JP6578690B2 - Liquid crystal compound having halogenated alkyl, liquid crystal composition, and liquid crystal display device - Google Patents

Description

  The present invention relates to a liquid crystal compound, a liquid crystal composition, and a liquid crystal display element. 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 including the composition.

  Liquid crystal display elements are widely used in displays such as personal computers and televisions. This element utilizes physical properties such as optical anisotropy and dielectric anisotropy of a liquid crystalline compound. As an operation mode of the liquid crystal display element, PC (phase change), TN (twisted nematic), STN (super twisted nematic), BTN (bistable twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), 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 properties is used. In order to further improve the characteristics of the device, it is preferable that the liquid crystalline compound contained in the composition has physical properties shown in the following (1) to (8). (1) high stability to heat and light, (2) high clearing point, (3) low minimum 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 device characteristics are as follows. As in (1), a compound having high stability to heat and light increases the voltage holding ratio of the device. This increases the lifetime of the device. A compound having a high clearing 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, a smectic phase, etc., in particular, a lower limit temperature of the nematic phase extends the usable temperature range of the device. As in (4), a compound having a small 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 is required as shown in (5). When the response time is shortened by reducing the cell gap of the element, 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 widens the usable temperature range of the device by increasing the maximum temperature of the nematic phase.

  Regarding (7), a compound having a large elastic constant shortens the response time of the device. A compound having a small elastic constant lowers 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 preferred. This is because liquid crystal compounds having different physical properties are mixed to adjust the physical properties of the composition.

  Until now, various liquid crystal compounds having a large dielectric anisotropy have been synthesized. Various liquid crystalline compounds having large optical anisotropy have been synthesized. This is because the new compound is expected to have excellent physical properties not found in conventional compounds. This is because it is expected that an appropriate balance between at least two physical properties in the composition can be obtained by adding the novel compound to the liquid crystal composition. Under such circumstances, a compound having an excellent balance between the physical properties (1) to (8) and an appropriate balance is desired.

In paragraph 0260 and use example 33 of Patent Document 1, the following compounds are described using the symbol F4-HHCF2OB (F, F) -F.

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

Japanese Patent Laid-Open No. 10-204016 Chinese Patent Application No. 1040999105 Chinese Patent Application No. 104130781 Chinese Patent Application No. 102633822

  The first challenge is high stability against heat and light, high clearing point (or high maximum temperature of nematic phase), low minimum temperature of liquid crystal phase, small viscosity, appropriate optical anisotropy, large dielectric anisotropy It is to provide a liquid crystalline compound satisfying at least one of physical properties such as an appropriate elastic constant and excellent compatibility with other liquid crystalline compounds. The object is to provide a compound which does not have a smectic phase and has a large elastic constant ratio compared to similar compounds. The second problem is that it contains this compound and has high stability to heat and light, high maximum temperature of nematic phase, low minimum temperature of nematic phase, small viscosity, appropriate optical anisotropy, large dielectric anisotropy Another object of the present invention is to provide a liquid crystal composition satisfying at least one of physical properties such as a large specific resistance and an appropriate elastic constant. An object of the present invention is to provide a liquid crystal composition having an appropriate balance regarding at least two physical properties. A third problem is to provide a liquid crystal display device comprising this composition and having a wide temperature range in which the device can be used, a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime. 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 the compound, and a liquid crystal display device including the composition.

In equation (1),
R ¹ X is alkyl having 1 to 10 carbons in which one or two hydrogens are replaced by 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 by halogen, tetrahydropyran- 2,5-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl, wherein ring A ¹ , ring A ² , ring A ⁴ , and ring A ⁵ are 1,4-cyclohexylene. May be;
Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently a single bond, —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 —;
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 each independently 0 or 1, and the sum of a, b, c, and d is 1 or 2.

  The first advantage is high stability to heat and light, high clearing point (or high maximum temperature of nematic phase), low minimum temperature of liquid crystal phase, small viscosity, appropriate optical anisotropy, large dielectric anisotropy It is to provide a liquid crystalline compound satisfying at least one of physical properties such as an appropriate elastic constant and excellent compatibility with other liquid crystalline compounds. It is to provide a compound that does not have a smectic phase and has a large elastic constant ratio compared to a similar compound (see Comparative Examples 1 and 2). The second advantage is that it contains this compound, high stability to heat and light, high maximum temperature of nematic phase, low minimum temperature of nematic phase, small viscosity, appropriate optical anisotropy, large dielectric anisotropy Another object of the present invention is to provide a liquid crystal composition satisfying at least one of physical properties such as a large specific resistance and an appropriate elastic constant. The advantage is to provide a liquid crystal composition having an appropriate balance regarding at least two physical properties. The third advantage is to provide a liquid crystal display device comprising this composition and having a wide temperature range in which the device can be used, a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime. 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. “Liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and does not have a liquid crystal phase, but adjusts physical properties of the composition such as maximum temperature, minimum temperature, viscosity, dielectric anisotropy. A generic 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 liquid crystal display panels and liquid crystal display modules. 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 ratio (content) of the liquid crystal compound is expressed as a percentage by weight (% by weight) based on the weight of the liquid crystal composition. This composition requires additives such as polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, and antifoaming agents. Added accordingly. The ratio (addition amount) of the additive is represented by a weight percentage (% by weight) based on the weight of the liquid crystal composition, similarly to the ratio of the liquid crystal compound. Weight parts per million (ppm) may be used. The ratio of the polymerization initiator or the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.

