBBH-4 (4-1) 3%
1O1-HBBH-5 (4-1) 3%
NI = 101.0 ° C.; η = 36.2 mPa · s; Δn = 0.119; Δε = 9.6.
When Op-05 was added to the above composition at a ratio of 0.25% by weight, the pitch was 65.2 μm.

[Usage example 6]
F5-BB (F) B (F, F) XB (F, F) -F (1) 6%
5-HB-F (5-2) 12%
6-HB-F (5-2) 9%
7-HB-F (5-2) 7%
2-HHB-OCF3 (6-1) 7%
3-HHB-OCF3 (6-1) 5%
4-HHB-OCF3 (6-1) 7%
5-HHB-OCF3 (6-1) 5%
3-HH2B-OCF3 (6-4) 4%
5-HH2B-OCF3 (6-4) 4%
3-HHB (F, F) -OCF2H (6-3) 3%
3-HHB (F, F) -OCF3 (6-3) 4%
3-HH2B (F) -F (6-5) 3%
3-HBB (F) -F (6-23) 8%
5-HBB (F) -F (6-23) 10%
5-HBBH-3 (4-1) 3%
3-HB (F) BH-3 (4-2) 3%
NI = 84.9 ° C; η = 17.9 mPa · s; Δn = 0.097; Δε = 5.8.

[Usage example 7]
F5-BB (F, F) XB (F, F) -F (1) 9%
5-HB-CL (5-2) 11%
3-HH-4 (2-1) 8%
3-HHB-1 (3-1) 4%
3-HHB (F, F) -F (6-3) 8%
3-HBB (F, F) -F (6-24) 17%
5-HBB (F, F) -F (6-24) 14%
3-HHEB (F, F) -F (6-12) 9%
4-HHEB (F, F) -F (6-12) 3%
5-HHEB (F, F) -F (6-12) 3%
2-HBEB (F, F) -F (6-39) 3%
3-HBEB (F, F) -F (6-39) 4%
5-HBEB (F, F) -F (6-39) 3%
3-HHBB (F, F) -F (7-6) 4%

[Usage example 8]
F3-BB (F, F) XB (F) B (F, F) -F (1) 7%
3-HB-CL (5-2) 6%
5-HB-CL (5-2) 4%
3-HHB-OCF3 (6-1) 5%
3-H2HB-OCF3 (6-13) 3%
5-H4HB-OCF3 (6-19) 15%
V-HHB (F) -F (6-2) 5%
3-HHB (F) -F (6-2) 5%
5-HHB (F) -F (6-2) 3%
3-H4HB (F, F) -CF3 (6-21) 8%
5-H4HB (F, F) -CF3 (6-21) 8%
5-H2HB (F, F) -F (6-15) 5%
5-H4HB (F, F) -F (6-21) 6%
2-H2BB (F) -F (6-26) 5%
3-H2BB (F) -F (6-26) 10%
3-HBEB (F, F) -F (6-39) 5%

[Usage example 9]
F5-HBBXB (F, F) -F (1) 10%
5-HB-CL (5-2) 17%
7-HB (F, F) -F (5-4) 3%
3-HH-4 (2-1) 10%
3-HH-5 (2-1) 5%
3-HB-O2 (2-5) 15%
3-HHB-1 (3-1) 7%
3-HHB-O1 (3-1) 4%
2-HHB (F) -F (6-2) 4%
3-HHB (F) -F (6-2) 5%
5-HHB (F) -F (6-2) 7%
3-HHB (F, F) -F (6-3) 5%
3-H2HB (F, F) -F (6-15) 4%
4-H2HB (F, F) -F (6-15) 4%
NI = 75.9 ° C.; η = 16.4 mPa · s; Δn = 0.081; Δε = 3.7.

[Usage example 10]
F5-BB (F) B (F, F) XB (F, F) -F (1) 8%
5-HB-CL (5-2) 3%
7-HB (F) -F (5-3) 7%
3-HH-4 (2-1) 9%
3-HH-5 (2-1) 10%
3-HB-O2 (2-5) 13%
3-HHEB-F (6-10) 8%
5-HHEB-F (6-10) 7%
3-HHEB (F, F) -F (6-12) 9%
4-HHEB (F, F) -F (6-12) 4%
3-GHB (F, F) -F (6-109) 4%
4-GHB (F, F) -F (6-109) 4%
5-GHB (F, F) -F (6-109) 5%
2-HHB (F, F) -F (6-3) 4%
3-HHB (F, F) -F (6-3) 5%
NI = 72.9 ° C.; η = 20.8 mPa · s; Δn = 0.077; Δε = 7.0.

