JP2011184388A - Indole ring-bearing compound, liquid crystal composition, and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystalline compound stable to heat and light, etc., turning to a nematic phase over a wide temperature range, low in viscosity, having appropriate optical anisotropy, and further, having high dielectric constant anisotropy and high compatibility with other liquid crystalline compounds. <P>SOLUTION: The liquid crystalline compound is a compound (1) of formula (1). For example, in the formula (1), R<SP>0</SP>and R<SP>1</SP>are each independently 1C-20C alkyl; rings A<SP>1</SP>to A<SP>8</SP>are each independently a 1,4-cyclohexylene group or 1,4-phenylene group; Z<SP>1</SP>to Z<SP>8</SP>are each independently a single bond, -CH<SB>2</SB>CH<SB>2</SB>-, -CH=CH-, -C≡C-, -COO-, -OCO-, -CF<SB>2</SB>O-, -OCF<SB>2</SB>-, -CH<SB>2</SB>O-, -OCH<SB>2</SB>- or -CF=CF-; and L<SP>1</SP>to L<SP>5</SP>are each independently H or a halogen atom. <P>COPYRIGHT: (C)2011,JPO&INPIT

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 an indole ring, a liquid crystal composition having a nematic phase containing this compound, and a liquid crystal display device containing this composition.

  A display element using a liquid crystal compound (in this application, the term liquid crystal compound is used as a general term for a compound having a liquid crystal phase and a compound having no liquid crystal phase but useful as a component of a liquid crystal composition). Is widely used in displays such as clocks, calculators, word processors. These display elements utilize the optical anisotropy and dielectric anisotropy of liquid crystalline compounds.

  A liquid crystal display element typified by a liquid crystal display panel, a liquid crystal display module, etc. utilizes the optical anisotropy, dielectric anisotropy, etc. of the liquid crystal compound. , PC (phase change) mode, TN (twisted nematic) mode, STN (super twisted nematic) mode, BTN (bistable twisted nematic) mode, ECB (electrically controlled birefringence) mode, OCB (optically compensated bend) mode, IPS (in) Various modes such as a -plane switching) mode, a VA (vertical alignment) mode, and a PSA (polymer sustained alignment) mode are known.

These liquid crystal display elements contain a liquid crystal composition having appropriate physical properties. In order to improve the characteristics of the liquid crystal display element, the liquid crystal composition preferably has appropriate physical properties. The general physical properties necessary for the liquid crystal compound that is a component of the liquid crystal composition are required to have the following characteristics (1) to (6). That is,
(1) being chemically stable and physically stable;
(2) having a high clearing point (liquid crystal phase-isotropic phase transition temperature);
(3) The lower limit temperature of the liquid crystal phase (nematic phase, smectic phase, etc.), especially the lower limit temperature of the nematic phase is low,
(4) having appropriate optical anisotropy;
(5) having an appropriate amount of dielectric anisotropy;
(6) Excellent compatibility with other liquid crystal compounds,
It is.

When a composition containing a chemically and physically stable liquid crystalline compound as in (1) is used for a liquid crystal display device, the voltage holding ratio can be increased.
In the composition containing a liquid crystal compound having a high clearing point or a low lower limit temperature of the liquid crystal phase as in (2) and (3), the temperature range of the nematic phase is wide, so that the device is used in a wide temperature range. It becomes possible.

  Furthermore, in the case of a display element using a composition containing a compound having an appropriate optical anisotropy as in (4), the contrast of the element can be improved. Depending on the element design, the optical anisotropy needs to be small to large. Recently, methods for improving the response speed by reducing the cell thickness have been studied, and accordingly, a liquid crystal composition having a large optical anisotropy is also required.

As is well known, the threshold voltage (V _th ) is expressed by the following equation (HJ Deuling, et al., Mol. Cryst. Liq. Cryst., 27 (1975) 81).

V _th = π (K / ε ₀ Δε) ^1/2

In the above equation, K is an elastic constant, and ε ₀ is a vacuum dielectric constant. As can be seen from the equation, there are two methods for decreasing _Vth , either increasing the value of Δε (dielectric anisotropy) or decreasing K. However, since it is still difficult to actually control K with the current technology, the current situation is that the requirement is usually dealt with using a liquid crystal material having a large Δε. Under such circumstances, as in (5), development of a liquid crystal compound having an appropriate dielectric anisotropy, particularly a liquid crystal compound having a large dielectric anisotropy, has been actively conducted.

  The liquid crystal compound is generally used as a composition prepared by mixing with many other liquid crystal compounds in order to develop characteristics that are difficult to be exhibited by a single compound. Therefore, it is preferable that the liquid crystalline compound used for the display element has good compatibility with other liquid crystalline compounds as in (6). In addition, since the display element may be used in a wide temperature range including below freezing point, it may be preferable that the display element is a compound showing good compatibility from a low temperature range.

  An example in which a compound having an indole ring is used as an additive in a liquid crystal display element (Patent Document 1) and an example in which a compound having an indole ring is used as a polarizing plate, an optical filter, a dye, etc. (Patent Documents 2, 3, and 4) have been reported. However, there is no example using a compound having an indole ring as a liquid crystal compound.

JP-A-7-53962 JP 2008-75015 A International Publication No. 2006/109618 Pamphlet International Publication No. 2004/069394 Pamphlet

  The first object of the present invention is to have stability against heat, light, etc., to become a nematic phase in a wide temperature range, to have a low viscosity, to have appropriate optical anisotropy, and to have a large dielectric anisotropy And a liquid crystal compound having excellent compatibility with other liquid crystal compounds, and particularly having a large dielectric anisotropy and excellent compatibility with other liquid crystal compounds It is.

  The second object of the present invention is to have stability against heat, light, etc., low viscosity, suitable optical anisotropy, large dielectric anisotropy, low threshold voltage, And a liquid crystal composition containing the compound and satisfying at least one of the characteristics that the upper limit temperature of the nematic phase (nematic phase-isotropic phase transition temperature) is high and the lower limit temperature of the nematic phase is low. Is to provide. Furthermore, it is to provide a liquid crystal composition having an appropriate balance regarding at least two characteristics.

  A third object of the present invention is to provide a liquid crystal display element containing a liquid crystal composition, which has a short response time, low power consumption and driving voltage, a large contrast, and can be used in a wide temperature range. It is.

The present invention provides the following liquid crystal compound, liquid crystal composition, and liquid crystal display device containing the liquid crystal composition. In the following, preferred examples of the terminal group, ring, bonding group and the like in the compound represented by the formula (1) will be described.

この式において、Ｒ^０およびＲ^１は独立して、水素、ハロゲン、または炭素数１〜２０のアルキルであり、このアルキルにおいて、任意の−ＣＨ_２−は−Ｏ−または−Ｓ−で置き換え換えられてもよく、任意の−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく、これらにおいて、任意の水素はハロゲンで置き換えられてもよく；環Ａ^１、環Ａ^２、環Ａ^３、環Ａ^４、環Ａ^５、環Ａ^６、環Ａ^７、および環Ａ^８は独立して、１，４−シクロヘキシレン、１，３−ジオキサン−２，５−ジイル、１，４−フェニレン、または任意の水素がハロゲンで置き換えられた１，４−フェニレンであり；Ｚ^１、Ｚ^２、Ｚ^３、Ｚ^４、Ｚ^５、Ｚ^６、Ｚ^７、およびＺ^８は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ＝ＣＦ−、−（ＣＨ_２）_４−、−（ＣＨ_２）_２ＣＦ_２Ｏ−、−（ＣＨ_２）_２ＯＣＦ_２−、−ＣＦ_２Ｏ（ＣＨ_２）_２−、−ＯＣＦ_２（ＣＨ_２）_２−、−ＣＨ＝ＣＨ−（ＣＨ_２）_２−、または−（ＣＨ_２）_２−ＣＨ＝ＣＨ−であり；Ｌ^１、Ｌ^２、Ｌ^３、Ｌ^４、およびＬ^５）は独立して、水素、ハロゲン、−ＣＨ_３、または−ＣＦ_３であり；ａ^１、ａ^２、ａ^３、ａ^４、ａ^５、ａ^６、ａ^７、およびａ^８は独立して、０または１であり、ａ^１、ａ^２、ａ^３、ａ^４、ａ^５、ａ^６、ａ^７、およびａ^８の和は２、３、または４であり；Ｒ^０−（Ａ^１Ｚ^１）ａ^１−（Ａ^２Ｚ^２）ａ^２−（Ａ^３Ｚ^３）ａ^３−（Ａ^４Ｚ^４）ａ^４−、Ｌ^１、およびＬ^２は、インドール環の1位、2位、および3位から選ばれた個別な１つずつにあり、Ｒ^１−（Ａ^８Ｚ^８）ａ^８−（Ａ^７Ｚ^７）ａ^７−（Ａ^６Ｚ^６）ａ^６−（Ａ^５Ｚ^５）ａ^５−、Ｌ^３、Ｌ^４、およびＬ^５はインドール環の４位、５位、６位、および７位から選ばれた個別な１つずつにある。 [1] A compound represented by formula (1).

In this formula, R ⁰ and R ¹ are independently hydrogen, halogen, or alkyl having 1 to 20 carbons, in which any —CH ₂ — is replaced by —O— or —S—. Any — (CH ₂ ) ₂ — may be replaced by —CH═CH—, in which any hydrogen may be replaced by a halogen; ring A ¹ , ring A ² , Ring A ³ , Ring A ⁴ , Ring A ⁵ , Ring A ⁶ , Ring A ⁷ , and Ring A ⁸ are each independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1, 4-phenylene, or 1,4-phenylene in which any hydrogen is replaced by halogen; Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , and Z ⁸ are independently a single _{bond, -CH 2 CH 2 -, -} CH = CH- _{-C≡C -, - COO -, -} OCO -, - CF 2 O -, - OCF 2 -, - CH 2 O -, - OCH 2 -, - CF = CF -, - (CH 2) 4 -, _{- (CH 2) 2 CF 2} O -, - (CH 2) 2 OCF 2 -, - CF 2 O (CH 2) 2 -, - OCF 2 (CH 2) 2 -, - CH = CH- (CH 2 ) _2- , or-(CH ₂ ) ₂ -CH = CH-; L ¹ , L ² , L ³ , L ⁴ , and L ⁵ ) are independently hydrogen, halogen, -CH ₃ , or- CF ₃ ; a ¹ , a ² , a ³ , a ⁴ , a ⁵ , a ⁶ , a ⁷ , and a ⁸ are independently 0 or 1, and a ¹ , a ² , a ³ , a ^{4, a 5, a 6,} a 7, and the sum of ^{a 8} is 2, 3 or ^{4,; R 0 - (a} 1 Z 1) a 1 - (a 2 Z 2) ^{2 - (A 3 Z 3)} a 3 - (A 4 Z 4) a 4 -, L 1, and ^{L 2,} 1-position of the indole ring, 2-position, and one at discrete selected from 3-position in ^{there, R 1 - (a 8 Z} 8) a 8 - (a 7 Z 7) a 7 - (a 6 Z 6) a 6 - (a 5 Z 5) a 5 -, L 3, L 4, and L ⁵ is in each individual one selected from the 4th, 5th, 6th and 7th positions of the indole ring.

In [2] formula ^{(1), R 0 - (} A 1 Z 1) a 1 - (A 2 Z 2) a 2 - (A 3 Z 3) a 3 - (A 4 Z 4) a 4 - indole The compound of claim 1 in the 1-position of the ring; and L ¹ and L ² are hydrogen.

In [3] Equation ^{(1), R 0 - (} A 1 Z 1) a 1 - (A 2 Z 2) a 2 - (A 3 Z 3) a 3 - (A 4 Z 4) a 4 - indole The compound according to item [1], wherein L ¹ and L ² are hydrogen; and positions 6 and 7 of the indole ring are hydrogen or fluorine.

In [4] Equation ^{(1), R 0 - (} A 1 Z 1) a 1 - (A 2 Z 2) a 2 - (A 3 Z 3) a 3 - (A 4 Z 4) a 4 - indole R ^1- (A ⁸ Z ⁸ ) a ^8- (A ⁷ Z ⁷ ) a ^7- (A ⁶ Z ⁶ ) a ^6- (A ⁵ Z ⁵ ) a ⁵ -is an indole ring at the 1-position of the ring The compound according to item [1], wherein L ¹ and L ² are hydrogen; and L ³ , L ⁴ , and L ⁵ are hydrogen or fluorine.

これらの式において、Ｒ^０は、炭素数１〜１５のアルキル、炭素数２〜１５のアルケニル、炭素数１〜１５のアルコキシ、または炭素数２〜１５のアルケニルオキシであり；Ｒ^１は、フッ素、塩素、−ＣＦ_３、−ＣＨＦ_２、−ＣＨ_２Ｆ、−ＯＣＦ_３、−ＯＣＨＦ_２、または−ＯＣＨ_２Ｆであり；環Ａ^１、環Ａ^２、環Ａ^３、環Ａ^４、環Ａ^５、環Ａ^６、環Ａ^７、および環Ａ^８は独立して、１，４−シクロヘキシレン、１，３−ジオキサン−２，５−ジイル、１，４−フェニレン、または任意の水素がフッ素で置き換えられた１，４−フェニレンであり；ａ^１、ａ^２、ａ^３、ａ^４、ａ^５、ａ^６、ａ^７、およびａ^８は独立して、０または１であり、ａ^１、ａ^２、ａ^３、ａ^４、ａ^５、ａ^６、ａ^７、およびａ^８の和は、２、３、または４であり；Ｚ^１、Ｚ^２、Ｚ^３、Ｚ^４、Ｚ^５、Ｚ^６、Ｚ^７、およびＺ^８は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＣＦ_２Ｏ−、−ＣＨ_２Ｏ−、または−ＯＣＨ_２−であり；Ｌ^３およびＬ^４は独立して、水素またはフッ素である。 [5] The compound according to item [1], which is represented by any one of formulas (1-1) to (1-2).

In these formulas, R ⁰ is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 15 carbons, or alkenyloxy having 2 to 15 carbons; R ¹ is fluorine. , Chlorine, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F; ring A ¹ , ring A ² , ring A ³ , ring A ⁴ , ring A ⁵ , Ring A ⁶ , Ring A ⁷ , and Ring A ⁸ are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, or any hydrogen is fluorine 1,4-phenylene substituted with; a ¹ , a ² , a ³ , a ⁴ , a ⁵ , a ⁶ , a ⁷ , and a ⁸ are independently 0 or 1, a ¹ , ^{a 2, a 3, a 4} , a 5, a 6, a 7, and ^{a 8} Sum is an 2, 3 or ^{4,; Z 1, Z 2} , Z 3, Z 4, Z 5, Z 6, Z 7, and ^{Z 8} are independently a single bond, _-CH 2 CH ₂ - , -CH = CH -, - C≡C -, - COO -, - CF 2 O -, - CH 2 O-, or -OCH ₂ - a and; ^{L 3} and ^{L 4} are each independently hydrogen or fluorine It is.