  The “clearing point” is a transition temperature between a liquid crystal phase and an isotropic phase in a liquid crystal compound. “Lower limit temperature of liquid crystal phase” is a transition temperature of a solid-liquid crystal phase (smectic phase, nematic phase, etc.) in a liquid crystal compound. The “maximum temperature of a nematic phase” is a transition temperature of a nematic phase to an isotropic phase in a mixture or liquid crystal composition of a liquid crystal compound and a mother liquid crystal, and may be abbreviated as “maximum temperature”. “Lower limit temperature of nematic phase” may be abbreviated as “lower limit temperature”. The expression “increasing dielectric anisotropy” means that when the composition has a positive dielectric anisotropy, the value increases positively, and the composition having a negative dielectric anisotropy When it is a thing, it means that the value increases negatively.

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

In the chemical formulas of the component compounds, the symbol of the terminal group R ¹ is used for a plurality of compounds. In these compounds, two groups represented by two arbitrary R ¹ may be the same or different. For example, there is a case where R ^{1 of} the compound (1-1) is ethyl and R ¹ of the compound (1-2) is ethyl. ^{R 1} is ethyl of the compound (1-1), another case ^{R 1} is propyl compound (1-2). This rule also applies to symbols such as R ¹¹ and Z ¹¹ . In compound (8), when i is 2, two rings D ¹ exist. In this compound, the two groups represented by the two rings D ¹ may be the same or different. When i is greater than 2, it also applies 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' is arbitrary. The expression “at least one 'A' may be replaced by 'B'” means that when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is 2 Even when there are more than two, it means that their positions can be selected without limitation. This rule also applies to the expression “at least one 'A' is replaced by 'B'”. The expression “at least one 'A' may be replaced with 'B', 'C', or 'D'" is used when any 'A' is replaced with 'B' When A 'is replaced with' C ', and when any' A 'is replaced with' D ', more than one' A 'can be' B ',' C ', and / or' D ' It means that the case where at least two are replaced is included. For example, “alkyl in which at least one —CH ₂ — may be replaced by —O— or —CH═CH—” includes alkyl, alkoxy, alkoxyalkyl, alkenyl, alkoxyalkenyl, alkenyloxyalkyl. Note that it is not preferable that two consecutive —CH ₂ — are replaced by —O— to form —O—O—. In alkyl and the like, it is not preferable that —CH ₂ — in the methyl moiety (—CH ₂ —H) is replaced with —O— to become —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 include cyclic alkyl. Linear alkyl is generally preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. The configuration of 1,4-cyclohexylene is preferably trans rather than cis for increasing the maximum temperature. 2-Fluoro-1,4-phenylene means the following two divalent groups. In the chemical formula, fluorine may be leftward (L) or rightward (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.

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. The compound represented by Formula (1).

In equation (1),
R ¹ X is alkyl having 1 to 10 carbons in which one or two hydrogens are replaced by 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 by halogen, tetrahydropyran- 2,5-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl, wherein ring A ¹ , ring A ² , ring A ⁴ , and ring A ⁵ are 1,4-cyclohexylene. May be;
Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently a single bond, —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 —;
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 each 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 alkyl having 1 to 10 carbons in which one or two hydrogens are replaced by 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 by 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 each independently a single bond, —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 —;
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 each 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−、−ＣＦ_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. In item 1 or 2, which is represented by any one of formula (1-1), formula (1-2), formula (1-3), formula (1-4), and formula (1-5) The described compound.

In the formula (1-1) to the formula (1-5),
R ¹ X is a C ^1-10 alkyl in which one or two hydrogens are replaced by 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 by fluorine or chlorine, or 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 a single bond, —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.

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 4. The compound according to any one of Items 1 to 3, which is represented by any one of Formula (1-1), Formula (1-3), and Formula (1-4).

In Formula (1-1), Formula (1-3), and Formula (1-4),
R ¹ X is a C ^1-10 alkyl in which one or two hydrogens are replaced by 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 by fluorine or chlorine, or tetrahydropyran-2 , 5-diyl and ring A ¹ and ring A ² may be 1,4-cyclohexylene;
Z ¹ , Z ² , and Z ³ are each independently a single bond, —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 4. The compound according to any one of Items 1 to 3, which is represented by any one of formulas (1-a) to (1-h).

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

Item 6. In the formula (1-a) to (1-h) according to item 5, R ¹ X is — (CH ₂ ) _h —CH ₂ F, and h is an integer of 0 to 9, The described compound.

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 4. The compound according to any one of Items 1 to 3, which is represented by any one of formulas (1-i) to (1-p).

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

Item 8. In the formula (1-i) to (1-p) according to item 7, R ¹ X is — (CH ₂ ) _h —CH ₂ F, and h is an integer of 1 to 9, The described compound.

Item 9. Item 9. A liquid crystal composition comprising 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 10. The liquid crystal composition according to item 9, further comprising at least one compound selected from the group of compounds represented by formulas (2) to (4).

In the equations (2) to (4),
R ¹¹ and R ¹² are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O—. Well, at least one hydrogen may be replaced by fluorine;
Ring B ¹ , Ring B ² , Ring B ³ , and Ring B ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene or pyrimidine-2,5-diyl;
Z ¹¹ , Z ¹² , and Z ¹³ are each independently a single bond, —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 11. The liquid crystal composition according to item 9 or 10, further comprising at least one compound selected from the group of compounds represented by formulas (5) to (7).

In equations (5) to (7),
R ¹³ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH ₂ — may be replaced by —O—, and at least one hydrogen is May be replaced by 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 in which at least one hydrogen may be replaced with 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 a single bond, —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 12. The liquid crystal composition according to any one of items 9 to 11, further comprising at least one compound selected from the group of compounds represented by formula (8).

In equation (8),
R ¹⁴ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH ₂ — may be replaced by —O—, and at least one hydrogen is May be replaced by fluorine;
X ¹² is —C≡N or —C≡C—C≡N;
Ring ^{D 1} is 1,4-cyclohexylene, at least one hydrogen replaced by or 1,4-phenylene with fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl Or pyrimidine-2,5-diyl, and when there are a plurality of rings D ¹ , they 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 Can 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 13. 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 formulas (9) to (15).