[Usage example 11]
F5-BB (F, F) XB (F, F) -F (1) 5%
3-HB-O1 (2-5) 15%
3-HH-4 (2-1) 5%
3-HB (2F, 3F) -O2 (9-1) 12%
5-HB (2F, 3F) -O2 (9-1) 12%
2-HHB (2F, 3F) -1 (10-1) 11%
3-HHB (2F, 3F) -1 (10-1) 11%
3-HHB (2F, 3F) -O2 (10-1) 11%
5-HHB (2F, 3F) -O2 (10-1) 11%
3-HHB-1 (3-1) 7%

[Usage example 12]
F3-BB (F, F) XB (F) B (F, F) -F (1) 10%
2-HH-5 (2-1) 3%
3-HH-4 (2-1) 14%
3-HH-5 (2-1) 3%
3-HB-O2 (2-5) 10%
3-H2B (2F, 3F) -O2 (9-4) 15%
5-H2B (2F, 3F) -O2 (9-4) 13%
3-HHB (2F, 3CL) -O2 (10-12) 4%
2-HBB (2F, 3F) -O2 (10-7) 4%
3-HBB (2F, 3F) -O2 (10-7) 7%
5-HBB (2F, 3F) -O2 (10-7) 8%
3-HHB-1 (3-1) 3%
3-HHB-3 (3-1) 3%
3-HHB-O1 (3-1) 3%

[Usage example 13]
F5-HBBXB (F, F) -F (1) 6%
2-HH-3 (2-1) 20%
3-HH-4 (2-1) 9%
1-BB-3 (2-8) 9%
3-HB-O2 (2-5) 2%
3-BB (2F, 3F) -O2 (9-3) 9%
5-BB (2F, 3F) -O2 (9-3) 6%
2-HH1OB (2F, 3F) -O2 (10-5) 11%
3-HH1OB (2F, 3F) -O2 (10-5) 18%
3-HHB-1 (3-1) 5%
3-HHB-O1 (3-1) 3%
5-B (F) BB-2 (3-8) 2%
NI = 76.3 ° C; η = 16.3 mPa · s; Δn = 0.101; Δε = -2.8.

[Usage example 14]
F5-BB (F) B (F, F) XB (F, F) -F (1) 9%
2-HH-3 (2-1) 16%
7-HB-1 (2-5) 10%
5-HB-O2 (2-5) 8%
3-HB (2F, 3F) -O2 (9-1) 15%
5-HB (2F, 3F) -O2 (9-1) 15%
3-HHB (2F, 3CL) -O2 (10-12) 3%
4-HHB (2F, 3CL) -O2 (10-12) 3%
5-HHB (2F, 3CL) -O2 (10-12) 2%
3-HH1OCro (7F, 8F) -5 (13-6) 3%
5-HBB (F) B-2 (4-5) 8%
5-HBB (F) B-3 (4-5) 8%
NI = 71.4 ° C; η = 25.3 mPa · s; Δn = 0.106; Δε = -2.2.

[Usage example 15]
F5-BB (F, F) XB (F, F) -F (1) 8%
1-BB-3 (2-8) 10%
3-HH-V (2-1) 27%
3-BB (2F, 3F) -O2 (9-3) 13%
2-HH1OB (2F, 3F) -O2 (10-5) 18%
3-HH1OB (2F, 3F) -O2 (10-5) 12%
3-HHB-1 (3-1) 6%
5-B (F) BB-2 (3-8) 6%

[Usage example 16]
F3-BB (F, F) XB (F) B (F, F) -F (1) 9%
2-HH-3 (2-1) 6%
3-HH-V1 (2-1) 8%
1V2-HH-1 (2-1) 7%
1V2-HH-3 (2-1) 7%
3-BB (2F, 3F) -O2 (9-3) 7%
5-BB (2F, 3F) -O2 (9-3) 4%
3-H1OB (2F, 3F) -O2 (9-5) 7%
2-HH1OB (2F, 3F) -O2 (10-5) 7%
3-HH1OB (2F, 3F) -O2 (10-5) 17%
3-HDhB (2F, 3F) -O2 (10-3) 6%
3-HHB-1 (3-1) 3%
3-HHB-3 (3-1) 2%
2-BB (2F, 3F) B-3 (11-1) 10%