これらの式において、Ｒ^０は、炭素数１〜１５のアルキル、炭素数２〜１５のアルケニル、炭素数１〜１５のアルコキシ、または炭素数２〜１５のアルケニルオキシであり；Ｒ^１は、フッ素、−ＣＦ_３、または−ＯＣＦ_３であり；環Ａ^１、は、１，４−シクロヘキシレン、１，４−フェニレン、または任意の水素がフッ素で置き換えられた１，４−フェニレンであり；Ｚ^１、Ｚ^２、Ｚ^３、Ｚ^６、Ｚ^７、およびＺ^８は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＣＦ_２Ｏ−、−ＣＨ_２Ｏ−、または−ＯＣＨ_２−であり；Ｙ¹、Ｙ^２、Ｙ^３、Ｙ^４、Ｙ^５、およびＹ^６は独立して、水素またはフッ素であり；Ｌ^３、Ｌ^４、およびＬ^５は独立して、水素またはフッ素であり；式（１−１３）および式（１−１４）において、Ｒ^１、Ｌ^３、Ｌ^４、およびＬ^５は、インドール環の４位、５位、６位、および７位から選ばれた個別な１つずつにある。 [6] The compound according to item [1], which is represented by any one of formulas (1-3) to (1-14).

In these formulas, R ⁰ is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 15 carbons, or alkenyloxy having 2 to 15 carbons; R ¹ is fluorine. , —CF ₃ , or —OCF ₃ ; ring A ¹ is 1,4-cyclohexylene, 1,4-phenylene, or 1,4-phenylene in which any hydrogen is replaced by fluorine; Z ¹ , Z ² , Z ³ , Z ⁶ , Z ⁷ , and Z ⁸ are each independently a single bond, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, —COO—, —CF ₂ O—, —CH ₂ O—, or —OCH ₂ —; Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , and Y ⁶ are independently hydrogen or fluorine; L ³ , L ^4, and ^{L 5} are independently hydrogen or fluorine; formula 1-13) and the formula ^{(1-14), R 1, L} 3, L 4, and ^{L 5,} the 4-position of the indole ring, 5-, 6-, and 7-position one discrete selected from One by one.

これらの式において、Ｒ^０は、炭素数１〜１５のアルキル、炭素数２〜１５のアルケニル、または炭素数１〜１５のアルコキシであり；Ｒ^１は、フッ素、−ＣＦ_３、または−ＯＣＦ_３であり；Ｙ¹、Ｙ^２、Ｙ^３、およびＹ^４は独立して、水素またはフッ素であり；Ｌ^３、およびＬ^４は独立して、水素またはフッ素である。 [7] The compound according to item [1], which is represented by any one of formulas (1-15) to (1-20).

In these formulas, R ⁰ is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, or alkoxy having 1 to 15 carbons; R ¹ is fluorine, —CF ₃ , or —OCF _3. Y ¹ , Y ² , Y ³ and Y ⁴ are independently hydrogen or fluorine; L ³ and L ⁴ are independently hydrogen or fluorine.

これらの式において、Ｒ^０は炭素数１〜１５のアルキルである。 [8] The compound according to item [1], which is represented by any one of formulas (1-21) to (1-24).

In these formulas, R ⁰ is alkyl having 1 to 15 carbons.

[9] A liquid crystal composition comprising two or more components, comprising at least one compound according to items [1] to [8] as one component.

これらの式において、Ｒ^２は炭素数１〜１０のアルキルまたは炭素数２〜１０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、任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ₂−は−Ｏ−で置き換えられてもよく；Ｘ^２は、フッ素、塩素、−ＯＣＦ₃、−ＯＣＨＦ₂、−ＣＦ₃、−ＣＨＦ₂、−ＣＨ₂Ｆ、−ＯＣＦ₂ＣＨＦ₂、または−ＯＣＦ₂ＣＨＦＣＦ₃であり；環Ｂ^１、環Ｂ^２、および環Ｂ^３は独立して、１，４−シクロヘキシレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、テトラヒドロピラン−２，５−ジイル、１，４−フェニレン、または任意の水素がフッ素で置き換えられた１，４−フェニレンであり；Ｚ^７およびＺ^８は独立して、−（ＣＨ₂）₂−、−（ＣＨ₂）₄−、−ＣＯＯ−、−ＣＦ₂Ｏ−、−ＯＣＦ₂−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ_２Ｏ−、または単結合であり；Ｌ^５およびＬ^６は独立して、水素またはフッ素である。 [10] The liquid crystal composition according to item [9], containing as a component at least one compound selected from the group of compounds represented by formulas (2), (3) and (4).

In these formulas, R ² is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in this alkyl and alkenyl, any hydrogen may be replaced by fluorine, and any —CH ₂ — May be replaced by —O—; X ² is fluorine, chlorine, —OCF ₃ , —OCHF ₂ , —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₂ CHF ₂ , or —OCF ₂ CHFCF ₃ ; ring B ¹ , ring B ² , and ring B ³ are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, tetrahydro Pyran-2,5-diyl, 1,4-phenylene, or 1,4-phenylene in which any hydrogen is replaced by fluorine; Z ⁷ and Z ⁸ are independently — (CH ₂ ) ₂ —, -(CH _{2 ) 4 -, - COO -,} - CF 2 O -, - OCF 2 -, - CH = CH -, - C≡C -, - CH 2 O-, or a single bond; ^{L 5} and ^{L 6} independently Hydrogen or fluorine.

これらの式において、Ｒ^３は炭素数１〜１０のアルキルまたは炭素数２〜１０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、任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ₂−は−Ｏ−で置き換えられてもよく；Ｘ^３は−Ｃ≡Ｎまたは−Ｃ≡Ｃ−Ｃ≡Ｎ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、１，４−フェニレン、任意の水素がフッ素で置き換えられた１，４−フェニレン、１，３−ジオキサン−２，５−ジイル、テトラヒドロピラン−２，５−ジイル、またはピリミジン−２，５−ジイルであり；Ｚ^９は−（ＣＨ₂）₂−、−ＣＯＯ−、−ＣＦ₂Ｏ−、−ＯＣＦ₂−、−Ｃ≡Ｃ−、−ＣＨ_２Ｏ−、または単結合であり；Ｌ^７およびＬ^８は独立して、水素またはフッ素であり；ｒは、０、１または２であり、ｓは０または１であり、ｒとｓとの和が、０、１、または２である。 [11] The liquid crystal composition according to item [9], containing at least one compound selected from the group of compounds represented by formula (5) as one component.

In these formulas, R ³ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in this alkyl and alkenyl, any hydrogen may be replaced by fluorine, and any —CH ₂ — May be replaced by —O—; X ³ is —C≡N or —C≡C—C≡N; Ring C ¹ , Ring C ² and Ring C ³ are independently 1,4- Cyclohexylene, 1,4-phenylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or pyrimidine-2 in which any hydrogen is replaced by fluorine Z ⁹ is — (CH ₂ ) ₂ —, —COO—, —CF ₂ O—, —OCF ₂ —, —C≡C—, —CH ₂ O—, or a single bond; L ⁷ and ^{L 8} are independently hydrogen or Be Tsu containing; r is 0, 1 or 2, s is 0 or 1, the sum of r and s, 0,1, or 2.

これらの式において、Ｒ^４およびＲ^５は独立して、炭素数１〜１０のアルキルまたは炭素数２〜１０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任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ₂−は−Ｏ−で置き換えられてもよく；環Ｄ^１、環Ｄ^２、環Ｄ^３、および環Ｄ^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、１，４−フェニレン、任意の水素がフッ素で置き換えられた１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、またはデカヒドロナフタレン−２，６−ジイルであり；Ｚ^１０、Ｚ^１１、Ｚ^１２、およびＺ^１３は独立して、−（ＣＨ₂）₂−、−ＣＯＯ−、−ＣＨ_２Ｏ−、−ＯＣＦ_２−、−ＯＣＦ_２（ＣＨ₂）₂−、または単結合であり；Ｌ^９およびＬ^１０は独立して、フッ素または塩素であり；ｔ、ｕ、ｘ、ｙ、およびｚは独立して０または１であり、ｕ、ｘ、ｙ、およびｚの和は、１または２である。 [12] The item [9], containing at least one compound selected from the group of compounds represented by formulas (6), (7), (8), (9) and (10) as one component. Liquid crystal composition.

In these formulas, R ⁴ and R ⁵ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which any hydrogen may be replaced by fluorine, Any —CH ₂ — may be replaced by —O—; Ring D ¹ , Ring D ² , Ring D ³ , and Ring D ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohex; Senylene, 1,4-phenylene, 1,4-phenylene in which arbitrary hydrogen is replaced by fluorine, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl; Z ¹⁰ , Z ¹¹ , Z ¹² , and Z ¹³ are each independently — (CH ₂ ) ₂ —, —COO—, —CH ₂ O—, —OCF ₂ —, —OCF ₂ (CH ₂ ) ₂ —, or a single bond. Yes; L ⁹ and L ¹⁰ are independently fluorine or chlorine; t, u, x, y, and z are independently 0 or 1, and the sum of u, x, y, and z is 1 or 2 It is.

これらの式において、Ｒ^６およびＲ^７は独立して、炭素数１〜１０のアルキルまたは炭素数２〜１０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、任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ₂−は−Ｏ−で置き換えられてもよく；環Ｅ^１、環Ｅ^２、および環Ｅ^３は独立して、１，４−シクロヘキシレン、ピリミジン−２，５−ジイル、１，４−フェニレン、２−フルオロ−１，４−フェニレン、３−フルオロ−１，４−フェニレン、または２，５−ジフルオロ１，４−フェニレンであり；Ｚ^１４およびＺ^１５は独立して、−Ｃ≡Ｃ−、−ＣＯＯ−、−（ＣＨ₂）₂−、−ＣＨ＝ＣＨ−、または単結合である。 [13] The liquid crystal composition according to item [9], containing as a component at least one compound selected from the group of compounds represented by formulas (11), (12) and (13).

In these formulas, R ⁶ and R ⁷ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in this alkyl and alkenyl, any hydrogen may be replaced with fluorine. Any —CH ₂ — may be replaced by —O—; ring E ¹ , ring E ² , and ring E ³ are independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, or 2,5-difluoro1,4-phenylene; Z ¹⁴ and Z ¹⁵ are independently —C≡C—, —COO—, — (CH ₂ ) ₂ —, —CH═CH—, or a single bond.

[14] The liquid crystal composition according to item [9], comprising at least two different compounds selected from the group of compounds represented by formula (5) according to item [11].

[15] The liquid crystal composition according to item [11], further comprising at least one compound selected from the group of compounds represented by formulas (11), (12) and (13) according to item [12]. .

[16] The liquid crystal composition according to item [12], further comprising at least one compound selected from the group of compounds represented by formulas (11), (12) and (13) according to item [13]. .

[17] The item [12], comprising at least two different compounds selected from the group of compounds represented by formulas (11), (12) and (13) of item [11] Liquid crystal composition.

[18] The liquid crystal composition according to item [9], further containing at least one optically active compound.

[19] The liquid crystal composition according to item [9], further comprising at least one antioxidant and / or ultraviolet absorber.

[20] A liquid crystal display device comprising the liquid crystal composition according to any one of items [9] to [19].

Terms used in this specification are as follows. A liquid crystal compound is a generic term for a compound having a liquid crystal phase such as a nematic phase or a smectic phase and a compound having no liquid crystal phase but useful as a component of a liquid crystal composition. A liquid crystal compound, a liquid crystal composition, and a liquid crystal display element may be abbreviated as a compound, a composition, and an element, respectively. A liquid crystal display element is a general term for a liquid crystal display panel and a liquid crystal display module. The upper limit temperature of the nematic phase is a nematic phase-isotropic phase transition temperature, and may simply be abbreviated as clearing point or upper limit temperature. The lower limit temperature of the nematic phase may simply be abbreviated as the lower limit temperature. The compound represented by formula (1) may be abbreviated as compound (1). This abbreviation may also apply to compounds represented by formula (2) and the like. In the formulas (1) to (13), symbols such as B, D, and E surrounded by hexagons correspond to the rings B, D, and E, respectively. The amount of the compound expressed as a percentage is a weight percentage (% by weight) based on the total weight of the composition. A plurality of the same symbols such as rings A ¹ , Y ¹ , and B are described in the same formula or different formulas, but these may be the same or different.

“Arbitrary” indicates that not only the position but also the number is arbitrary, but the case where the number is 0 is not included. The expression that any A may be replaced by B, C or D is in addition to any A being replaced by B, any A being replaced by C and any A being replaced by D. Thus, it is meant to include the case where a plurality of A are replaced by at least two of B to D. For example, alkyl in which any —CH ₂ — may be replaced by —O— or —CH═CH— includes alkyl, alkenyl, alkoxy, alkoxyalkyl, alkoxyalkenyl, alkenyloxyalkyl, and the like. In the present invention, it is not preferable that two consecutive —CH ₂ — are replaced with —O— to become —O—O—. In addition, it is not preferable that the terminal —CH ₂ — in alkyl is replaced by —O—. The present invention is further described below.

  The compound of the present invention has the general physical properties required for the compound, stability to heat, light, etc., a wide temperature range of the liquid crystal phase, good compatibility with other compounds, a large dielectric anisotropy and appropriate optical properties. Has a direction. The liquid crystal composition of the present invention contains at least one of these compounds and has a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, and a low threshold voltage. The liquid crystal display element of the present invention contains this composition and has a wide temperature range that can be used, a short response time, a small power consumption, a large contrast ratio, and a low driving voltage.

式（１）において、Ｒ^０−（Ａ^１Ｚ^１）ａ^１−（Ａ^２Ｚ^２）ａ^２−（Ａ^３Ｚ^３）ａ^３−（Ａ^４Ｚ^４）ａ^４−、Ｌ^１、およびＬ^２は、インドール環の1位、2位、および3位から選ばれた個別な１つずつにあり、Ｒ^１−（Ａ^８Ｚ^８）ａ^８−（Ａ^７Ｚ^７）ａ^７−（Ａ^６Ｚ^６）ａ^６−（Ａ^５Ｚ^５）ａ^５−、Ｌ^３、Ｌ^４、およびＬ^５はインドール環の４位、５位、６位、および７位から選ばれた個別な１つずつにある。 1-1 Compound of the Present Invention The first aspect of the present invention relates to a compound represented by the formula (1).