In the equations (9) to (15),
R ¹⁵ and R ¹⁶ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O—. Well, at least one hydrogen may be replaced by fluorine;
R ¹⁷ is hydrogen, fluorine, alkyl having 1 to 10 carbons, or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, 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 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, wherein at least one hydrogen may be replaced with fluorine, 4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl, the same when there are a plurality of ring E ¹ , ring E ² , ring E ³ , and ring E ⁴ May or may not be;
Ring E ⁵ and Ring E ⁶ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6. -Diyl;
^{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 when there are a plurality of 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, 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 consisting of a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a dye, and an antifoaming agent. Item 14. The liquid crystal composition according to any one of items 9 to 13, further contained.

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

  The present invention also includes the following items. (A) one selected from the group of a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a dye, and an antifoaming agent The above composition 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. (C) The above liquid crystal display element in which the operation mode of the liquid crystal display element is a TN mode, an ECB mode, an OCB mode, an IPS mode, or an FPA mode, and the driving method of the liquid crystal display element is an active matrix (AM) method .

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

1. Embodiment of Compound (1) The compound (1) of the present invention has a halogenated alkyl and a CF ₂ O bonding group. This CF ₂ O linking group is present 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 characteristic that it has a large optical anisotropy as compared with the compound described in Patent Document 1.

The first feature of the compound (1) is that it does not have a smectic phase. Even when the similar compound has a smectic phase, the compound (1) has a nematic 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 element becomes steep. This means that a large change in transmittance occurs due to a small voltage difference.

  For the smectic phase, refer to JP 2007-308707 A. Paragraph 0007 states that “modern commercial mixtures need to operate over a wide temperature range, so crystallization and smectic phase formation at low temperatures must be eliminated. Use of liquid crystal materials in the development of nematic mixtures One of the most important preconditions for the property is good solubility, and for this reason compounds with a high melting temperature and a tendency to form smectic phases are not suitable. " That is, it is preferable that no smectic phase exists.

A preferred example of compound (1) will be described. Terminal groups R ¹ X and X ¹ in compound (1), ring A ¹ , ring A ² , ring A ³ , ring A ⁴ , and ring A ⁵ , linking groups Z ¹ , Z ² , Z ³ , and Z ⁴ , And preferred examples of the substituents L ¹ and L ² also apply to the sub-formula of compound (1). In the compound (1), physical properties can be arbitrarily adjusted by appropriately combining these groups. Since there is no significant difference in the physical properties of the compound, the compound (1) may contain an isotope such as ² H (deuterium) and ¹³ C in an amount larger than the natural abundance. In addition, the definition of the symbol of the compound (1) is as described in item 1.

In the formula (1), R ¹ X is alkyl having 1 to 10 carbons in which one or two hydrogens are replaced by halogen.

R ¹ X is monohaloalkyl or dihaloalkyl. Preferred halogen is fluorine or chlorine. Preferred monohaloalkyl is 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 with chlorine.

Preferred dihaloalkyl is alkyl in which two hydrogens are replaced by fluorine or chlorine. Examples of _{difluoroalkyl, -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. 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 with 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, 1,4 with at least one hydrogen replaced with halogen -Phenylene, tetrahydropyran-2,5-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl, wherein ring A ¹ , ring A ² , ring A ⁴ , and ring A ⁵ are 1, 4-cyclohexylene may be sufficient.

Preferred ring A ¹ to ring 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 ring A ¹ to ring A ⁵ are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, or tetrahydropyran- 2,5-diyl. Particularly preferred ring A ¹ to ring 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 ring A ¹ to ring A ⁵ is 1,4-cyclohexylene, the clearing point is high and the viscosity is small. When at least one of these is 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine, the optical anisotropy is large and the orientational order parameter ) Is relatively large. When at least one of these is 1,4-phenylene in which at least one hydrogen is replaced by fluorine, the dielectric anisotropy is large.

In Formula (1), Z ¹ , Z ² , Z ³ , and Z ⁴ are independently a single bond, —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 —.

Preferred Z ¹ to Z ⁴ are a single bond, —COO—, —OCH ₂ —, —CF ₂ O—, or —CH ₂ CH ₂ —. Further preferred Z ¹ to Z ⁴ are a single bond, —COO—, —OCH ₂ —, or —CF ₂ O—. Particularly preferred Z ¹ to Z ⁴ are a single bond or —CF ₂ O—. 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 small, the dielectric anisotropy is large, and the maximum 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 desirable 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. Most preferred X ¹ is —OCF ₃ . When X ¹ is fluorine, the viscosity is small. 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 a combination of hydrogen and fluorine. Preferred L ¹ and L ² are fluorine and a combination of 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 the 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 preferable from the viewpoint of small viscosity. When the sum of a, b, c, and d is 2, compound (1) has four rings. This compound is preferable from the viewpoint of a high clearing point.

  Examples of preferred compound (1) are compounds (1-1) to (1-5) described in item 3. More preferred examples of the 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.

  The compound (1-1) is preferable from the viewpoint of high stability to heat and light and small viscosity. The compound (1-3) is preferable from the viewpoints of a high clearing point and excellent compatibility. The compound (1-4) is preferable from the viewpoint of a high clearing point and a 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 organic synthetic chemistry methods. Methods for introducing the desired linking group, ring, or terminal group into the starting material are described by 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.

2-1. Generation of linking group Z A scheme is first shown for the method of generating linking groups Z ¹ to Z ⁴ . Next, the reaction will be described. In this scheme, MSG ¹ (or MSG ² ) is a monovalent organic group having at least one ring. The monovalent organic groups represented by a 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. A compound having —OCO— can also be synthesized by this synthesis method. The same applies to other asymmetrical linking groups.