[Usage example 17]
F5-HBBXB (F, F) -F (1) 7%
1V2-BEB (F, F) -C (8-15) 4%
3-HB-C (8-1) 17%
2-BTB-1 (2-10) 10%
5-HH-VFF (2-1) 30%
3-HHB-1 (3-1) 3%
VFF-HHB-1 (3-1) 7%
VFF2-HHB-1 (3-1) 10%
3-H2BTB-2 (3-17) 4%
3-H2BTB-3 (3-17) 4%
3-H2BTB-4 (3-17) 4%
NI = 85.0 ° C.; η = 13.8 mPa · s; Δn = 0.131; Δε = 6.0.

[Usage example 18]
F5-BB (F) B (F, F) XB (F, F) -F (1) 6%
5-HB (F) B (F, F) XB (F, F) -F (7-41) 3%
3-BB (F) B (F, F) XB (F, F) -F (7-47) 3%
4-BB (F) B (F, F) XB (F, F) -F (7-47) 5%
5-BB (F) B (F, F) XB (F, F) -F (7-47) 3%
3-HH-V (2-1) 41%
3-HH-V1 (2-1) 7%
3-HHEH-5 (3-13) 3%
3-HHB-1 (3-1) 3%
V-HHB-1 (3-1) 5%
V2-BB (F) B-1 (3-6) 5%
1V2-BB-F (5-1) 3%
3-BB (F, F) XB (F, F) -F (6-97) 10%
3-HHBB (F, F) -F (7-6) 3%
NI = 81.9 ° C; η = 13.6 mPa · s; Δn = 0.107; Δε = 6.6.

[Usage example 19]
F5-BB (F, F) XB (F, F) -F (1) 6%
F3-BB (F, F) XB (F) B (F, F) -F (1) 5%
3-GB (F) B (F, F) XB (F, F) -F (7-57) 4%
3-BB (F) B (F, F) XB (F, F) -F (7-47) 3%
4-BB (F) B (F, F) XB (F, F) -F (7-47) 3%
5-BB (F) B (F, F) XB (F, F) -F (7-47) 3%
3-HH-V (2-1) 38%
3-HH-V1 (2-1) 7%
3-HHEH-5 (3-13) 3%
3-HHB-1 (3-1) 4%
V-HHB-1 (3-1) 5%
V2-BB (F) B-1 (3-6) 5%
1V2-BB-F (5-1) 3%
3-BB (F, F) XB (F, F) -F (6-97) 4%
3-GB (F, F) XB (F, F) -F (6-113) 4%
3-HHBB (F, F) -F (7-6) 3%

The liquid crystal compound of the present invention has excellent physical characteristics. A liquid crystal composition containing this compound can be widely used in a liquid crystal display element used in a personal computer, a television, or the like.

Claims (13)

At least one compound selected from the compounds represented by the formula (1) and the formula (3) and (4) a liquid crystal composition containing a small without even one compound of the compounds represented by.

In equation (1)
R ¹ X is an alkyl with 1 to 10 carbon atoms in which one or two hydrogens have been replaced with halogen;
Ring ^{A 1,} ring ^{A 2,} ring ^{A 3,} ring ^{A 4,} and ring ^{A 5} are each independently 1,4-phenylene, at least one hydrogen is 1,4-phenylene which is replaced by halogen, Rings A ¹ and A ² may be 1,4-cyclohexylene , pyridine-2,5-diyl, or pyrimidine-2,5-diyl ;
Z ¹ , Z ² , Z ³ , and Z ⁴ are independently single-bonded, -COO-, -OCH _2- , -CF ₂ O-, -CH ₂ CH _2- , -CF ₂ CF ₂ -,- CF = CF -, - C≡C - , - (CH 2) 4 -, or _{-CH 2} CH = CHCH 2 - and is;
X ¹ is hydrogen, halogen, -CF ₃ , or -OCF ₃ ;
L ¹ and L ² are independently hydrogen, fluorine, or chlorine;
a, b, c, and d are independently 0 or 1, and the sum of a, b, c, and d is 1 or 2; and