In the formula (1), R ^0- (A ¹ Z ¹ ) a ^1- (A ² Z ² ) a ^2- (A ³ Z ³ ) a ^3- (A ⁴ Z ⁴ ) a ^4- , L ¹ , and L ² is in each one selected from the 1-position, 2-position and 3-position of the indole ring, and R ^1- (A ⁸ Z ⁸ ) a ^8- (A ⁷ Z ⁷ ) a ^7- ( A ⁶ Z ⁶ ) a ^6- (A ⁵ Z ⁵ ) a ^5- , L ³ , L ⁴ and L ⁵ are each an individual 1 selected from the 4th, 5th, 6th and 7th positions of the indole ring One by one.

「Ｒ^１−（Ａ^８Ｚ^８）ａ^８−（Ａ^７Ｚ^７）ａ^７−（Ａ^６Ｚ^６）ａ^６−（Ａ^５Ｚ^５）ａ^５−」とは、下記の基を示す。

「個別な１つずつ」とは、それぞれが違ったものを選択することを示す。「Ｒ^０−（Ａ^１Ｚ^１）ａ^１−（Ａ^２Ｚ^２）ａ^２−（Ａ^３Ｚ^３）ａ^３−（Ａ^４Ｚ^４）ａ^４−、Ｌ^１、およびＬ^２は、インドール環の１位、２位、および３位から選ばれた個別な１つずつ」とは、例えば、Ｒ^０−（Ａ^１Ｚ^１）ａ^１−（Ａ^２Ｚ^２）ａ^２−（Ａ^３Ｚ^３）ａ^３−（Ａ^４Ｚ^４）ａ^４−がインドール環の１位にあり、Ｌ^１がインドール環の２位にあり、そしてＬ^２はインドール環の３位にある場合である。 ^{"R 0 - (A 1 Z 1} ) a 1 - (A 2 Z 2) a 2 - (A 3 Z 3) a 3 - (A 4 Z 4) a 4 - " and indicates the following groups.

^{"R 1 - (A 8 Z 8} ) a 8 - (A 7 Z 7) a 7 - (A 6 Z 6) a 6 - (A 5 Z 5) a 5 - " and refers to a group of the following.

“Individual one by one” indicates that each selects a different one. “R ^0- (A ¹ Z ¹ ) a ^1- (A ² Z ² ) a ^2- (A ³ Z ³ ) a ^3- (A ⁴ Z ⁴ ) a ^4- , L ¹ , and L ² are indole 1 position of the ring, position 2, and one discrete selected from 3-position "is, for ^{example, R 0 - (a 1 Z} 1) a 1 - (a 2 Z 2) a 2 - (a 3 This is the case when Z ³ ) a ^3- (A ⁴ Z ⁴ ) a ⁴ -is in position ¹ of the indole ring, L ¹ is in position ² of the indole ring, and L ² is in position 3 of the indole ring.

R ⁰ and R ¹ are independently hydrogen, halogen, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, thioalkyl, thioalkylalkoxy, alkenyl, alkenyloxy, alkenyloxyalkyl, alkoxyalkenyl and the like, and any hydrogen is It may be replaced by halogen. In these groups, straight chain is preferable to branch. Even when R ⁰ or R ¹ is a branched group, it is preferable when it is optically active. The preferred configuration of —CH═CH— in alkenyl depends on the position of the double bond. _{-CH = CHCH 3, -CH = CHC} 2 H 5, -CH = CHC 3 H 7, -CH = CHC 4 H 9, -C 2 H 4 CH = CHCH 3, and _{-C 2 H} 4 CH = CHC 2 In alkenyl having a double bond at odd positions such as H ₅ , the trans configuration is preferable. -CH ₂ CH ₌ CHCH _3, alkenyl having a double bond at an even position, such as _{-CH 2 CH = CHC 2 H 5} , and _-CH 2 CH = _CHC 3 _{H 7,} the cis configuration is preferred. Alkenyl having a preferred configuration has a high maximum temperature or a wide temperature range of the liquid crystal phase. Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327 have detailed descriptions.

Alkyl may be linear or branched, and specific examples of alkyl include —CH ₃ , —C ₂ H ₅ , —C ₃ H ₇ , —C ₄ H ₉ , —C ₅ H ₁₁ , —C _{6. H 13, -C 7 H 15,} -C 8 H 17, -C 9 H 19, -C 10 H 21, -C 11 H 23, -C 12 H 25, -C 13 H 27, -C 14 H 29 , and _-C are 15 _{H 31.}

Alkoxy may be straight or branched, specific examples of the _{alkoxy, -OCH 3, -OC 2 H 5} , -OC 3 H 7, -OC 4 H 9, -OC 5 H 11, -OC 6 H ₁₃ and _{-OC 7 H 15, -OC 8 H} 17, -OC 9 H 19, -OC 10 H 21, -OC 11 H 23, -OC 12 H 25, -OC 13 H 27, and _{-OC 14} H ₂₉ .

The alkoxyalkyl may be linear or branched, and specific examples of alkoxyalkyl include —CH ₂ OCH ₃ , —CH ₂ OC ₂ H ₅ , —CH ₂ OC ₃ H ₇ , — (CH ₂ ) _{2. -OCH 3, - (CH 2)} 2 -OC 2 H 5, - (CH 2) 2 -OC 3 H 7, - (CH 2) 3 -OCH 3, - (CH 2) 4 -OCH 3, and - it is a _{(CH 2)} 5 -OCH _3.

Alkenyl may be linear or branched, and specific examples of alkenyl include —CH═CH ₂ , —CH═CHCH ₃ , —CH ₂ CH═CH ₂ , —CH═CHC ₂ H ₅ , —CH. _{2 CH = CHCH 3, - (} CH 2) 2 -CH = CH 2, -CH = CHC 3 H 7, -CH 2 CH = CHC 2 H 5, - (CH 2) 2 -CH = CHCH 3, and - _{(CH 2)} a 3 -CH = CH _2.

Alkenyloxy may be linear or branched, specific examples of _{alkenyloxy, -OCH 2 CH = CH 2,} -OCH 2 CH = CHCH 3, and are -OCH ₂ CH = _{CHC 2 H 5} .

Specific examples of alkyl in which arbitrary hydrogen is replaced by _{halogen, -CH 2 F, -CHF 2,} -CF 3, - (CH 2) 2 -F, -CF 2 CH 2 F, -CF 2 CHF _{2, -CH 2 CF 3, -CF} 2 CF 3, - (CH 2) 3 -F, - (CF 2) 3 -F, -CF 2 CHFCF 3, -CHFCF 2 CF 3, - (CH 2) 4 _{-F, - (CF 2) 4} -F, - (CH 2) 5 -F, and - _{(CF 2)} a 5 -F.

Specific examples of alkoxy in which arbitrary hydrogen is replaced by _{halogen, -OCH 2 F, -OCHF 2,} -OCF 3, -O- (CH 2) 2 -F, -OCF 2 CH 2 F, -OCF _{2 CHF 2, -OCH 2 CF 3} , -O- (CH 2) 3 -F, -O- (CF 2) 3 -F, -OCF 2 CHFCF 3, -OCHFCF 2 CF 3, -O (CH 2) _{4 -F, -O- (CF 2)} 4 -F, is -O- _{(CH 2)} 5 -F, and -O- _{(CF 2)} 5 -F.

Specific examples of alkenyl in which arbitrary hydrogen is replaced by _{halogen, -CH = CHF, -CH = CF} 2, -CF = CHF, -CH = CHCH 2 F, -CH = CHCF 3, - (CH 2 ) ₂ —CH═CF ₂ , —CH ₂ CH═CHCF ₃ , and —CH═CHCF ₂ CF ₃ .

R ⁰ or R ¹ is halogen, alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkyl having 1 to 15 carbons in which any hydrogen is replaced by halogen, or any hydrogen being replaced by halogen The obtained C2-C15 alkoxy is preferable. The most preferred examples of R ⁰ or R ¹ are fluorine, chlorine, —CH ₃ , —C ₂ H ₅ , —C ₃ H ₇ , —C ₄ H ₉ , —C ₅ H ₁₁ , —C ₆ H _{13. , -C 7 H 15, -C 8} H 17, -C 9 H 19, -C 10 H 21 -C 11 H 23, -C 12 H 25, -C 13 H 27, -C 14 H 29, -C ₁₅ H ₃₁ , —CH═CH ₂ , —CH═CHCH ₃ , —CH ₂ CH═CH ₂ , —CH═CHC ₂ H ₅ , —CH ₂ CH═CHCH ₃ , — (CH ₂ ) ₂ —CH═CH _{2, -CH = CHC 3 H 7} , -CH 2 CH = CHC 2 H 5, - (CH 2) 2 -CH = CHCH 3, - (CH 2) 3 -CH = CH 2, -CF 3, -CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ or —OCH ₂ F It is.

In formula (1), ring A ¹ , ring A ² , ring A ³ , ring A ⁴ , ring A ⁵ , ring A ⁶ , ring A ⁷ , and ring A ⁸ are each independently 1,4-cyclohexylene ( 14-1), 1,3-dioxane-2,5-diyl (14-2), 1,4-phenylene (14-3), or 1,4-phenylene in which any hydrogen is replaced by halogen . Examples of 1,4-phenylene in which arbitrary hydrogen is replaced by halogen are groups represented by the following formulas (14-4) to (14-20). Preferred examples are groups represented by formulas (14-4) to (14-9).

Preferred examples of ring A ¹ , ring A ² , ring A ³ , ring A ⁴ , ring A ⁵ , ring A ⁶ , ring A ⁷ , or ring A ⁸ are 1,4-cyclohexylene (14-1), 1 , 3-Dioxane-2,5-diyl (14-2), 1,4-phenylene (14-3), 2-fluoro-1,4-phenylene (14-4) (14-5), 2,3 -Difluoro-1,4-phenylene (14-6), 2,5-difluoro-1,4-phenylene (14-8), 2,6-difluoro-1,4-phenylene (14-7) (14- 9).

The most preferred examples of ring A ¹ , ring A ² , ring A ³ , ring A ⁴ , ring A ⁵ , ring A ⁶ , ring A ⁷ , or ring A ⁸ are 1,4-cyclohexylene, 1,3-dioxane. -2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, and 2,6-difluoro-1,4-phenylene.

In Formula (1), Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , and Z ⁸ are independently a single bond, —CH ₂ CH ₂ —, —CH═CH—. , —C≡C—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH ₂ O—, —OCH ₂ —, —CF═CF—, — (CH ₂ ) ₄ — _{, - (CH 2) 2 -CF} 2 O -, - (CH 2) 2 -OCF 2 -, - CF 2 O- (CH 2) 2 -, - OCF 2 (CH 2) 2 -, - CH = CH - _{(CH 2) 2} -, or _{- (CH} 2) a 2 -CH = CH-.

Preferred examples of Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , or Z ⁸ are a single bond, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—. _{, -COO -, - CF 2 O} -, - CH 2 O-, and -OCH ₂ - is. In these bonds, double bonds of linking groups such as —CH═CH—, —CF═CF—, —CH═CH— (CH ₂ ) ₂ —, and — (CH ₂ ) ₂ —CH═CH— The configuration of is preferably trans rather than cis. Most preferred Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , or Z ⁸ is a single bond.

In formula (1), L ¹ , L ² , L ³ , L ⁴ , and L ⁵ are independently hydrogen, halogen, —CH ₃ , or —CF ₃ . L ¹ , L ² , L ³ , L ⁴ , or L ⁵ is preferably hydrogen or fluorine.

In the formula (1), a ¹ , a ² , a ³ , a ⁴ , a ⁵ , a ⁶ , a ⁷ , and a ⁸ are independently 0 or 1, and a ¹ , a ² , a ³ , The sum of a ⁴ , a ⁵ , a ⁶ , a ⁷ , and a ⁸ is 2, 3, or 4.

In the formula (1), R ^0- (A ¹ Z ¹ ) a ^1- (A ² Z ² ) a ^2- (A ³ Z ³ ) a ^3- (A ⁴ Z ⁴ ) a ⁴ -represents an indole ring 1 It is preferable to be in a position.

In the formula (1), R ^1- (A ⁵ Z ⁵ ) a ^5- (A ⁶ Z ⁶ ) a ^6- (A ⁷ Z ⁷ ) a ^7- (A ⁸ Z ⁸ ) a ⁸ -is an indole ring It is preferably in the 4th or 5th position.

1-2 Properties of Compound of the Present Invention and Preparation Method Thereof The compound (1) of the present invention will be described in more detail. This compound is extremely physically and chemically stable under the conditions in which the device is normally used, and has good compatibility with other liquid crystal compounds. A composition containing this compound is stable under conditions in which the device is normally used. Even when the composition is stored at a low temperature, the compound does not precipitate as crystals (or a smectic phase). This compound has general physical properties necessary for the compound, appropriate optical anisotropy, and appropriate dielectric anisotropy. Compound (1) has a large positive dielectric anisotropy. A compound having a large dielectric anisotropy is useful as a component for lowering the threshold voltage of the composition.

In the compound (1), R ⁰ , R ¹ , ring A ¹ , ring A ² , ring A ³ , ring A ⁴ , ring A ⁵ , ring A ⁶ , ring A ⁷ ring A ⁸ , Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , Z ⁸ , L ¹ , L ² , L ³ , L ⁴ , L ⁵ , a ¹ , a ² , a ³ , a ⁴ , a ⁵ , a ⁶ , a ⁷ and a ⁸ combination, and R ^1- (A ¹ Z ¹ ) a ^1- (A ² Z ² ) a ^2- (A ³ Z ³ ) a ^3- (A ⁴ Z ⁴ ) a ^{4- , L 1, L 2, R} 2 - (A 8 Z 8) a 8 - (A 7 Z 7) a 7 - (A 6 Z 6) a 6 - (A 5 Z 5) a 5 -, L 3, By appropriately selecting the bonding positions of L ⁴ and L ⁵ , it is possible to arbitrarily adjust physical properties such as clearing point, optical anisotropy and dielectric anisotropy. The effects of these on the physical properties of the compound (1) will be described below.

^{R 0 - (A 1 Z 1} ) a 1 - (A 2 Z 2) a 2 - (A 3 Z 3) a 3 - (A 4 Z 4) a 4 -, and ^{R 1 - (A 8 Z 8} ) ^{a 8 - (a 7 Z 7} ) a 7 - (a 6 Z 6) a 6 - (a 5 Z 5) a 5 - is, when in the 1 and 4 positions, respectively indole ring, the temperature of the liquid crystal phase Wide range and high clearing point. ^{R 0 - (A 1 Z 1} ) a 1 - (A 2 Z 2) a 2 - (A 3 Z 3) a 3 - (A 4 Z 4) a 4 -, and ^{R 1 - (A 8 Z 8} ) ^{a 8 - (a 7 Z 7} ) a 7 - (a 6 Z 6) a 6 - (a 5 Z 5) a 5 - is, when in 1-position and 5-position of the respective indole ring, and other compounds The compatibility is high and the dielectric anisotropy is large.