(1) Generation of a single bond

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

(2) Formation of —COO—

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

(3) Formation 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 (1C) is synthesized by reacting compound (18) with compound (19) in the presence of a base such as potassium carbonate.

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) Formation of —CF ₂ O—

Compound (1B) is treated with a sulfurizing agent such as Lawson's reagent to obtain compound (20). The compound (20) is fluorinated with a hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize a compound (1D) having —CF ₂ O—. See M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1D) can also be synthesized by fluorinating compound (1B) with (diethylamino) sulfur trifluoride (DAST). See WH Bunnelle et al., J. Org. Chem. 1990, 55, 768. These linking groups can also be generated by the method described in Peer. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480.

(5) Formation of —CH ₂ CH ₂ —

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

(6) Formation of — (CF ₂ ) ₂ —
According to the method described in J. Am. Chem. Soc., 2001, 123, 5414., a diketone (—COCO—) is fluorinated with sulfur tetrafluoride in the presence of a hydrogen fluoride catalyst to produce — (CF ₂ ). A compound having _2- is obtained.

(7) Generation of -CF = CF-

  The compound (13) is treated with n-butyllithium and then reacted with tetrafluoroethylene to obtain the compound (22). Compound (12) is treated with n-butyllithium and then reacted with compound (22) to synthesize compound (1F).

(8) Formation of —C≡C—

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

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) Formation of — (CH ₂ ) ₄ —

Using phosphonium salt (24) instead of phosphonium salt (21), a compound having — (CH ₂ ) ₂ —CH═CH— is obtained according to the method of item (5). This is hydrogenated in the presence of a catalyst such as palladium carbon to synthesize compound (1H).

(10) Formation of —CH ₂ CH═CHCH ₂ —

  A phosphorus ylide is prepared by allowing a base such as potassium t-butoxide to act on a phosphonium salt (25) synthesized by a known method. This is reacted with aldehyde (26) to synthesize compound (1I).

2-2. Formation of Ring A ¹ to Ring A ⁵ A synthesis method for ring A ¹ to ring A ⁵ in compound (1) will be described. 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 having 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 any position of the alkyl, it can be synthesized in the same manner.

  The halogenated alkyl halide (31) is reacted with triphenylphosphine to obtain the phosphonium salt (32). The phosphorus ylide generated by treating compound (32) with a base such as potassium t-butoxide is reacted with aldehyde (16). The obtained olefin (33) is hydrogenated in the presence of a catalyst such as palladium carbon to synthesize the compound (1J).

  Compound (1K) can also be synthesized by halogenating compound (34) synthesized by a known method with (diethylamino) sulfur trifluoride (DAST), triphenylphosphine and carbon tetrahalide.

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

  This composition preferably contains compound (1) as component A and further contains a liquid crystalline compound selected from 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). The composition may contain other liquid crystal compounds different from the compounds (2) to (15). When preparing this composition, it is preferable to select components B, C, D, and E in consideration of the sign of dielectric anisotropy and the magnitude. A composition with appropriately selected ingredients has high stability to heat and light, high maximum temperature, low minimum temperature, low viscosity, appropriate optical anisotropy (ie, large optical anisotropy or small optical anisotropy) , Large dielectric anisotropy, large specific resistance, and appropriate elastic constant (ie, large elastic constant or small elastic constant).

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

  Component B has a small dielectric anisotropy. Component B is close to neutrality. Compound (2) has an effect of decreasing the viscosity or adjusting the optical anisotropy. Compounds (3) and (4) have the effect of increasing the temperature range of the nematic phase by increasing the maximum temperature or adjusting the optical anisotropy.

  As the content of component B is increased, the viscosity of the composition decreases, but the dielectric anisotropy decreases. Therefore, as long as the threshold voltage requirement of the element is satisfied, the content is preferably large. When preparing a composition for a mode such as IPS or 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. Preferable examples of 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 alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which 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 very excellent in stability to heat and light, and is used when preparing a composition for a mode such as IPS, FFS, OCB. The content of Component C is suitably in the range of 1% to 99% by weight based on the weight of the liquid crystal composition, preferably in the range of 10% to 97% by weight, more preferably in the range of 40% to 95%. % Range. When component C is added to a composition having a negative dielectric anisotropy, the content of component C is preferably 30% by weight or less. By adding the component C, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the device can be adjusted.

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

  Since component D has a positive dielectric anisotropy and a large value, it is used when preparing a composition for a mode such as the TN mode. By adding this component D, the dielectric anisotropy of the composition can be increased. Component D has the effect of expanding 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 the TN mode, the content of component D is suitably in the range of 1% to 99% by weight, preferably 10% by weight, based on the weight of the liquid crystal composition. To 97% by weight, more preferably 40% to 95% by weight. When component D is added to a composition having a negative dielectric anisotropy, the content of component D is preferably 30% by weight or less. By adding component D, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the device can be adjusted.

Component E is compounds (9) to (15). These compounds have phenylene in which the lateral position is substituted with two halogens, such as 2,3-difluoro-1,4-phenylene. Preferred examples of component E include 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). In these compounds, R ¹⁵ and R ¹⁶ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH ₂ — is —O—. And at least one hydrogen may be replaced by fluorine; R ¹⁷ is hydrogen, fluorine, alkyl having 1 to 10 carbons, or alkenyl having 2 to 10 carbons, and the alkyl and In alkenyl, at least one —CH ₂ — may be replaced with —O— and at least one hydrogen may be replaced with fluorine.

  Component E has a large negative dielectric anisotropy. Component E is used when preparing a composition for a mode such as IPS, VA, or PSA mode. As the content of component E is increased, the dielectric anisotropy of the composition increases negatively, but the viscosity increases. Therefore, as long as the threshold voltage requirement 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 for sufficient voltage driving.