In equations ( 3 ) to (4),
R ¹¹ and R ¹² are independently alkyls with 1 to 10 carbons or alkenyl with 2 to 10 carbons, even if at least one -CH ₂ − is replaced with -O- in the alkyl and alkenyl. Well, at least one hydrogen may be replaced by fluorine;
Ring B ¹ , Ring B ² , Ring B ³ and Ring B ⁴ are independent, 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 are independently single-bonded, −CH ₂ CH _2- , −CH = CH−, −C≡C−, or −COO−. In equation (1)
R ¹ X is an alkyl with 1 to 10 carbon atoms in which one or two hydrogens have been replaced with fluorine or chlorine;
Ring A ¹ , Ring A ² , Ring A ³ , Ring A ⁴ , and Ring A ⁵ are independently 1,4-phenylene, a 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine. , Ring A ¹ and Ring A ² may be 1,4-cyclohexylene;
Z ¹ , Z ² , Z ³ , and Z ⁴ are independently single-bonded, -COO-, -OCH _2- , -CF ₂ O-, -CH ₂ CH _2- , -CF ₂ CF ₂ -,- CF = CF -, - C≡C - , - (CH 2) 4 -, or _{-CH 2} CH = CHCH 2 - and is;
X ¹ is fluorine, chlorine, -CF ₃ , or -OCF ₃ ;
L ¹ and L ² are independently hydrogen, fluorine, or chlorine;
The liquid crystal composition according to claim 1, wherein a, b, c, and d are independently 0 or 1, and the sum of a, b, c, and d is 1 or 2. The compound represented by the formula (1) is any one of the formula (1-1), the formula (1-2), the formula (1-3), the formula (1-4), and the formula (1-5). The liquid crystal composition according to claim 1 or 2, which is a compound represented by one.

In equations (1-1) to (1-5),
R ¹ X is an alkyl with 1 to 10 carbon atoms in which one or two hydrogens have been replaced with fluorine or chlorine;
Ring ^{A 1,} ring ^{A 2,} ring ^{A 3,} ring ^{A 4,} and ring ^{A 5} are each independently 1,4-phenylene, at least one hydrogen in the 1,4-phenylene which is replaced by fluorine or chlorine Yes, ring A ¹ and ring A ² may be 1,4-cyclohexylene;
Z ¹ , Z ² , Z ³ , and Z ⁴ are independently single-bonded, -COO-, -OCH _2- , -CF ₂ O-, or -CH ₂ CH _2- ;
X ¹ is fluorine, chlorine, -CF ₃ , or -OCF ₃ ;
L ¹ and L ² are independently hydrogen, fluorine, or chlorine. Claims 1 to 3 wherein the compound represented by the formula (1) is a compound represented by any one of the formula (1-1), the formula (1-3), and the formula (1-4). The liquid crystal composition according to any one of the above.

In equations (1-1), (1-3), and (1-4),
R ¹ X is an alkyl with 1 to 10 carbon atoms in which one or two hydrogens have been replaced with fluorine;
Ring ^{A 1,} ring ^{A 2,} ring ^{A 3,} and ring ^{A 4} are each independently 1,4-phenylene, 1,4-phenylene which is replaced by at least one hydrogen fluorine or chlorine, ring A ¹ and ring A ² may be 1,4-cyclohexylene;
Z ¹ , Z ² , and Z ³ are independently single-bonded, -COO-, -OCH _2- , -CF ₂ O-, or -CH ₂ CH _2- ;
X ¹ is fluorine, -CF ₃ , or -OCF ₃ ;
L ¹ and L ² are independently hydrogen or fluorine. The liquid crystal according to any one of claims 1 to 4, wherein the compound represented by the formula (1) is a compound represented by any one of the formulas (1-a) to (1-h). Composition.

In formulas (1-a) through (1-h), R ¹ X is an alkyl having 1 to 10 carbon atoms in which one hydrogen is replaced with fluorine; X ¹ is fluorine, -CF ₃ , or-. OCF ₃ ; L ¹ and L ² are independently hydrogen or fluorine. The liquid crystal composition according to claim 5, wherein in the formulas (1-a) to (1-h), R ¹ X is − (CH ₂ ) _{h − CH 2 F, and h is an integer from 0 to 9.} Stuff. The liquid crystal according to any one of claims 1 to 4, wherein the compound represented by the formula (1) is a compound represented by any one of the formulas (1-i) to (1-p). Composition.