When all of L ¹ , L ² , L ³ , L ⁴ , and L ⁵ are hydrogen, the temperature range of the liquid crystal phase is wide and the clearing point is high. When at least one of L ¹ , L ² , L ³ , L ⁴ , and L ⁵ is fluorine, the dielectric anisotropy is large.

In the case of a combination of a ¹ , a ² , a ³ , a ⁴ , a ⁵ , a ⁶ , a ⁷ , and a ⁸ and the sum thereof is 2, the compatibility with other compounds is high, and the sum is In the case of the combination of 3, the temperature range of the liquid crystal phase is wide and the clearing point is high.

When ring A ¹ , ring A ² , ring A ³ , ring A ⁴ , ring A ⁵ , ring A ⁶ , ring A ⁷ , and ring A ⁸ are all 1,4-cyclohexylene, the clearing point is high. The viscosity is small. When at least one of ring A ¹ , ring A ² , ring A ³ , ring A ⁴ , ring A ⁵ , ring A ⁶ , ring A ⁷ , and ring A ⁸ is 1,4-phenylene, the optical anisotropy is It is relatively large and the orientational order parameter is relatively large. When ring A ¹ , ring A ² , ring A ³ , ring A ⁴ , ring A ⁵ , ring A ⁶ , ring A ⁷ , and ring A ⁸ are all 1,4-phenylene, optical anisotropy Is particularly large.

When R ⁰ and R ¹ are linear, the temperature range of the liquid crystal phase is wide and the viscosity is small. When R ⁰ or R ¹ is a branched chain, the compatibility with other liquid crystal compounds is good. A compound in which R ⁰ or R ¹ is an optically active group is useful as a chiral dopant. By adding this compound to the composition, a reverse twisted domain generated in the device can be prevented. Compounds in which R ⁰ and R ¹ are not optically active groups are useful as components of the composition. When R ⁰ or R ¹ is alkenyl, the preferred configuration depends on the position of the double bond. Alkenyl having a preferred configuration has a high maximum temperature or a wide temperature range of the liquid crystal phase. When R ⁰ and R ¹ have halogen, the dielectric anisotropy is large.

Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , or Z ⁸ is a single bond, —CH ₂ CH ₂ —, —CH═CH—, —CF ₂ O—, —OCF _2- , —CH ₂ O—, —OCH ₂ —, —CF═CF—, — (CH ₂ ) ₃ —O—, —O— (CH ₂ ) ₃ —, — (CH ₂ ) ₂ —CF ₂ O _{-, - OCF 2 - (CH} 2) 2 -, or - _{(CH 2) 4} - is when a has a smaller viscosity. Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , or Z ⁸ Z ^m , a single bond, — (CH ₂ ) ₂ —, —CF ₂ O—, —OCF ₂ —, or When -CH = CH-, the viscosity is smaller. When Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , or Z ⁸ is —CH═CH—, the temperature range of the liquid crystal phase is wide, and the elastic constant ratio K ₃₃ / K ₁₁ (K ₃₃ : bend elastic constant, K ₁₁ : spray elastic constant) is large. When Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , or Z ⁸ is —C≡C—, the optical anisotropy is large. Z ^m is a single _{bond, - (CH 2) 2 -} , - CH 2 O -, - CF 2 O -, - OCF 2 -, - (CH 2) 4 - is when a is a relatively chemically stable It is relatively difficult to deteriorate.

  As described above, a compound having desired physical properties can be obtained by appropriately selecting the kind of ring A, terminal group R, linking group Z and the like. Therefore, the compound (1) is useful as a component of a composition used for devices such as PC, TN, STN, ECB, OCB, IPS, and VA.

これらの式において、Ｒ^０は、炭素数１〜１５のアルキル、炭素数２〜１５のアルケニル、炭素数１〜１５のアルコキシ、または炭素数２〜１５のアルケニルオキシであり；Ｒ^１は、フッ素、塩素、−ＣＦ_３、−ＣＨＦ_２、−ＣＨ_２Ｆ、−ＯＣＦ_３、−ＯＣＨＦ_２、または−ＯＣＨ_２Ｆであり；環Ａ^１、環Ａ^２、環Ａ^３、環Ａ^４、環Ａ^５、環Ａ^６、環Ａ^７、および環Ａ^８は独立して、１，４−シクロヘキシレン、１，３−ジオキサン−２，５−ジイル、１，４−フェニレン、または任意の水素がフッ素で置き換えられた１，４−フェニレンであり；Ｚ^１、Ｚ^２、Ｚ^３、Ｚ^４、Ｚ^５、Ｚ^６、Ｚ^７、およびＺ^８は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＣＦ_２Ｏ−、−ＣＨ_２Ｏ−、または−ＯＣＨ_２−であり；Ｌ^３およびＬ^４は独立して、水素またはフッ素である。 1-3 Specific Examples of Compound (1) Preferred examples of the compound (1) are the formulas (1-1) to (1-2) shown in the item [5]. More preferable examples are the formulas (1-3) to (1-14) shown in the item [6]. Further preferred examples are formulas (1-15) to (1-20) shown in item [7]. Most preferred examples are the formulas (1-20) to (1-24) shown in item [8].

In these formulas, R ⁰ is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 15 carbons, or alkenyloxy having 2 to 15 carbons; R ¹ is fluorine. , Chlorine, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F; ring A ¹ , ring A ² , ring A ³ , ring A ⁴ , ring A ⁵ , Ring A ⁶ , Ring A ⁷ , and Ring A ⁸ are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, or any hydrogen is fluorine 1,4-phenylene replaced by: Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , and Z ⁸ are independently a single bond, —CH ₂ CH ₂ — , -CH = CH -, - C≡C -, - COO -, - CF 2 O , _-CH 2 O-, or -OCH ₂ - a and; ^{L 3} and ^{L 4} are each independently hydrogen or fluorine.

これらの式において、Ｒ^０は炭素数１〜１５のアルキル、炭素数２〜１５のアルケニル、炭素数１〜１５のアルコキシ、または炭素数２〜１５のアルケニルオキシであり；Ｒ^１は、フッ素、−ＣＦ_３、または−ＯＣＦ_３であり；環Ａ^１、は独立して、１，４−シクロヘキシレン、１，４−フェニレン、または任意の水素がフッ素で置き換えられた１，４−フェニレンであり；Ｚ^１、Ｚ^２、Ｚ^３、Ｚ^６、Ｚ^７、およびＺ^８は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＣＦ_２Ｏ−、−ＣＨ_２Ｏ−、または−ＯＣＨ_２−であり；Ｙ¹、Ｙ^２、Ｙ^３、Ｙ^４、Ｙ^５、およびＹ^６は独立して、水素またはフッ素であり；Ｌ^３、Ｌ^４、およびＬ^５は独立して、水素またはフッ素であり；式（１−１３）および式（１−１４）において、Ｒ^２、Ｌ^３、Ｌ^４、およびＬ^５は、インドール環の４位、５位、６位、および７位から選ばれた個別な１つずつにある。

In these formulas, R ⁰ is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 15 carbons, or alkenyloxy having 2 to 15 carbons; R ¹ is fluorine, -CF ₃ or -OCF ₃ ; ring A ¹ is independently 1,4-cyclohexylene, 1,4-phenylene, or 1,4-phenylene in which any hydrogen is replaced by fluorine Z ¹ , Z ² , Z ³ , Z ⁶ , Z ⁷ , and Z ⁸ are each independently a single bond, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, —COO—, —CF ₂ O—, —CH ₂ O—, or —OCH ₂ —; Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , and Y ⁶ are independently hydrogen or fluorine; L ^{3, L 4,} and ^{L 5} are independently hydrogen or fluorine der ; In the formula (1-13) and formula ^{(1-14), R 2, L} 3, L 4, and ^{L 5,} the 4-position of the indole ring, 5-position, 6-position, and the individual selected from 7-position One by one.

これらの式において、Ｒ^０は炭素数１〜１５のアルキル、炭素数２〜１５のアルケニル、または炭素数１〜１５のアルコキシであり；Ｒ^１は、フッ素、−ＣＦ_３、または−ＯＣＦ_３であり；Ｙ¹、Ｙ^２、Ｙ^３、およびＹ^４は独立して、水素またはフッ素であり；Ｌ^３およびＬ^４は独立して、水素またはフッ素である。

In these formulas, R ⁰ is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, or alkoxy having 1 to 15 carbons; R ¹ is fluorine, —CF ₃ , or —OCF ₃ Yes; Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or fluorine; L ³ and L ⁴ are independently hydrogen or fluorine.

これらの式において、Ｒ^０は炭素数１〜１５のアルキルである。

In these formulas, R ⁰ is alkyl having 1 to 15 carbons.

1-4 Synthesis of Compound (1) Next, synthesis of compound (1) will be described. Compound (1) can be synthesized by appropriately combining techniques in organic synthetic chemistry. Methods for introducing the desired end groups, rings and linking groups into the starting materials are Organic Syntheses (John Wiley & Sons, Inc), Organic Reactions (John Wiley & Sons, Inc), Comprehensive・ It is described in the organic synthesis (Comprehensive Organic Synthesis, Pergamon Press), new experimental chemistry course (Maruzen).

1-4-1. Method for Generating Bonding Group Z An example of a method for generating the bonding group Z in the compound (1) is as shown in the following scheme. In this scheme, MSG ¹ or MSG ² is a monovalent organic group having at least one ring. A plurality of MSG ¹ (or MSG ² ) used in the scheme may be the same or different. Compounds (1A) to (1J) correspond to compound (1).

  Next, with respect to the linking group Z in the compound (1), methods for generating various bonds will be described in the following items (I) to (XI).

(I) Formation of a single bond A compound obtained by reacting an arylboric acid (15) with a compound (16) synthesized by a known method in the presence of a catalyst such as an aqueous carbonate solution and tetrakis (triphenylphosphine) palladium. Synthesize (1A). This compound (1A) is obtained by reacting compound (17) 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.

(II) Formation of —COO— and —OCO— The compound (17) is reacted with n-butyllithium and subsequently with carbon dioxide to obtain a carboxylic acid (18). Compound (18) and phenol (19) synthesized by a known method are dehydrated in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) to have -COO- Synthesize (1B). A compound having —OCO— is also synthesized by this method.

(III) Formation of —CF ₂ O— and —OCF ₂ — Compound (1B) is treated with a sulfurizing agent such as Lawesson'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 (1C) having —CF ₂ O—. See M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1C) can also be synthesized by fluorinating compound (20) with (diethylamino) sulfur trifluoride (DAST). See WH Bunnelle et al., J. Org. Chem. 1990, 55, 768. A compound having —OCF ₂ — is also synthesized by this method. These linking groups can also be generated by the method described in Peer. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480.

(IV) Formation of —CH═CH— Compound (17) is treated with n-butyllithium and then reacted with formamide such as N, N-dimethylformamide (DMF) to obtain aldehyde (22). A phosphoryl ylide generated by treating a phosphonium salt (21) synthesized by a known method with a base such as potassium tert-butoxide is reacted with an aldehyde (22) to synthesize a compound (1D). Since a cis isomer is generated depending on the reaction conditions, the cis isomer is isomerized to a trans isomer by a known method as necessary.

(V) Formation of — (CH ₂ ) ₂ — Compound (1E) is synthesized by hydrogenating compound (1D) in the presence of a catalyst such as palladium carbon.

(VI) Formation of — (CH ₂ ) ₄ — A compound having — (CH ₂ ) ₂ —CH═CH— is prepared by using the phosphonium salt (23) instead of the phosphonium salt (21) and according to the method of the item (IV). obtain. This is catalytically hydrogenated to synthesize compound (1F).

(VII) Formation of —C≡C— After reacting compound (17) with 2-methyl-3-butyn-2-ol in the presence of a catalyst of dichloropalladium and copper halide, under basic conditions Deprotection gives compound (24). Compound (1G) is synthesized by reacting compound (24) with compound (16) in the presence of a catalyst of dichlorobistriphenylphosphine palladium and copper halide.

(VIII) Formation of —CF═CF— The compound (17) is treated with n-butyllithium and then reacted with tetrafluoroethylene to obtain the compound (25). Compound (16) is treated with n-butyllithium and then reacted with compound (25) to synthesize compound (1H).

(IX) Formation of —CH ₂ O— or —OCH ₂ — Compound (26) is obtained by reducing compound (22) with a reducing agent such as sodium borohydride. This is halogenated with hydrobromic acid or the like to obtain compound (27). Compound (27) is reacted with compound (19) in the presence of potassium carbonate or the like to synthesize compound (1I).

Formation of (X)-(CH ₂ ) ₃ O— or —O (CH ₂ ) ₃ — Compound (1J) was prepared in the same manner as in (IX) above using Compound (28) instead of Compound (22). ).

1-4-2 Method for synthesizing ring A 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3- Such as difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2,3,5,6-tetrafluoro-1,4-phenylene, etc. For rings, starting materials are commercially available or synthetic methods are well known.

1-4-3 Method for Synthesizing Compound (1) There are a plurality of methods for synthesizing the compound represented by Formula (1), and examples thereof are shown here. After coupling the indole derivative (31) and the boronic acid derivative (32) in the presence of tetrakistriphenylphosphine palladium, potassium carbonate and the like to lead to the indole derivative (33), the iodine derivative (34), diethylcyclohexanediamine ( 35) can be coupled to the compound (1) in the presence of copper iodide, potassium carbonate or the like.

これらの式において、Ｒ^０、Ｒ^１、環Ａ^１、環Ａ^２、環Ａ^３、環Ａ^４、環Ａ^５、環Ａ^６、環Ａ^７、環Ａ^８、Ｚ^１、Ｚ^２、Ｚ^３、Ｚ^４、Ｚ^６、Ｚ^７、Ｚ^８、ａ^１、ａ^２、ａ^３、ａ^４、ａ^５、ａ^６、ａ^７およびａ^８は、項［１］と同じ定義である。

In these formulas, R ⁰ , R ¹ , ring A ¹ , ring A ² , ring A ³ , ring A ⁴ , ring A ⁵ , ring A ⁶ , ring A ⁷ , ring A ⁸ , Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁶ , Z ⁷ , Z ⁸ , a ¹ , a ² , a ³ , a ⁴ , a ⁵ , a ⁶ , a ⁷ and a ⁸ have the same definition as in the term [1].