  Among the components E, since the compound (9) is a bicyclic compound, it has an effect of decreasing the viscosity, adjusting the optical anisotropy, or increasing the dielectric anisotropy. Since the compounds (10) and (11) are tricyclic compounds, they have the effect of increasing the maximum 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, or PSA mode, the content of component E is preferably 40% by weight or more, more preferably 50% by weight based on the weight of the liquid crystal composition. % To 95% by weight. When component E is added to a composition having a positive dielectric anisotropy, the content of component E is preferably 30% by weight or less. By adding the component E, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the device can be adjusted.

  High stability to heat and light, high maximum temperature, low minimum temperature, low viscosity, appropriate optical anisotropy, large dielectric anisotropy by appropriately combining components B, C, D and E described above A liquid crystal composition satisfying at least one of physical properties such as property, large specific resistance, and appropriate elastic constant can be prepared. If necessary, a liquid crystal compound different from the components B, C, D, and E may be added.

3-2. Additive The liquid crystal composition is prepared by a known method. For example, the component compounds are mixed and dissolved in each other by heating. Depending on the application, additives may be added to the composition. Examples of the additive include a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a dye, and an antifoaming agent. Such additives are well known to those skilled in the art and are described in the literature.

  In a liquid crystal display element 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 polymerizing the polymerizable compound by irradiating ultraviolet rays with a voltage applied between the electrodes. By this method, an appropriate pretilt is achieved, and thus a device with a shortened response time and improved image burn-in is produced.

  Preferred examples of the polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), and vinyl ketone. Further preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. Further preferred examples include compounds having both acryloyloxy and methacryloyloxy.

Further 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; t and u are independently 1 to 10 It is an integer. L ²¹ to L ²⁶ are independently hydrogen or fluorine, and when there are a plurality of L ²⁵ and L ²⁶ , they may be the same or different; L ²⁷ and L ²⁸ are independently Hydrogen, fluorine, or methyl.

  The polymerizable compound can be polymerized quickly by adding a polymerization initiator. By optimizing the reaction temperature, the amount of the remaining polymerizable compound can be reduced. Examples of photo radical polymerization initiators are BASF's Darocur series to TPO, 1173, and 4265, and Irgacure series to 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850. , 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-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyl Dimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate, benzophenone / methyltriethanolamine mixture It is.

  After adding a radical photopolymerization initiator to the liquid crystal composition, the polymerization can be carried out by irradiating ultraviolet rays with an electric field applied. However, an unreacted polymerization initiator or a decomposition product of the polymerization initiator may cause display defects such as image burn-in on the device. In order to prevent this, photopolymerization may be performed without adding a polymerization initiator. A preferable wavelength of light to be irradiated is in a range of 150 nm to 500 nm. A more preferred wavelength is in the range of 250 nm to 450 nm, and a most preferred wavelength is in the range of 300 nm to 400 nm.

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

The optically active compound has an effect of preventing reverse twisting by inducing a helical structure in liquid crystal molecules to give a necessary twist angle. The helical 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 helical pitch. Preferable 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 alkyl having 1 to 10 carbons.

  Antioxidants are effective for maintaining a large voltage holding ratio. Preferred examples of the antioxidant 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 maximum temperature. Preferred examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Specific examples 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).

  Light stabilizers such as sterically hindered amines are preferred in order to maintain a large voltage holding ratio. 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 preferred example is IRGAFOS 168 (trade name; BASF). A dichroic dye such as an azo dye or an anthraquinone dye is added to the composition in order to adapt to a GH (guest host) mode device. Antifoaming agents are effective for preventing foaming. Preferable examples of the antifoaming agent are dimethyl silicone oil, methylphenyl silicone oil and the like.

In the compound (AO-1), R ⁴⁰ is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, —COOR ⁴¹ , or —CH ₂ CH ₂ COOR ⁴¹ , where R ⁴¹ is 1 carbon atom. To 20 alkyls. In the compounds (AO-2) and (AO-5), ^R42 is alkyl having 1 to 20 carbons. In the 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, 3.

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

  This composition is also suitable for a nematic curvilinear aligned phase (NCAP) element, in which the composition is microencapsulated. This composition can also be used for polymer dispersed liquid crystal display elements (PDLCD) and polymer network liquid crystal display elements (PNLCD). In these compositions, a large amount of a polymerizable compound is added. On the other hand, when the addition amount of the polymerizable compound is 10% by weight or less based on the weight of the liquid crystal composition, a PSA mode liquid crystal display element is produced. A desirable ratio is in the range of 0.1% by weight to 2% by weight. A more desirable ratio is in the range of 0.2% to 1.0% by weight. A PSA mode element can be driven by a driving method such as an active matrix or a passive matrix. Such an element can be applied to any of a reflection type, a transmission type, and a transflective type.

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

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 properties of the compound and composition and the characteristics of the device were measured by the following methods.

NMR analysis: For measurement, DRX-500 manufactured by Bruker BioSpin Corporation was used. ^In the measurement of ¹ H-NMR, the sample was dissolved in a deuterated solvent such as CDCl ₃ and measured under the conditions of room temperature, 500 MHz, and 16 integrations. Tetramethylsilane was used as an internal standard. ^{For 19} 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 is a singlet, d is a doublet, t is a triplet, q is a quartet, quint is a quintet, sex is a sextet, m is a multiplet, and br is broad.

  Gas chromatographic analysis: A GC-2010 gas chromatograph manufactured by Shimadzu Corporation was used for measurement. As the column, 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 vaporizing 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. For the recorder, a GC Solution system manufactured by Shimadzu Corporation was used.

  HPLC analysis: Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used for 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. As an eluent, acetonitrile and water were appropriately mixed and used. As a detector, a UV detector, an RI detector, a CORONA detector or the like was appropriately used. When a UV detector was used, the detection wavelength was 254 nm. A sample was dissolved in acetonitrile to prepare a 0.1 wt% solution, and 1 μL of this solution was introduced into the sample chamber. As a recorder, C-R7 Plus manufactured by Shimadzu Corporation was used.