In formulas (1-i) to (1-p), R ¹ X is an alkyl having 1 to 10 carbon atoms in which one hydrogen is replaced with fluorine; X ¹ is fluorine, -CF ₃ , or-. OCF ₃ ; L ¹ and L ² are independently hydrogen or fluorine. In equations (1-i) to (1-p), R ¹ X is − (CH ₂ ) _{h − CH 2} F.
The liquid crystal composition according to claim 7, wherein h is an integer from 1 to 9. The liquid crystal composition according to any one of claims 1 to 8, further comprising at least one compound selected from the group of compounds represented by the formulas (5) to (7).

In equations (5) to (7)
R ¹³ is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one -CH ₂ − may be replaced by -O-, and at least one hydrogen is contained in the alkyl and alkenyl. May be replaced with fluorine;
X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F.
, -OCF ₂ CHF ₂ , or -OCF ₂ CHFCF ₃ ;
Ring C ¹ , Ring C ² , and Ring C ³ are independently 1,4-cyclohexylene, 1,4-phenylene, where 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 ¹⁴ , Z ¹⁵ and Z ¹⁶ are independently single-bonded, -CH ₂ CH _2- , -CH = CH-, -C≡C-, -COO-, -CF ₂ O-, -OCF _2- , _-CH 2 O-, or - _{(CH 2) 4} - a and;
L ¹¹ and L ¹² are independently hydrogen or fluorine. The liquid crystal composition according to any one of claims 1 to 9, further comprising at least one compound selected from the group of compounds represented by the formula (8).

In equation (8)
R ¹⁴ is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one −CH ₂ − may be replaced by −O − and at least one hydrogen is present. May be replaced with fluorine;
X ¹² is -C ≡ N or -C ≡ C-C ≡ N;
Ring D 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 a pyrimidine-2,5-diyl, if ring D ¹ has a plurality may be the same or different;
Z ¹⁷ represents a single _{bond, -CH 2 CH 2 -, -} C≡C -, - COO -, - CF 2 O -, - OCF 2 -, or _-CH 2 is ^{O-, if Z 17} has a plurality May be the same or different;
L ¹³ and L ¹⁴ are independently hydrogen or fluorine;
i is 1, 2, 3, or 4. The liquid crystal composition according to any one of claims 1 to 10, further comprising at least one compound selected from the group of compounds represented by the formulas (9) to (15).

In equations (9) to (15)
R ¹⁵ and R ¹⁶ are independently alkyls with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, even if at least one -CH ₂ − is replaced with -O- in the alkyl and alkenyl. Well, at least one hydrogen may be replaced by fluorine;
R ¹⁷ is hydrogen, fluorine, an alkyl having 1 to 10 carbon atoms, or an alkenyl having 2 to 10 carbon atoms, in which at least one −CH ₂ − may be replaced by −O−. , At least one hydrogen may be replaced by fluorine;
Ring E ¹ , Ring E ² , Ring E ³ , and Ring E ⁴ may independently replace 1,4-cyclohexylene, 1,4-cyclohexenylene, and at least one hydrogen with fluorine 1, 4-Phenylene, Tetrahydropyran-2,5-Diyl, or Decahydronaphthalen-2
, 6-Diyl, and ^{if there are multiple rings E 1} , ring E ² , ring E ³ , and ring E ⁴ , they may be the same or different;
Ring ^{E 5} and ring ^{E 6} are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene, 2,6 -Jeil;
^{Z 18, Z 19, Z 20} , and ^{Z 21} are independently a single _{bond, -CH 2 CH 2 -, -} COO -, - CH 2 O -, - OCF 2 -, or -OCF ₂ CH ₂ CH ₂ -And if there are multiple Z ¹⁸ , Z ¹⁹ , Z ²⁰ , and Z ²¹ , they may be the same or different;
L ¹⁵ and L ¹⁶ are independently fluorine or chlorine;
S ¹¹ is hydrogen or methyl;
X is -CHF- or -CF _2- ;
j, k, m, n, p, q, r, and s are independently 0 or 1, and the sum of k, m, n, and p is 1 or 2, q, r, and The sum of s is 0, 1, 2, or 3, and t is 1, 2, or 3. At least one additive selected from the group of polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, and defoamers. The liquid crystal composition according to any one of claims 1 to 11, further contained. A liquid crystal display device containing the liquid crystal composition according to any one of claims 1 to 12.