Among the compounds represented by the formula (1), when (a ¹ = a ² = a ³ = a ⁴ = 0), it can also be synthesized by the following method.

  The indole derivative (33) synthesized by the method described above can be coupled to the compound (1) by coupling in the presence of bromide (36) and potassium hydroxide.

これらの式において、Ｒ^０、Ｒ^１、Ａ^５、Ａ^６、Ａ^７、Ａ^８、Ｚ^６、Ｚ^７、Ｚ^８、ａ^５、ａ^６、ａ^７、およびａ^８は、項［１］と同じ定義である。

In these formulas, R ⁰ , R ¹ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , Z ⁶ , Z ⁷ , Z ⁸ , a ⁵ , a ⁶ , a ⁷ , and a ⁸ are the terms [1]. Is the same definition as

2 Composition of the Present Invention The second aspect of the present invention is a composition containing a compound represented by the formula (1), and is preferably a liquid crystal composition that can be used for a liquid crystal material. The liquid crystal composition of the present invention needs to contain as the component A the compound represented by the formula (1) of the present invention. The composition of only component A or the composition of component A and other components not specifically indicated in the present specification may be used, but components B, C, D, and By adding a component selected from E, the liquid crystal composition of the present invention having various characteristics can be provided.

The component added to Component A was selected from Component B consisting of at least one compound selected from the group consisting of Formulas (2), (3) and (4), or from the group consisting of Formula (5). Mixing component C consisting of at least one compound or component D consisting of at least one compound selected from the group consisting of formulas (6), (7), (8), (9) and (10) Is preferred.
Furthermore, by mixing component E consisting of at least one compound selected from the group consisting of formulas (11), (12) and (13), threshold voltage, liquid crystal phase temperature range, optical anisotropy The value, dielectric anisotropy value, viscosity and the like can be adjusted.

  In addition, each component of the liquid crystal composition used in the present invention is not greatly different in physical properties even if it is an analog composed of an isotope element of each element.

  Among the components B, formulas (2-1) to (2-16) are preferred examples of the compound represented by formula (2), and formula (3-1) is a preferred example of the compound represented by formula (3). ) To (3-112) and preferred examples of the compound represented by formula (4) include formulas (4-1) to (4-52), respectively.

これらの式において、Ｒ^２およびＸ^２は、項［１０］と同じ定義である。

In these formulas, R ² and X ² have the same definition as the term [10].

Since the compounds represented by the formulas (2) to (4), that is, the component B, have a positive dielectric anisotropy value and are very excellent in thermal stability and chemical stability, they are used for TFTs. It is used when preparing a liquid crystal composition. The content of component B in the liquid crystal composition of the present invention is suitably in the range of about 1 to about 99% by weight with respect to the total weight of the liquid crystal composition, preferably about 10 to about 97% by weight, more preferably about 40 to about 95% by weight. The viscosity can be adjusted by further containing a compound (component E) represented by formulas (11) to (13).
Preferred examples of the compound represented by formula (5), that is, component C include formulas (5-1) to (5-62).

これらの式において、Ｒ^３およびＸ^３は、項［１１］と同じ定義である。

In these formulas, R ³ and X ³ have the same definition as the term [11].

  The compound represented by the formula (5), that is, the component C, is mainly used when preparing a liquid crystal composition for STN and TN because the dielectric anisotropy value is positive and the value is very large. By containing this component C, the threshold voltage of the composition can be reduced. Further, the viscosity, the optical anisotropy value, and the liquid crystal phase temperature range can be expanded. It can also be used to improve steepness.

  When the liquid crystal composition for STN or TN is prepared, the content of component C is preferably in the range of about 0.1 to about 99.9% by weight, more preferably about 10 to 10%, based on the total amount of the composition. It is in the range of about 97% by weight, more preferably in the range of about 40 to about 95% by weight. In addition, the threshold voltage, the liquid crystal phase temperature range, the optical anisotropy value, the dielectric anisotropy value, the viscosity, and the like can be adjusted by mixing the components described later.

  Component D comprising at least one compound selected from the group consisting of formulas (6) to (8) and formula (10) is a dielectric anisotropy used in a vertical alignment mode (VA mode) and the like. Is a preferred component when preparing the liquid crystal composition of the present invention in which is negative.

  Preferable examples of the compound (component D) represented by the formulas (6) to (8) and the formula (10) are the formulas (6-1) to (6-5) and the formulas (7-1) to (7-1), respectively. 7-11), formula (8-1), and formulas (10-1) to (10-11).

これらの式において、Ｒ^４およびＲ^５は、項［１２］と同じ定義である。

In these formulas, R ⁴ and R ⁵ are as defined in the term [12].

  These compounds of component D are mainly used in liquid crystal compositions for VA mode having a negative dielectric anisotropy value. Increasing the content lowers the threshold voltage of the composition, but increases the viscosity. Therefore, it is preferable to reduce the content as long as the required value of the threshold voltage is satisfied. However, since the absolute value of the dielectric anisotropy value is about 5, if the content is less than about 40% by weight, voltage driving may not be possible.

  Since the compound represented by the formula (6) among the component D is a bicyclic compound, it is mainly effective in adjusting the threshold voltage, adjusting the viscosity, or adjusting the optical anisotropy value. Further, since the compounds represented by the formulas (7) and (8) are tricyclic compounds, the clearing point is increased, the nematic range is increased, the threshold voltage is decreased, and the optical anisotropy value is increased. The effect of doing etc. is acquired.

  When preparing a composition for VA mode, the content of component D is preferably about 40% by weight or more, more preferably in the range of about 50 to about 95% by weight, based on the total amount of the composition. It is. Further, by mixing the component D, it is possible to control the elastic constant and control the voltage transmittance curve of the composition. When component D is mixed with a composition having a positive dielectric anisotropy value, the content is preferably about 30% by weight or less based on the total amount of the composition.

  Preferable examples of the compound (component E) represented by the formulas (11), (12) and (13) are the formulas (11-1) to (11-11) and the formulas (12-1) to (12-18), respectively. ) And formulas (13-1) to (13-6).

これらの式において、Ｒ^６およびＲ^７は、項［１３］と同じ定義である

In these formulas, R ⁶ and R ⁷ have the same definition as the term [13].

  The compound (component E) represented by the formulas (11) to (13) is a compound having a small absolute value of dielectric anisotropy and close to neutrality. The compound represented by the formula (11) mainly has an effect of adjusting the viscosity or the optical anisotropy value, and the compounds represented by the formulas (12) and (13) are nematic such as increasing the clearing point. It has the effect of widening the range or adjusting the refractive index anisotropy value.

Increasing the content of the compound represented by Component E increases the threshold voltage of the liquid crystal composition and decreases the viscosity. Therefore, as long as the required value of the threshold voltage of the liquid crystal composition is satisfied, the content is More is desirable. When preparing a liquid crystal composition for TFT, the content of component E is preferably about 30% by weight or more, more preferably about 50% by weight or more based on the total amount of the composition. Further, when preparing a liquid crystal composition for STN or TN, the content of component E is preferably about 30% by weight or more, more preferably about 40% by weight or more based on the total amount of the composition.
The liquid crystal composition of the present invention contains at least one compound represented by the formula (1) of the present invention in a proportion of about 0.1 to about 99% by weight in order to develop excellent characteristics. preferable.

  The liquid crystal composition of the present invention is generally prepared by a known method, for example, a method of dissolving necessary components at a high temperature. Further, an additive well known to those skilled in the art is added depending on the application, for example, the liquid crystal composition (e) of the present invention containing the optically active compound as described below, and the GH type to which a dye is added. A liquid crystal composition can be prepared. Usually, additives are well known to those skilled in the art and are described in detail in the literature.

The liquid crystal composition (e) of the present invention further contains one or more optically active compounds in addition to the liquid crystal composition of the present invention described above.
A known chiral dopant is added as an optically active compound. This chiral dopant has the effect of inducing the helical structure of the liquid crystal to adjust the necessary twist angle and preventing reverse twist. Examples of the chiral dopant include the following optically active compounds (Op-1) to (Op-13).

  In the liquid crystal composition (e) of the present invention, these optically active compounds are usually added to adjust the twist pitch. The twist pitch is preferably adjusted in the range of 40 to 200 μm in the case of a liquid crystal composition for TFT and TN. If it is the liquid crystal composition for STN, it is preferable to adjust to the range of 6-20 micrometers. In the case of the bistable TN (Bistable TN) mode, it is preferably adjusted to a range of 1.5 to 4 μm. Two or more optically active compounds may be added for the purpose of adjusting the temperature dependence of the pitch.

  The liquid crystal composition of the present invention can be obtained as a liquid crystal composition for the GH type by adding a dichroic dye such as merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone, and tetrazine. It can also be used.

  In addition, the liquid crystal composition of the present invention includes NCAP produced by encapsulating nematic liquid crystal, and polymer dispersed liquid crystal display element (PDLCD) produced by forming a three-dimensional network polymer in liquid crystal, for example, a polymer. It can be used as a liquid crystal composition for birefringence control (ECB) type and DS type as well as for network liquid crystal display elements (PNLCD).

[[Example]]
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited by these Examples. Unless otherwise specified, “%” means “% by weight”.

Since the obtained compound was identified by a nuclear magnetic resonance spectrum obtained by ¹ H-NMR analysis, a gas chromatogram obtained by gas chromatography (GC) analysis, etc., the analysis method will be described first.

¹ H-NMR analysis: DRX-500 (manufactured by Bruker Biospin Co., Ltd.) was used as a measurement apparatus. The measurement was carried out by dissolving the sample produced in Examples and the like in a deuterated solvent in which a sample such as CDCl ₃ is soluble, and at room temperature under conditions of 500 MHz and 24 times of integration. In the description of the obtained nuclear magnetic resonance spectrum, s is a singlet, d is a doublet, t is a triplet, q is a quartet, and m is a multiplet. Tetramethylsilane (TMS) was used as a reference material for the zero point of the chemical shift δ value.

  GC analysis: GC-14B type gas chromatograph made by Shimadzu Corporation was used as a measuring apparatus. As the column, a capillary column CBP1-M25-025 (length 25 m, inner diameter 0.22 mm, film thickness 0.25 μm) manufactured by Shimadzu Corporation; dimethylpolysiloxane; nonpolar) was used as the stationary liquid phase. Helium was used as the carrier gas, and the flow rate was adjusted to 1 ml / min. 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 toluene to prepare a 1% by weight solution, and 1 μl of the resulting solution was injected into the sample vaporization chamber.
As a recorder, a C-R6A type Chromatopac manufactured by Shimadzu Corporation or an equivalent thereof was used. The obtained gas chromatogram shows the peak retention time and peak area value corresponding to the component compounds.

  As a sample dilution solvent, for example, chloroform or hexane may be used. In addition, as columns, Agilent Technologies Inc. capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm), Agilent Technologies Inc. HP-1 (length 30 m, inner diameter 0) .32 mm, film thickness 0.25 μm), Rtx-1 from Restek Corporation (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm), BP-1 from SGE International Pty. Ltd (length 30 m, inner diameter) 0.32 mm, film thickness of 0.25 μm) or the like may be used.

  The area ratio of peaks in the gas chromatogram corresponds to the ratio of component compounds. In general, the weight% of the component compound of the analysis sample is not completely the same as the area% of each peak of the analysis sample. However, when the above-described column is used in the present invention, the correction factor is substantially 1. Therefore, the weight% of the component compound in the analysis sample substantially corresponds to the area% of each peak in the analysis sample. This is because there is no significant difference in the correction coefficients of the component liquid crystal compounds. In order to obtain the composition ratio of the liquid crystal compound in the liquid crystal composition more accurately by the gas chromatogram, an internal standard method based on the gas chromatogram is used. The liquid crystal compound component (test component) weighed in a certain amount accurately and the reference liquid crystal compound (reference material) are simultaneously measured by gas chromatography, and the area ratio between the peak of the obtained test component and the peak of the reference material Is calculated in advance. When correction is performed using the relative intensity of the peak area of each component with respect to the reference substance, the composition ratio of the liquid crystal compound in the liquid crystal composition can be determined more accurately from gas chromatography analysis.

[Samples for measuring physical properties of liquid crystal compounds, etc.]
There are two types of samples for measuring the physical property values of the liquid crystal compound: when the compound itself is used as a sample, and when the compound is mixed with a mother liquid crystal as a sample.

  In the latter case using a sample in which a compound is mixed with mother liquid crystals, the measurement is performed by the following method. First, 15% by weight of the obtained liquid crystal compound and 85% by weight of the mother liquid crystal are mixed to prepare a sample. Then, an extrapolated value is calculated from the measured value of the obtained sample according to the extrapolation method based on the following formula. This extrapolated value is taken as the physical property value of this compound.

  <Extrapolated value> = (100 × <Measured value of sample> − <Weight% of mother liquid crystal> × <Measured value of mother liquid crystal>) / <Weight% of liquid crystal compound>

  Even when the ratio between the liquid crystal compound and the mother liquid crystal is this ratio, when the smectic phase or crystal is precipitated at 25 ° C., the ratio between the liquid crystal compound and the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight. : 95% by weight, 1% by weight: 99% by weight In order, the physical property value of the sample was measured with a composition in which the smectic phase or crystals did not precipitate at 25 ° C., and the extrapolated value was calculated according to the above formula. This is determined as the physical property value of the liquid crystal compound.

There are various types of mother liquid crystals used for measurement. For example, the composition (% by weight) of the mother liquid crystals A is as follows.
Mother liquid crystal A:

[Method for measuring physical properties of liquid crystal compounds, etc.]
The physical property values were measured by the method described later. Many of these measuring methods are the methods described in the Standard of Electric Industries Association of Japan, EIAJ ED-2521A, or a modified method thereof. Moreover, TFT was not attached to the TN element used for the measurement.

  Among the measured values, when the liquid crystal compound itself was used as a sample, the obtained value was described as experimental data. When a mixture of a liquid crystal compound and mother liquid crystals was used as a sample, values obtained by extrapolation were described as experimental data.

Phase structure and phase transition temperature (° C.): Measurement was performed by the following methods (1) and (2).
(1) A compound is placed on a hot plate (Mettler FP-52 type hot stage) equipped with a polarizing microscope, and the phase state and its change are observed with a polarizing microscope while heating at a rate of 3 ° C./min. , Identified the type of liquid crystal phase.
(2) Using a scanning calorimeter DSC-7 system or Diamond DSC system manufactured by PerkinElmer, Inc., the temperature is raised and lowered at a rate of 3 ° C./min. The phase transition temperature was determined by onset.