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

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

  When a sample in which a compound was mixed with mother liquid crystals was used, an extrapolated value was calculated according to the following formula, and this value was described. <Extrapolated value> = (100 × <Measured value of sample> − <Weight% of mother liquid crystal> × <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 wt%.

  The ratio of the compound and the mother liquid crystal (A) was 15% by weight: 85% by weight. When crystals (or smectic phases) are precipitated at this rate 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 phases) did not precipitate at 25 ° C. in the order of weight%. Unless otherwise specified, the ratio of the compound to the mother liquid crystal (A) was 15% by weight: 85% by weight.

  Measuring method: Physical properties were measured by the following methods. Many of these are described in the JEITA standard (JEITA ED-2521B) established by the Japan Electronics and Information Technology Industries Association (JEITA). A modified version of this was also used. No thin film transistor (TFT) was attached to the TN device used for the measurement.

(1) Phase structure: A sample was placed on a hot plate (Mettler FP-52 type hot stage) of a melting point measuring apparatus 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 the measurement, a scanning calorimeter manufactured by Perkin Elmer, Diamond DSC system, or a high-sensitivity differential scanning calorimeter manufactured by SII Nanotechnology, Inc., X-DSC7000 was used. The temperature of the sample was raised and lowered at a rate of 3 ° C./min, the end point of the endothermic peak or exothermic peak accompanying the phase change of the sample was obtained by extrapolation, and the transition temperature was determined. The melting point and polymerization initiation temperature of the compound were also measured using this apparatus. 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 liquid crystal phase”. The temperature at which the compound transitions from the liquid crystal phase to the liquid may be abbreviated as “clearing point”.

The crystal was represented as C. When the types of crystals could be distinguished, each was represented as C ₁ or C ₂ . The smectic phase is represented as S and the nematic phase is represented as N. In the smectic phase, when a smectic A phase, a smectic B phase, a smectic C phase, or a smectic F phase can be distinguished, they are represented as S _A , S _B , S _C , or S _F , respectively. The liquid (isotropic) was designated as I. The transition temperature is expressed as “C 50.0 N 100.0 I”, for example. 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 a mother liquid crystal and a 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 sample in glass bottle. The glass bottle was stored in a freezer at −10 ° C. or −20 ° C. for a certain period, and then it was observed whether crystals or smectic phases were precipitated.

(4) Maximum temperature of nematic phase (T _NI or NI; ° C.): A sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when a part of the sample changed from a nematic phase to an isotropic liquid. When the sample was a mixture of compound (1) and mother liquid crystals, it was indicated by the symbol _TNI . When the sample was a mixture of compound (1) and compounds such as components B, C and D, it was 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, when the sample remained in the nematic phase at −20 ° C. and changed to a crystalline or smectic phase at −30 ° C., the _TC was described as <−20 ° 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 performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). I followed. A sample was put in a TN device having a twist angle of 0 ° and a distance (cell gap) between two glass substrates of 5 μm. A voltage was applied to this device in steps of 0.5 V in the range of 16 V to 19.5 V. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular 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 value of rotational viscosity was obtained from these measured values and the paper by M. Imai et al., Formula (8) on page 40. The value of dielectric anisotropy necessary for this calculation was determined 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 performed with an Abbe refractometer using light having a wavelength of 589 nm and a polarizing plate attached to the eyepiece. After rubbing the surface of the main prism in one direction, the sample was dropped on the main prism. The refractive index (n‖) was measured when the direction of polarized light was parallel to the direction of rubbing. The refractive index (n⊥) was measured when the direction of polarized light was perpendicular to the direction of rubbing. The value of optical anisotropy (Δn) was calculated from the equation: Δn = n∥−n⊥.

(9) Dielectric anisotropy (Δε; measured at 25 ° C.): A sample was put in a TN device in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. Sine waves (10 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε‖) in the major axis direction of the liquid crystal molecules was measured. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured. The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.

(10) Elastic constant (K; measured at 25 ° C .; pN): An HP4284A LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd. was used for the measurement. A sample was put in a horizontal alignment element in which the distance between two glass substrates (cell gap) was 20 μm. A charge of 0 to 20 volts was applied to the device, and the capacitance and applied voltage were measured. Using the formula (2.98) and formula (2.101) on page 75 of “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun), the values of the measured capacitance (C) and applied voltage (V) are calculated. Fitting was performed, and values of K ₁₁ and K ₃₃ were obtained from the equation (2.99). Then the equation (3.18) on page 171, to calculate the _{K 22} using the values of _{K 11} and _{K 33} was determined previously. The elastic constant K was expressed as an average value of K ₁₁ , K ₂₂ , and K ₃₃ thus obtained.

(11) Threshold voltage (Vth; measured at 25 ° C .; V): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. A sample was put in a normally white mode TN device in which the distance (cell gap) between two glass substrates was 0.45 / Δn (μm) and the twist angle was 80 degrees. The voltage (32 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 10V by 0.02V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount reached the maximum and the transmittance was 0% when the light amount was the minimum. The threshold voltage was expressed as a voltage when the transmittance reached 90%.

(12) Voltage holding ratio (VHR-1; measured at 25 ° C .;%): The TN device used for the measurement had a polyimide alignment film, and the distance between two glass substrates (cell gap) was 5 μm. . This element was sealed with an adhesive that was cured by ultraviolet rays after the sample was placed. The device was charged by applying a pulse voltage (5 V, 60 microseconds) at 25 ° C. The decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined. Area B was the area when it was not attenuated. The voltage holding ratio was expressed as a percentage of area A with respect to area B.

(13) Voltage holding ratio (VHR-2; measured at 80 ° C .;%): The voltage holding ratio was measured by the above method except that it was measured at 80 ° C. instead of 25 ° C. The obtained result was shown by the symbol VHR-2.

(14) Specific resistance (ρ; measured at 25 ° C .; Ωcm): A sample (1.0 mL) was poured into a container equipped with electrodes. A DC voltage (10 V) was applied to the container, and the DC current after 10 seconds was measured. The specific resistance was calculated from the following equation. (Resistivity) = {(Voltage) × (Capacity of container)} / {(DC current) × (Dielectric constant of vacuum)}.

(15) Response time (τ; measured at 25 ° C .; ms): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. The low-pass filter was set to 5 kHz. A sample was put in a normally white mode TN device in which the distance between two glass substrates (cell gap) was 5.0 μm and the twist angle was 80 degrees. A rectangular wave (60 Hz, 5 V, 0.5 seconds) was applied to this element. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. It was considered that the transmittance was 100% when the light amount was the maximum, and the transmittance was 0% when the light amount was the 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 to change the transmittance from 10% to 90%. The response time was expressed as the sum of the rise time and the fall time thus obtained.

  Raw material: Solmix (registered trademark) A-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (1.1%), and was obtained from Nippon Alcohol Sales 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 for 12 hours under a nitrogen stream. The reaction mixture was washed with a saturated aqueous sodium chloride solution (200 mL) and water (200 mL) in this 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 needle 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. 9 g) was added to toluene (100 mL) under a stream of nitrogen. The mixture was refluxed for 3 hours while removing water by azeotropic distillation. After returning to room temperature, it was washed with a saturated aqueous sodium hydrogen carbonate solution (100 mL), water (100 mL), and a saturated aqueous sodium chloride solution (100 mL) in this 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-4) (5.6 g, 20.1 mmol) as colorless needle 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, 28.7 mmol), PEPPSI-IPr (0.10 g, 0.15 mmol), water (10 mL), ethanol (50 mL) and toluene (50 mL) were refluxed under a nitrogen stream for 3 hours. The reaction mixture was washed with a saturated aqueous sodium chloride solution (100 mL) and water (100 mL) in this 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 needle 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 (50 mL) of the mixture was stirred at 90 ° C. for 3 hours under a nitrogen stream. The reaction mixture was washed with a saturated aqueous sodium hydrogen carbonate solution (100 mL), water (100 mL), and a saturated aqueous sodium chloride solution (100 mL) in this 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-7) (4.6 g, 9.1 mmol) as colorless needle crystals.

Step 5: 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 stirred for 1 hour. A solution of compound (S-7) (4.6 g, 9.1 mmol) in tetrahydrofuran (20 mL) was added dropwise, gradually returned to room temperature, and stirred overnight. The reaction mixture was poured into saturated aqueous ammonium chloride (100 mL) and extracted with toluene (3 × 200 mL). 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.

Step 6: 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) and A mixture of ethanol (20 mL) was stirred at room temperature under a hydrogen atmosphere. The catalyst was filtered off and concentrated under reduced pressure. The residue was purified by silica gel chromatography (heptane: ethyl acetate = 20: 1) and recrystallization (heptane: ethanol = 1: 1) to give compound (1-4-059) (0.4 g, 0.6 mmol) Was obtained as colorless needle crystals.

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

  Phase transition temperature: C 48.6 N 105.8 Maximum temperature (NI) = 88.4 ° C; dielectric 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) Isopropylmagnesium chloride-lithium chloride complex (1.3M, 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 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 (500 mL) and extracted with ethyl acetate (3 × 200 mL). The combined organic layers were washed with saturated aqueous sodium chloride solution (500 mL) and water (500 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give compound (T-3) as 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 mixture was refluxed for 2 hours while removing water by azeotropic distillation. The reaction mixture was cooled to room temperature, and then washed with water (500 mL), a saturated aqueous sodium hydrogen carbonate solution (500 mL), and water (500 mL) in this order. 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), 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. 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 needle crystals.

Fourth Step: 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 for 2 hours under a nitrogen stream. The reaction mixture was washed with water (200 mL), saturated aqueous sodium hydrogen carbonate solution (200 mL), and water (200 mL) in this order. This solution was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain compound (T-7) (10.1 g, 22.6 mmol) as a colorless solid.

Step 5: 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 stirred for 1 hour. A solution of compound (T-7) (10.1 g, 22.6 mmol) in tetrahydrofuran (25 mL) was added dropwise, gradually returned to room temperature, and stirred overnight. The reaction mixture was poured into saturated aqueous ammonium chloride (200 mL) and extracted with toluene (3 × 200 mL). 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 for 4 hours under a nitrogen stream. The reaction mixture was washed with water (200 mL), saturated aqueous sodium hydrogen carbonate solution (200 mL), and water (200 mL) in this order. This 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. Aqueous sodium hydroxide (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 (3 x 200 mL). 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 needle crystals.

Step 7: 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 stirred for 1 hour. A solution of compound (T-10) (1.8 g, 3.9 mmol) in tetrahydrofuran (20 mL) was added dropwise, gradually returned to room temperature, and stirred overnight. The reaction mixture was poured into saturated aqueous ammonium chloride (100 mL) and extracted with toluene (3 × 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.

Step 8: Synthesis of (1-4-010) Compound (T-12) (1.4 g, 2.8 mmol) and tosyl hydrazide (6.3 g, 33.9 mmol) were 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 further refluxed for 4 hours. The reaction mixture was poured into water (80 mL) and extracted with toluene (3 × 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) and recrystallization (heptane: ethanol = 1: 1) to give compound (1-4-010) (0.7 g, 1.3 mmol) Was obtained as colorless needle crystals.