Hereinafter, the crystal is expressed as C, and when the crystal can be distinguished, it is expressed as C ₁ or C ₂ , respectively. Further, the smectic phase is represented as S and the nematic phase is represented as N. The liquid (isotropic) was designated as I. 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. As a representation of the phase transition temperature, for example, “C 50.0 N 100.0 I” means that the phase transition temperature (CN) from the crystal to the nematic phase is 50.0 ° C., and the phase from the nematic phase to the liquid The transition temperature (NI) is 100.0 ° C. The same applies to other notations.

Maximum temperature of nematic phase (T _NI ; ° C.): A sample (mixture of liquid crystal compound and mother liquid crystal) is placed on a hot plate (Mettler FP-52 type hot stage) of a melting point measuring apparatus equipped with a polarizing microscope. The polarizing microscope was observed while heating at a rate of ° C / min. The temperature at which a part of the sample changed from a nematic phase to an isotropic liquid was defined as the upper limit temperature of the nematic phase. Hereinafter, the upper limit temperature of the nematic phase may be simply abbreviated as “upper limit temperature”.

  Low temperature compatibility: A sample in which a mother liquid crystal and a liquid crystal compound were mixed so that the liquid crystal compound was in an amount of 20% by weight, 15% by weight, 10% by weight, 5% by weight, 3% by weight, and 1% by weight. Make and place 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 a crystal or smectic phase was precipitated.

  Viscosity (bulk viscosity; η; measured at 20 ° C .; mPa · s): A mixture of a liquid crystal compound and a mother liquid crystal was measured using an E-type rotational viscometer.

  Optical anisotropy (refractive index anisotropy; Δn): Measurement was performed at 25 ° C. with an Abbe refractometer using light with a wavelength of 589 nm and a polarizing plate attached to an eyepiece. After rubbing the surface of the main prism in one direction, a sample (mixture of liquid crystal compound and mother liquid crystal) was dropped onto 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 refractive index anisotropy (Δn) was calculated from the equation: Δn = n∥−n⊥.

  Dielectric anisotropy (Δε; measured at 25 ° C.): Put a sample (mixture of liquid crystal compound and mother liquid crystal) into a liquid crystal cell with a gap (gap) between two glass substrates of about 9 μm and a twist angle of 80 degrees. It was. 20 volts was applied to the cell, and the dielectric constant (ε 率) in the major axis direction of the liquid crystal molecules was measured. 0.5 V was applied, and 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⊥.

  Synthesis of 1-propyl-4- (3 ', 4', 5'-trifluorobiphenyl-4-yl) -1H-indole (No. 23)

Step 1 To a reactor under a nitrogen atmosphere, 1.1 g of 1-bromopropane (e-1), 1.2 g of 4-bromo-1H-indole (e-2), 1.7 g of potassium hydroxide and 25 ml of DMF And stirred at room temperature for 1 hour. Thereto, 100 ml of water and 100 ml of toluene were added to separate into an organic layer and an aqueous layer, and an extraction operation was performed. The obtained organic layer was separated, washed sequentially with water, and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure, and the resulting residue was subjected to column chromatography using a mixed solvent of toluene and heptane (volume ratio of toluene: heptane = 1: 9) as a developing solvent and silica gel as a filler. The product was purified by a preparative operation according to, and dried to obtain 1.5 g of 4-bromo-1-propyl-1H-indole (e-3).

Second Step To reactor under nitrogen atmosphere 4-Bromo-1-propyl-1H-indole (e-3) 1.5 g, 3 ′, 4 ′, 5′-trifluorobiphenylboronic acid (e-4) 1 6.6 g, 10% aqueous potassium carbonate solution 8.1 ml, Pd (Ph ₃ P) ₄ 0.2 g, and dimethoxyethane 30 ml were added and heated to reflux for 5 hours. After cooling the reaction solution to 25 ° C., 100 ml of water and 100 ml of toluene were added, and the organic layer and the aqueous layer were separated to perform extraction operation. The obtained organic layer was separated, washed with water, and dried over anhydrous magnesium sulfate. The resulting solution is concentrated under reduced pressure, and the residue is fractionated by column chromatography using a mixed solvent of toluene and heptane (volume ratio of toluene: heptane = 1: 5) as a developing solvent and silica gel as a filler. Purified. Further purified by recrystallization from heptane and dried, 0.5 g of 1-propyl-4- (3 ′, 4 ′, 5′-trifluorobiphenyl-4-yl) -1H-indole (No. 23) was obtained. Obtained. The yield based on the compound (e-2) was 27%.

The chemical shift δ (ppm) of ¹ H-NMR analysis is as follows, and the obtained compound was 1-propyl-4- (3 ′, 4 ′, 5′-trifluorobiphenyl-4-yl)- It was identified to be 1H-indole (No. 23). Note that the measurement solvent is CDCl ₃ .

  Chemical shift δ (ppm); 7.81-7.79 (m, 2H), 7.62-7.60 (m, 2H), 7.39-7.18 (m, 6H), 6.67 ( d, 1H), 4.14 (t, 2H), 1.92 (m, 2H), 0.97 (t, 3H).

The transition temperature of compound (No. 23) obtained is as described below.
Transition temperature: C 66.5 I

Physical Properties of Compound (No. 23) 85% by weight of mother liquid crystals A and 1-propyl-4- (3 ′, 4 ′, 5′-trifluorobiphenyl-4-yl) -1H— obtained in Example 1 A liquid crystal composition B comprising 15% by weight of indole (No. 23) was prepared. The physical property of the obtained liquid crystal composition B was measured, and the extrapolated value of the physical property of the compound (No. 23) was calculated by extrapolating the measured value. The values were as follows:

Maximum temperature (T _NI ) = − 15.0 ° C .; dielectric anisotropy (Δε) = 30.27; optical anisotropy (Δn) = 0.124.
From these facts, it was found that the compound (No. 23) is a compound having excellent compatibility with other liquid crystal compounds and high dielectric anisotropy (Δε).

  Synthesis of 1- (4-propylphenyl) -4- (3,4,5-trifluorophenyl) -1H-indole (No. 57)

First Step To a reactor under a nitrogen atmosphere, 4-bromo-1H-indole (e-2) 3.3 g, 3,4,5-trifluorophenylboronic acid (e-5) 3.3 g, 10% carbonic acid 23.1 ml of an aqueous potassium solution, 0.6 g of Pd (Ph ₃ P) ₄ and 70 ml of dimethoxyethane were added and heated to reflux for 5 hours. After cooling the reaction solution to 25 ° C., 200 ml of water and 200 ml of toluene were added, and the organic layer and the aqueous layer were separated to perform extraction operation. The obtained organic layer was separated, washed with water, and dried over anhydrous magnesium sulfate. The resulting solution is concentrated under reduced pressure, and the residue is fractionated by column chromatography using a mixed solvent of toluene and heptane (volume ratio toluene: heptane = 2: 1) as a developing solvent and silica gel as a packing material. Purified. The product was further purified by recrystallization from heptane and dried to obtain 3.0 g of 4- (3,4,5-trifluorophenyl) -1H-indole (e-6). The yield based on the compound (e-2) was 72%.

Second Step To a reactor under a nitrogen atmosphere, 3.0 g of 4- (3,4,5-trifluorophenyl) -1H-indole (e-6), 1-iodo-4-propylbenzene (e-7) 3.6 g, copper (I) iodide 1.2 g, (1R, 2S) -N1, N2-dimethylcyclohexane-1,2-diamine (e-8) 0.9 g, tripotassium phosphate 5.4 g, toluene 30 ml was added and stirred at 110 ° C. for 8 hours. After cooling the reaction solution to 25 ° C., 100 ml of water and 70 ml of toluene were added, and the organic layer and the aqueous layer were separated to perform an extraction operation. The obtained organic layer was separated, washed with water, and dried over anhydrous magnesium sulfate. The resulting solution is concentrated under reduced pressure, and the residue is fractionated by column chromatography using a mixed solvent of toluene and heptane (volume ratio of toluene: heptane = 1: 9) as a developing solvent and silica gel as a filler. Purified with Further purification by recrystallization from heptane and drying yielded 3.0 g of 1- (4-propylphenyl) -4- (3,4,5-trifluorophenyl) -1H-indole (No. 57). . The yield based on the compound (e-6) was 66%.

The chemical shift δ (ppm) of ¹ H-NMR analysis is as follows, and the resulting compound is 1- (4-propylphenyl) -4- (3,4,5-trifluorophenyl) -1H— It was identified as indole (No. 57). Note that the measurement solvent is CDCl ₃ .

  Chemical shift δ (ppm); 7.56 (d, 1H), 7.42-7.28 (m, 8H), 7.15 (d, 1H), 6.77 (d, 1H), 2.68 (T, 2H), 1.72 (m, 2H), 1.01 (t, 3H).

The transition temperature of compound (No. 57) obtained is as described below.
Transition temperature: C 62.5 I

Physical properties of compound (No. 57) 85% by weight of mother liquid crystals A and 1- (4-propylphenyl) -4- (3,4,5-trifluorophenyl) -1H-indole obtained in Example 2 ( A liquid crystal composition C comprising 15% by weight of No. 57) was prepared. The physical property of the obtained liquid crystal composition C was measured, and the extrapolated value of the physical property of the compound (No. 57) was calculated by extrapolating the measured value. The values were as follows:

Maximum temperature (T _NI ) = − 18.3 ° C .; dielectric anisotropy (Δε) = 21.03; optical anisotropy (Δn) = 0.110.
From these results, it was found that the compound (No. 57) is a compound having excellent compatibility with other liquid crystal compounds and high dielectric anisotropy (Δε).

  Synthesis of 1- (4-propylphenyl) -5- (3,4,5-trifluorophenyl) -1H-indole (No. 63)

First Step To a reactor under a nitrogen atmosphere, 5-bromo-1H-indole (e-9) 5.0 g, 3,4,5-trifluorophenylboronic acid (e-5) 4.9 g, 10% carbonic acid 35.0 ml of aqueous potassium solution, 0.9 g of Pd (Ph ₃ P) ₄ and 100 ml of dimethoxyethane were added, and the mixture was heated to reflux for 5 hours. After cooling the reaction solution to 25 ° C., 200 ml of water and 200 ml of toluene were added, and the organic layer and the aqueous layer were separated to perform extraction operation. The obtained organic layer was separated, washed with water, and dried over anhydrous magnesium sulfate. The resulting solution is concentrated under reduced pressure, and the residue is fractionated by column chromatography using a mixed solvent of toluene and heptane (volume ratio toluene: heptane = 2: 1) as a developing solvent and silica gel as a packing material. Purified. The product was further purified by recrystallization from heptane and dried to obtain 4.1 g of 5- (3,4,5-trifluorophenyl) -1H-indole (e-10). The yield based on the compound (e-9) was 58%.

Second Step To a reactor under a nitrogen atmosphere, 5- (3,4,5-trifluorophenyl) -1H-indole (e-10) 4.1 g, 1-iodo-4-propylbenzene (e-7) 4.9 g, copper (I) iodide 1.6 g, (1R, 2S) -N1, N2-dimethylcyclohexane-1,2-diamine (e-8) 1.2 g, tripotassium phosphate 7.4 g, toluene 40 ml was added and it stirred at 110 degreeC for 8 hours. After cooling the reaction solution to 25 ° C., 100 ml of water and 60 ml of toluene were added, and an organic layer and an aqueous layer were separated to perform extraction operation. The obtained organic layer was separated, washed with water, and dried over anhydrous magnesium sulfate. The resulting solution is concentrated under reduced pressure, and the residue is fractionated by column chromatography using a mixed solvent of toluene and heptane (volume ratio of toluene: heptane = 1: 9) as a developing solvent and silica gel as a filler. Purified with The product was further purified by recrystallization from heptane and dried to obtain 3.8 g of 1- (4-propylphenyl) -5- (3,4,5-trifluorophenyl) -1H-indole (No. 63). . The yield based on the compound (e-10) was 63%.

The chemical shift δ (ppm) of ¹ H-NMR analysis is as follows, and the obtained compound is 1- (4-propylphenyl) -5- (3,4,5-trifluorophenyl) -1H— It was identified as indole (No. 63). Note that the measurement solvent is CDCl ₃ .

  Chemical shift δ (ppm); 7.80 (d, 1H), 7.59 (d, 1H), 7.45-7.21 (m, 8H), 6.72 (d, 1H), 2.68 (T, 2H), 1.72 (m, 2H), 1.01 (t, 3H).

The transition temperature of compound (No. 63) obtained is as follows.
Transition temperature: C 64.2 I

Physical properties of compound (No. 63) 85% by weight of mother liquid crystals A and 1- (4-propylphenyl) -5- (3,4,5-trifluorophenyl) -1H-indole obtained in Example 3 A liquid crystal composition D comprising 15% by weight of No. 63) was prepared. The physical property of the obtained liquid crystal composition D was measured, and the extrapolated value of the physical property of the compound (No. 63) was calculated by extrapolating the measured value. The values were as follows:

Maximum temperature (T _NI ) = − 27.6 ° C .; dielectric anisotropy (Δε) = 21.13; optical anisotropy (Δn) = 0.104.
From these facts, it was found that the compound (No. 63) has excellent compatibility with other liquid crystal compounds and has a high dielectric anisotropy (Δε).

  Synthesis of 1- (4- (4-propylcyclohexyl) phenyl) -4- (3,4,5-trifluorophenyl) -1H-indole (No. 193)

First Step: 4- (3,4,5-trifluorophenyl) -1H-indole (e-6) 1.0 g, 1-iodo synthesized by the method described in Example 2 into a reactor under a nitrogen atmosphere -4- (4-propylcyclohexyl) benzene (e-11) 1.6 g, copper iodide (I) 0.4 g, (1R, 2S) -N1, N2-dimethylcyclohexane-1,2-diamine (e- 8) 0.3 g, tripotassium phosphate 1.8 g, and toluene 10 ml were added and stirred at 110 ° C. for 8 hours. After cooling the reaction solution to 25 ° C., 50 ml of water and 40 ml of toluene were added, and the organic layer and the aqueous layer were separated to perform extraction operation. The obtained organic layer was separated, washed with water, and dried over anhydrous magnesium sulfate. The resulting solution is concentrated under reduced pressure, and the residue is fractionated by column chromatography using a mixed solvent of toluene and heptane (volume ratio of toluene: heptane = 1: 9) as a developing solvent and silica gel as a filler. Purified. Further purified by recrystallization from heptane, dried and 1- (4- (4-propylcyclohexyl) phenyl) -4- (3,4,5-trifluorophenyl) -1H-indole (No. 193) 1 .5 g was obtained. The yield based on the compound (e-6) was 84%.

The chemical shift δ (ppm) of ¹ H-NMR analysis is as follows, and the obtained compound is 1- (4- (4-propylcyclohexyl) phenyl) -4- (3,4,5-trifluoro. Phenyl) -1H-indole (No. 193). Note that the measurement solvent is CDCl ₃ .