¹ H-NMR (CDCl ₃ ; δ ppm): 7.73 (d, J = 8.4 Hz, 2H), 7.68 (d, J = 8.4 Hz, 2H), 7.54 (d, J = 8 .2 Hz, 2H), 7.32 (d, J = 8.2 Hz, 2H), 6.97 (dd, J = 6.1, 7.8 Hz, 2H), 4.46 (td, J = 6. 3, 47.3 Hz, 2H), 2.53 (tt, J = 3.2, 12.1 Hz, 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 (δ ppm; CDCl ₃ ): −66.62 (s, 2F), −133.17 (dd, J = 8.0, 20.3 Hz, 2F), −164.31 (tt, J = 6.0, 21.2 Hz, 1F), -218.45 (tt, J = 25.2, 47.3 Hz, 1F).

  Phase transition temperature: C 63.6 N 177.4 Maximum temperature (NI) = 148.4 ° C .; dielectric anisotropy (Δε) = 16.57; optical anisotropy (Δn) = 0.157; viscosity (η) = 57.9 mPa · s.

  The following compounds can be synthesized with reference 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 terminal 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 H-NMR (CDCl ₃ ; δ ppm): 7.54 (d, J = 8.2 Hz, 2H), 7.48 (d, J = 4.5 Hz, 2H), 7.42 (d, J = 12 .6 Hz, 1H), 7.59 (d, J = 8.2 Hz, 2H), 7.27 (s, 1H), 7.00 (dd, J = 6.3, 7.6 Hz, 2H), 2 .67 (t, J = 7.6 Hz, 2H), 1.66 (quin, J = 7.6 Hz, 2H), 1.37-1.34 (m, 4H), 0.91 (t, J = 6.9 Hz, 3H). ¹⁹ F-NMR (δ ppm; CDCl ₃ ): −62.18 (t, J = 26.7 Hz, 2F), −111.16 (dt, J = 10.7, 26.7 Hz, 2F), −117. 28--117.33 (m, 1F), -132.90 (dd, J = 7.6, 19.8 Hz, 2F), -163.58 (tt, J = 6.1, 21.4 Hz, 1F) ). Phase transition temperature: C 61.1 SA 62.8 N 121.8

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) exhibited a smectic phase (S _A ) in the range of 61.1 ° C. to 62.8 ° C. On the other hand, it was found that the compound (1-4-059) is excellent in that it exhibits only a nematic phase and does not have a smectic phase (S _A ).

[Comparative Example 2]
The following compound (C-2) was selected for comparison. This is because the left terminal 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 H-NMR (CDCl ₃ ; δ ppm): 7.73 (d, J = 8.5 Hz, 2H), 7.68 (d, J = 8.5 Hz, 2H), 7.54 (d, J = 8 .2 Hz, 2H), 7.32 (d, J = 8.2 Hz, 2H), 6.97 (dd, J = 6.1, 7.9 Hz, 2H), 2.53 (tt, J = 3. 1, 12.1 Hz, 1H), 1.91 (t, J = 14.9 Hz, 4H), 1.53-1.46 (m, 2H), 1.33-1.22 (m, 9H), 1.11-1.04 (m, 2H), 0.90 (t, J = 7.1 Hz, 3H). ¹⁹ F-NMR (δ ppm; CDCl ₃ ): −66.62 (s, 2F), −133.19 (dd, J = 8.5, 21.2 Hz, 2F), −164.33 (tt, J = 6.0, 21.3 Hz, 1F). Phase transition temperature: C 51.4 SC 97.5 SA 97.5 N 184.3 Elastic constant ratio (K ₃₃ / K ₁₁ ) = 1.99 (K ₃₃ : Bend elastic constant, K ₁₁ : Spray elastic constant).

Table 2 summarizes the physical properties 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, it was found that the compound (1-4-010) is excellent in that it exhibits only a nematic phase and does not have a smectic phase. It was found that the compound (1-4-010) was also excellent in terms of a large elastic constant ratio (K ₃₃ / K ₁₁ ).

2. Composition Examples Examples illustrate the compositions of the present invention in detail. The present invention includes a mixture of the composition of Use Example 1 and the composition of Use Example 2. The present invention also includes a mixture in which at least two of the compositions of the use examples are mixed. The compounds in the use examples were represented by symbols based on the definitions in Table 3 below. In Table 3, the configuration regarding 1,4-cyclohexylene is trans. In the usage examples, the number in parentheses after the symbol represents the chemical formula to which the compound belongs. The symbol (−) means other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition. Finally, the physical properties 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-HBBBXB (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-HBBBXB (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.
The pitch when Op-05 was added to the above composition at a ratio of 0.25% by weight 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-HBBBXB (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-HBBBXB (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-HBBBXB (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 properties. Liquid crystal compositions containing this compound can be widely used for liquid crystal display elements used in personal computers, televisions and the like.

Claims (5)

Formula (1-a) from (1-f) any one represented is Ru of compounds of.

In formulas (1-a) to (1-f) , R ¹ X is alkyl having 1 to 10 carbons in which one hydrogen is replaced by fluorine; X ¹ is fluorine, —CF ₃ , or — OCF ₃ ; L ¹ and L ² are independently hydrogen or fluorine. The formulas (1-a) to (1-f ) according to claim 1 , wherein R ¹ X is-(CH ₂ ) _h -CH ₂ F, and h is an integer of 0 to 9. 1. The compound according to 1 . Formula (1-i) from (1-n) any one represented is Ru of compounds of.

In formulas (1-i) to (1-n) , R ¹ X is alkyl having 1 to 10 carbons in which one hydrogen is replaced by fluorine; X ¹ is fluorine, —CF ₃ , or — OCF ₃ ; L ¹ and L ² are independently hydrogen or fluorine. The formula (1-i) to (1-n ) according to claim 3 , wherein R ¹ X is-(CH ₂ ) _h -CH ₂ F, and h is an integer of 1 to 9. 3. The compound according to 3 . A liquid crystal composition comprising at least one compound according to any one of claims 1 to 4 .