  Chemical shift δ (ppm); 7.57 (d, 1H), 7.43-7.27 (m, 8H), 7.15 (d, 1H), 6.76 (d, 1H), 2.57 (M, 1H), 1.94 (m, 4H), 1.51 (m, 2H), 1.41-1.30 (m, 3H), 1.25 (m, 2H), 1.09 ( m, 2H), 0.92 (t, 3H).

The transition temperature of compound (No. 193) obtained is as follows.
Transition temperature: C 120.2 N 137.7 I

Physical properties of compound (No. 193) 90% by weight of mother liquid crystals A and 1- (4- (4-propylcyclohexyl) phenyl) -4- (3,4,5-trifluorophenyl) obtained in Example 4 A liquid crystal composition E comprising 10% by weight of -1H-indole (No. 193) was prepared. The physical property of the obtained liquid crystal composition E was measured, and the extrapolated value of the physical property of the compound (No. 193) was calculated by extrapolating the measured value. The values were as follows:

Maximum temperature (T _NI ) = 17.7 ° C .; dielectric anisotropy (Δε) = 19.8; optical anisotropy (Δn) = 0.167.
From these results, it was found that the compound (No. 193) has excellent compatibility with other liquid crystal compounds and has high dielectric anisotropy (Δε).

Compounds (No. 1) to (No. 395) shown below can be synthesized by a method similar to the synthesis method described in Examples 1, 2, 3, and 4. The appended data is a value measured according to the method described above. The transition temperature is a measured value of the compound itself, and the maximum temperature (T _NI ), dielectric anisotropy (Δε), and optical anisotropy (Δn) are measured in a sample in which the compound is mixed with the mother liquid crystal (i). It is a physical property value converted according to the extrapolation method.

[Examples of liquid crystal composition]
Hereinafter, the liquid crystal composition obtained by the present invention will be described in detail with reference to examples. The liquid crystalline compounds used in the examples are represented by symbols based on the definitions in the following table. In the table, 1,4-cyclohexylene has a trans configuration. The ratio (percentage) of each compound is a weight percentage (% by weight) based on the total weight of the composition unless otherwise specified. The characteristics of the composition obtained at the end of each example are shown.

  In addition, the number described in the portion of the liquid crystal compound used in each example corresponds to the formula number indicating the liquid crystal compound contained in the liquid crystal composition of the present invention described above, and the formula number is not described. In addition, when “-” is simply described, this means that this compound is another compound.

  The notation method by the symbol of a compound is shown below.

  The characteristics were measured according to the following method. Many of these are the methods described in the Standard of Electric Industries Association of Japan EIAJ ED-2521A or a modified method thereof.

(1) Maximum temperature of nematic phase (NI; ° C)
A sample was placed on a hot plate of a melting point measurement 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. Hereinafter, the upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”.

(2) Minimum temperature of nematic phase (TC; ° C)
A sample having a nematic phase was stored in a freezer at 0 ° C., −10 ° C., −20 ° C., −30 ° C., and −40 ° C. for 10 days, and then the liquid crystal phase was observed. For example, when the sample remained in a nematic phase at −20 ° C. and changed to a crystalline or smectic phase at −30 ° C., the TC was described as ≦ −20 ° C. Hereinafter, the lower limit temperature of the nematic phase may be abbreviated as “lower limit temperature”.

(3) Optical anisotropy (Δn; measured at 25 ° C.)
Measurement was performed using an Abbe refractometer with a polarizing plate attached to the eyepiece using light having a wavelength of 589 nm. First, after rubbing the surface of the main prism in one direction, the sample was dropped on the main prism. Then, the refractive index (n‖) when the polarization direction was parallel to the rubbing direction and the refractive index (n⊥) when the polarization direction was perpendicular to the rubbing direction were measured. The value of optical anisotropy (Δn) was calculated from the equation (Δn) = (n∥) − (n∥).

(4) Viscosity (bulk viscosity; η; measured at 20 ° C .; mPa · s)
An E-type viscometer was used for the measurement.

(5) Dielectric anisotropy (Δε; measured at 25 ° C.)
An ethanol (20 mL) solution of octadecyltriethoxysilane (0.16 mL) was applied to a well-cleaned glass substrate. The glass substrate was rotated with a spinner and then heated at 150 ° C. for 1 hour. A VA device having an interval (cell gap) of 20 μm was assembled from two glass substrates.

  In the same manner, a polyimide alignment film was prepared on a glass substrate. After the alignment film of the obtained glass substrate was rubbed, a TN device in which the distance between the two glass substrates was 9 μm and the twist angle was 80 degrees was assembled.

  A sample (a liquid crystal composition or a mixture of a liquid crystal compound and a mother liquid crystal) is placed in the obtained VA element, 0.5 V (1 kHz, sine wave) is applied, and the dielectric constant (in the major axis direction of the liquid crystal molecules ( ε‖) was measured.

In addition, a sample (a liquid crystal composition or a mixture of a liquid crystal compound and a mother liquid crystal) is put into the obtained TN device, 0.5 V (1 kHz, sine wave) is applied, and the dielectric in the minor axis direction of the liquid crystal molecules. The rate (ε⊥) was measured.
The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.
A composition having a negative value is a composition having a negative dielectric anisotropy.

(6) Voltage holding ratio (VHR; measured at 25 ° C. and 100 ° C .;%)
A sample was put in a cell having a polyimide alignment film and a distance (cell gap) between two glass substrates of 6 μm to produce a TN device. At 25 ° C., the TN device was charged by applying a pulse voltage (5 V, 60 microseconds). The waveform of the voltage applied to the TN device was observed with a cathode ray oscilloscope, and the area between the voltage curve and the horizontal axis in a unit cycle (16.7 milliseconds) was determined. The area was similarly determined from the waveform of the voltage applied after removing the TN element. The value of the voltage holding ratio (%) was calculated from the value of (voltage holding ratio) = (area value when there is a TN element) / (area value when there is no TN element) × 100.

  The voltage holding ratio thus obtained is indicated as “VHR-1”. Next, this TN device was heated at 100 ° C. for 250 hours. After returning the TN device to 25 ° C., the voltage holding ratio was measured by the same method as described above. The voltage holding ratio obtained after this heating test was shown as “VHR-2”. This heating test is an accelerated test, and was used as a test corresponding to the long-term durability test of the TN device.

3-BIn (1,5) B (F, F) -F (No. 63) 3%
3-BIn (1,4) B (F, F) -F (No. 57) 3%
2-BEB (F) -C (5-14) 5%
3-BEB (F) -C (5-14) 4%
4-BEB (F) -C (5-14) 12%
1V2-BEB (F, F) -C (5-15) 16%
3-HB-O2 (11-5) 10%
3-HH-4 (11-1) 3%
3-HHB-F (3-1) 3%
3-HHB-1 (12-1) 8%
3-HHB-O1 (12-1) 4%
3-HBEB-F (3-37) 4%
3-HHEB-F (3-10) 5%
5-HHEB-F (3-10) 3%
3-H2BTB-2 (12-16) 4%
3-H2BTB-3 (12-16) 4%
3-H2BTB-4 (12-16) 4%
3-HB (F) TB-2 (12-17) 5%
NI = 73.4 ° C .; Δn = 0.140; Δε = 29.2; Vth = 1.01V.

3-HBIn (1,4) B (F, F) -F (No. 193) 3%
3-In (1,4) BB (F, F) -F (No. 23) 3%
2-HB-C (5-1) 5%
3-HB-C (5-1) 12%
3-HB-O2 (11-5) 15%
2-BTB-1 (11-10) 3%
3-HHB-F (3-1) 4%
3-HHB-1 (12-1) 8%
3-HHB-O1 (12-1) 5%
3-HHB-3 (12-1) 14%
3-HHEB-F (3-10) 4%
2-HHB (F) -F (3-2) 7%
3-HHB (F) -F (3-2) 7%
5-HHB (F) -F (3-2) 7%
3-HHB (F, F) -F (3-3) 3%
NI = 92.5 ° C .; Δn = 0.101; Δε = 5.8; Vth = 2.11 V; η = 23.8 mPa · sec.

3-BIn (1,5) B (F, F) -F (No. 63) 4%
3-HBIn (1,4) B (F, F) -F (No. 193) 3%
3-BEB (F) -C (5-14) 8%
3-HB-C (5-1) 8%
V-HB-C (5-1) 8%
1V-HB-C (5-1) 8%
3-HB-O2 (11-5) 3%
3-HH-2V (11-1) 14%
3-HH-2V1 (11-1) 7%
V2-HHB-1 (12-1) 15%
3-HHB-1 (12-1) 5%
3-HHEB-F (3-10) 3%
3-H2BTB-2 (12-16) 6%
3-H2BTB-3 (12-16) 3%
3-H2BTB-4 (12-16) 5%
NI = 86.7 ° C .; Δn = 0.129; Δε = 9.4; Vth = 1.86 V; η = 23.1 mPa · sec.
When 0.25 part by weight of the optically active compound (Op-5) was added to 100 parts by weight of the composition, the pitch was 60.9 μm.

3-BIn (1,4) B (F, F) -F (No. 57) 3%
3-In (1,4) BB (F, F) -F (No. 23) 3%
5-BEB (F) -C (5-14) 5%
V-HB-C (5-1) 11%
5-PyB-C (5-8) 6%
4-BB-3 (11-8) 11%
3-HH-2V (11-1) 10%
5-HH-V (11-1) 11%
V-HHB-1 (12-1) 3%
V2-HHB-1 (12-1) 15%
3-HHB-1 (12-1) 9%
1V2-HBB-2 (12-4) 10%
3-HHEBH-3 (12-16) 3%
NI = 79.2 ° C .; Δn = 0.116; Δε = 6.2; Vth = 1.87 V; η = 23.7 mPa · sec.

3-BIn (1,5) B (F, F) -F (No. 63) 4%
3-BIn (1,4) B (F, F) -F (No. 57) 4%
1V2-BEB (F, F) -C (5-15) 6%
3-HB-C (5-1) 10%
2-BTB-1 (11-10) 10%
5-HH-VFF (11-1) 30%
3-HHB-1 (12-1) 4%
VFF-HHB-1 (12-1) 8%
VFF2-HHB-1 (12-1) 11%
3-H2BTB-2 (12-16) 5%
3-H2BTB-3 (12-16) 4%
3-H2BTB-4 (12-16) 4%
NI = 76.1 ° C .; Δn = 0.128; Δε = 7.2; Vth = 1.87 V; η = 22.2 mPa · sec. .

3-HBIn (1,4) B (F, F) -F (No. 193) 4%
3-In (1,4) BB (F, F) -F (No. 23) 4%
5-HB-CL (2-2) 16%
3-HH-4 (11-1) 12%
3-HH-5 (11-1) 4%
3-HHB-F (3-1) 4%
3-HHB-CL (3-1) 3%
4-HHB-CL (3-1) 4%
3-HHB (F) -F (3-2) 6%
4-HHB (F) -F (3-2) 5%
5-HHB (F) -F (3-2) 9%
7-HHB (F) -F (3-2) 8%
5-HBB (F) -F (3-23) 4%
1O1-HBBH-5 (13-1) 3%
3-HHBB (F, F) -F (4-6) 2%
4-HHBB (F, F) -F (4-6) 3%
5-HHBB (F, F) -F (4-6) 3%
3-HH2BB (F, F) -F (4-15) 3%
4-HH2BB (F, F) -F (4-15) 3%
NI = 110.9 ° C .; Δn = 0.096; Δε = 5.2; Vth = 2.10 V; η = 31.3 mPa · sec.

3-BIn (1,5) B (F, F) -F (No. 63) 4%
3-In (1,4) BB (F, F) -F (No. 23) 3%
3-HHB (F, F) -F (3-3) 9%
3-H2HB (F, F) -F (3-15) 8%
4-H2HB (F, F) -F (3-15) 8%
5-H2HB (F, F) -F (3-15) 8%
3-HBB (F, F) -F (3-24) 21%
5-HBB (F, F) -F (3-24) 20%
3-H2BB (F, F) -F (3-27) 8%
5-HHBB (F, F) -F (4-6) 3%
5-HHEB-F (3-10) 2%
3-HH2BB (F, F) -F (4-15) 3%
1O1-HBBH-5 (13-1) 3%
NI = 83.0 ° C .; Δn = 0.113; Δε = 10.3; Vth = 1.34V.

3-BIn (1,4) B (F, F) -F (No. 57) 4%
3-HBIn (1,4) B (F, F) -F (No. 193) 4%
5-HB-F (2-2) 12%
6-HB-F (2-2) 9%
7-HB-F (2-2) 7%
2-HHB-OCF3 (3-1) 7%
3-HHB-OCF3 (3-1) 7%
4-HHB-OCF3 (3-1) 7%
5-HHB-OCF3 (3-1) 5%
3-HH2B-OCF3 (3-4) 4%
5-HH2B-OCF3 (3-4) 4%
3-HHB (F, F) -OCF2H (3-3) 4%
3-HHB (F, F) -OCF3 (3-3) 5%
3-HH2B (F) -F (3-5) 3%
3-HBB (F) -F (3-23) 5%
5-HBB (F) -F (3-23) 7%
5-HBBH-3 (13-1) 3%
3-HB (F) BH-3 (13-2) 3%
NI = 82.4 ° C .; Δn = 0.092; Δε = 5.4; Vth = 2.12 V; η = 23.9 mPa · sec.

3-BIn (1,5) B (F, F) -F (No. 63) 3%
3-BIn (1,4) B (F, F) -F (No. 57) 3%
5-HB-CL (2-2) 11%
3-HH-4 (11-1) 8%
3-HHB-1 (12-1) 5%
3-HHB (F, F) -F (3-3) 8%
3-HBB (F, F) -F (3-24) 20%
5-HBB (F, F) -F (3-24) 15%
3-HHEB (F, F) -F (3-12) 10%
4-HHEB (F, F) -F (3-12) 3%
2-HBEB (F, F) -F (3-39) 3%
3-HBEB (F, F) -F (3-39) 5%
3-HHBB (F, F) -F (4-6) 6%
NI = 73.3 ° C .; Δn = 0.104; Δε = 9.0; Vth = 1.34V; η = 28.4 mPa · sec.

3-HBIn (1,4) B (F, F) -F (No. 193) 3%
3-In (1,4) BB (F, F) -F (No. 23) 3%
3-HB-CL (2-2) 3%
5-HB-CL (2-2) 4%
3-HHB-OCF3 (3-1) 5%
3-H2HB-OCF3 (3-13) 5%
5-H4HB-OCF3 (3-19) 15%
V-HHB (F) -F (3-2) 5%
3-HHB (F) -F (3-2) 5%
5-HHB (F) -F (3-2) 5%
3-H4HB (F, F) -CF3 (3-21) 8%
5-H4HB (F, F) -CF3 (3-21) 10%
5-H2HB (F, F) -F (3-15) 5%
5-H4HB (F, F) -F (3-21) 7%
2-H2BB (F) -F (3-26) 5%
3-H2BB (F) -F (3-26) 7%
3-HBEB (F, F) -F (3-38) 5%
NI = 70.4 ° C .; Δn = 0.100; Δε = 9.4; Vth = 1.66V.

3-BIn (1,5) B (F, F) -F (No. 63) 5%
3-HBIn (1,4) B (F, F) -F (No. 193) 4%
5-HB-CL (2-2) 8%
7-HB (F, F) -F (2-4) 3%
3-HH-4 (11-1) 10%
3-HH-5 (11-1) 5%
3-HB-O2 (11-5) 15%
3-HHB-1 (12-1) 8%
3-HHB-O1 (12-1) 5%
2-HHB (F) -F (3-2) 7%
3-HHB (F) -F (3-2) 7%
5-HHB (F) -F (3-2) 7%
3-HHB (F, F) -F (3-3) 6%
3-H2HB (F, F) -F (3-15) 5%
4-H2HB (F, F) -F (3-15) 5%
NI = 74.4 ° C .; Δn = 0.080; Δε = 4.1; Vth = 1.72 V; η = 27.6 mPa · sec.

3-BIn (1,4) B (F, F) -F (No. 57) 3%
3-In (1,4) BB (F, F) -F (No. 23) 4%
5-HB-CL (2-2) 3%
7-HB (F) -F (2-3) 7%
3-HH-4 (11-1) 9%
3-HH-EMe (11-2) 23%
3-HHEB-F (3-10) 8%
5-HHEB-F (3-10) 8%
3-HHEB (F, F) -F (3-12) 10%
4-HHEB (F, F) -F (3-12) 5%
4-HGB (F, F) -F (3-103) 5%
5-HGB (F, F) -F (3-103) 6%
2-H2GB (F, F) -F (3-106) 4%
3-H2GB (F, F) -F (3-106) 3%
5-GHB (F, F) -F (3-109) 2%
NI = 75.4 ° C .; Δn = 0.068; Δε = 6.2; Vth = 1.35 V; η = 28.1 mPa · sec.

3-BIn (1,5) B (F, F) -F (No. 63) 3%
3-BIn (1,4) B (F, F) -F (No. 57) 3%
3-HB-O2 (11-5) 10%
5-HB-CL (2-2) 13%
3-HBB (F, F) -F (3-3) 7%
3-PyB (F) -F (2-15) 10%
5-PyB (F) -F (2-15) 10%
3-PyBB-F (3-80) 10%
4-PyBB-F (3-80) 10%
5-PyBB-F (3-80) 10%
5-HBB (F) B-2 (13-5) 7%
5-HBB (F) B-3 (13-5) 7%
NI = 83.9 ° C .; Δn = 0.182; Δε = 9.0; Vth = 1.55V.

3-HBIn (1,4) B (F, F) -F (No. 193) 5%
3-In (1,4) BB (F, F) -F (No. 23) 3%
3-HH-V (11-1) 33%
3-BB (F, F) XB (F, F) -F (3-97) 18%
3-HHB-1 (12-1) 2%
2-HBB-F (3-22) 3%
3-HBB-F (3-22) 4%
3-HHB-CL (3-1) 3%
1-BB (F) B-2V (12-6) 6%
2-BB (F) B-2V (12-6) 6%
3-BB (F) B-2V (12-6) 3%
3-HHB (F, F) -F (3-3) 4%
4-BB (F) B (F, F) XB (F, F) -F (4-46) 10%
NI = 84.4 ° C .; Δn = 0.137; Δε = 8.9; Vth = 1.45 V; η = 28.5 mPa · sec.

  The compound of the present invention has general physical properties necessary for the compound, stability to heat, light, etc., good compatibility with other compounds, large dielectric anisotropy and appropriate optical anisotropy. The liquid crystal composition of the present invention contains at least one of these compounds and has good compatibility and a large dielectric anisotropy from a low temperature range. Since the liquid crystal display element of the present invention contains this composition and has a wide temperature range that can be used, a short response time, a small power consumption, a large contrast ratio, and a low driving voltage, a clock, a calculator, a word processor, etc. Can be widely used for display.

Claims (20)

The compound represented by Formula (1).

In this formula, R ⁰ and R ¹ are independently hydrogen, halogen, or alkyl having 1 to 20 carbons, in which any —CH ₂ — is replaced by —O— or —S—. And any — (CH ₂ ) ₂ — may be replaced with —CH═CH—, in which any hydrogen may be replaced with a halogen; ring A ¹ , ring A ² , ring A ³ , Ring A ⁴ , Ring A ⁵ , Ring A ⁶ , Ring A ⁷ , and Ring A ⁸ are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4 -Phenylene, or 1,4-phenylene in which any hydrogen is replaced by halogen; Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , and Z ⁸ are independently single _{bond, -CH 2 CH 2 -, -} CH = CH -, - _{≡C -, - COO -, -} OCO -, - CF 2 O -, - OCF 2 -, - CH 2 O -, - OCH 2 -, - CF = CF -, - (CH 2) 4 -, - ( _{CH 2) 2 CF 2 O -} , - (CH 2) 2 OCF 2 -, - CF 2 O (CH 2) 2 -, - OCF 2 (CH 2) 2 -, - CH = CH- (CH 2) 2 -, or _{- (CH 2) 2 -CH =} CH- and ^{is; L 1, L 2, L} 3, L 4, and ^{L 5} are independently hydrogen, halogen, -CH ₃ or -CF _3, Yes; a ¹ , a ² , a ³ , a ⁴ , a ⁵ , a ⁶ , a ⁷ , and a ⁸ are independently 0 or 1, and a ¹ , a ² , a ³ , a ⁴ , a ^5, the sum of ^a 6, ^{a 7,} and ^{a 8} is an 2, 3 or ^{4,; R 1 - (a} 1 Z 1) a 1 - (a 2 Z 2) a 2 ^{(A 3 Z 3) a 3} - (A 4 Z 4) a 4 -, L 1, and ^{L 2,} 1-position of the indole ring, there are two-position, and 3-position by one discrete selected from ^{, R 2 - (A 8 Z} 8) a 8 - (A 7 Z 7) a 7 - (A 6 Z 6) a 6 - (A 5 Z 5) a 5 -, L 3, L 4, and ^{L 5} Are each in an individual one selected from the 4th, 5th, 6th and 7th positions of the indole ring. In the formula (1), R ^0- (A ¹ Z ¹ ) a ^1- (A ² Z ² ) a ^2- (A ³ Z ³ ) a ^3- (A ⁴ Z ⁴ ) a ⁴ -is an indole ring 1 The compound of claim 1 in which L ¹ and L ² are hydrogen. In the formula (1), R ^0- (A ¹ Z ¹ ) a ^1- (A ² Z ² ) a ^2- (A ³ Z ³ ) a ^3- (A ⁴ Z ⁴ ) a ⁴ -is an indole ring 1 The compound of claim 1, wherein L ¹ and L ² are hydrogen; and the 6- and 7-positions of the indole ring are hydrogen or fluorine. In the formula (1), R ^0- (A ¹ Z ¹ ) a ^1- (A ² Z ² ) a ^2- (A ³ Z ³ ) a ^3- (A ⁴ Z ⁴ ) a ⁴ -is an indole ring 1 located position, and ^{R 1 - (a 8 Z 8} ) a 8 - (a 7 Z 7) a 7 - (a 6 Z 6) a 6 - (a 5 Z 5) a 5 - 4-position of the indole ring The compound of claim 1, wherein L ¹ and L ² are hydrogen; and L ³ , L ⁴ , and L ⁵ are hydrogen or fluorine. The compound according to claim 1, which is represented by any one of formulas (1-1) to (1-2).

In these formulas, R ⁰ is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 15 carbons, or alkenyloxy having 2 to 15 carbons; R ¹ is fluorine. , Chlorine, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F; ring A ¹ , ring A ² , ring A ³ , ring A ⁴ , ring A ⁵ , Ring A ⁶ , Ring A ⁷ , and Ring A ⁸ are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, or any hydrogen is fluorine 1,4-phenylene replaced by: Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , and Z ⁸ are independently a single bond, —CH ₂ CH ₂ — , -CH = CH -, - C≡C -, - COO -, - CF 2 O , _-CH 2 O-, or -OCH ₂ - a ^{is; a 1, a 2, a} 3, a 4, a 5, a 6, a 7, and ^{a 8} are independently 0 or 1, the sum of a ¹ , a ² , a ³ , a ⁴ , a ⁵ , a ⁶ , a ⁷ , and a ⁸ is 2, 3, or 4; Y ¹ and Y ² are independently hydrogen or fluorine It is. The compound according to claim 1 represented by any one of formulas (1-3) to (1-14).

In these formulas, R ⁰ is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 15 carbons, or alkenyloxy having 2 to 15 carbons; R ¹ is fluorine. , —CF ₃ , or —OCF ₃ ; ring A ¹ is 1,4-cyclohexylene, 1,4-phenylene, or 1,4-phenylene in which any hydrogen is replaced by fluorine; Z ¹ , Z ² , Z ³ , Z ⁶ , Z ⁷ , and Z ⁸ are each independently a single bond, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, —COO—, —CF _2. O—, —CH ₂ O—, or —OCH ₂ —; Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , and Y ⁶ are independently hydrogen or fluorine; L ³ , L ⁴ and L ⁵ are independently hydrogen or fluorine; 1-13) and formula (1-14), R ¹ , L ³ , L ⁴ , and L ⁵ are each an individual selected from the 4-position, 5-position, 6-position, and 7-position of the indole ring One by one. The compound according to claim 1 represented by any one of formulas (1-15) to (1-20).

In these formulas, R ⁰ is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, or alkoxy having 1 to 15 carbons; R ¹ is fluorine, —CF ₃ , or —OCF _3. Y ¹ , Y ² , Y ³ and Y ⁴ are independently hydrogen or fluorine; L ³ and L ⁴ are independently hydrogen or fluorine. The compound according to claim 1, which is represented by any one of formulas (1-21) to (1-24).

In these formulas, R ⁰ is alkyl having 1 to 15 carbons.   A liquid crystal composition comprising two or more components, containing at least one compound according to claim 1 as one component. The liquid crystal composition according to claim 9, comprising at least one compound selected from the group of compounds represented by formulas (2), (3) and (4) as one component.

In these formulas, R ² is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in this alkyl and alkenyl, any hydrogen may be replaced by fluorine, and any —CH ₂ - it may be is replaced by -O-; ^{X 2} is fluorine, _{chlorine, -OCF 3, -OCHF 2, -CF} 3, -CHF 2, -CH 2 F, -OCF 2 CHF 2 or -OCF, ₂ CHFCF ₃ ; ring B ¹ , ring B ² , and ring B ³ are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, tetrahydropyran-2,5-diyl, 1,4-phenylene or arbitrary hydrogen is 1,4-phenylene which is replaced by fluorine,; ^{Z 7} and ^{Z 8} are each independently, - (CH _{2 2 -, - (CH 2)} 4 -, - COO -, - CF 2 O -, - OCF 2 -, - CH = CH -, - C≡C -, - CH 2 O-, or a single bond; L ⁵ and L ⁶ are independently hydrogen or fluorine. The liquid crystal composition according to claim 9, comprising at least one compound selected from the group of compounds represented by formula (5) as one component.

In these formulas, R ³ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in this alkyl and alkenyl, any hydrogen may be replaced by fluorine, and any —CH ₂ — May be replaced by —O—; X ³ is —C≡N or —C≡C—C≡N; Ring C ¹ , Ring C ² and Ring C ³ are independently 1,4- Cyclohexylene, 1,4-phenylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl, tetrahydropyran-2,5-diyl, or pyrimidine-2 in which any hydrogen is replaced by fluorine Z ⁹ is — (CH ₂ ) ₂ —, —COO—, —CF ₂ O—, —OCF ₂ —, —C≡C—, —CH ₂ O—, or a single bond ; ^{L 7} and ^{L 8} are independently water Or is fluorine; r is 0, 1 or 2, s is 0 or 1, the sum of r and s, 0,1, or 2. The liquid crystal composition according to claim 9, comprising at least one compound selected from the group of compounds represented by formulas (6), (7), (8), (9), and (10) as one component. object.

In these formulas, R ⁴ and R ⁵ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which any hydrogen may be replaced with fluorine. Any —CH ₂ — may be replaced by —O—; Ring D ¹ , Ring D ² , Ring D ³ , and Ring D ⁴ are independently 1,4-cyclohexylene, 1,4- Cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which any hydrogen is replaced by fluorine, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl; Z ¹⁰ , ^{Z 11,} Z ^12, and ^{Z 13} are _{independently, - (CH 2) 2 -} , - COO -, - CH 2 O -, - OCF 2 -, - OCF 2 (CH 2) 2 -, or a single bond There; ^{L 9} and ^{L 10} are independently fluorine or chlorine; t, u, x, y, and z are independently 0 or 1, the sum of u, x, y, and z, 1 or 2. The liquid crystal composition according to claim 9, comprising at least one compound selected from the group of compounds represented by formulas (11), (12) and (13) as one component.

In these formulas, R ⁶ and R ⁷ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in this alkyl and alkenyl, any hydrogen may be replaced with fluorine. Any —CH ₂ — may be replaced by —O—; ring E ¹ , ring E ² , and ring E ³ are independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, or 2,5-difluoro1,4-phenylene; Z ¹⁴ and Z ¹⁵ are independently —C≡C—, —COO—, — (CH ₂ ) ₂ —, —CH═CH—, or a single bond.   The liquid crystal composition according to claim 9, comprising at least two different compounds selected from the group of compounds represented by formula (5) according to claim 11.   The liquid crystal composition according to claim 11, further comprising at least one compound selected from the group of compounds represented by formulas (11), (12) and (13) according to claim 13.   The liquid crystal composition according to claim 12, further comprising at least one compound selected from the group of compounds represented by formulas (11), (12) and (13) according to claim 13.   The liquid crystal composition according to claim 12, comprising at least two different compounds selected from the group of compounds represented by formulas (11), (12) and (13) according to claim 13.   The liquid crystal composition according to claim 9, further comprising at least one optically active compound.   The liquid crystal composition according to claim 9, further comprising at least one antioxidant and / or ultraviolet absorber.   The liquid crystal display element containing the liquid-crystal composition of any one of Claims 9-19.