JP6487281B2 - Liquid crystal composition and liquid crystal display element - Google Patents

Description

  The present invention relates to a liquid crystal composition, a liquid crystal display device containing the composition, and the like. The present invention relates to a liquid crystal display element containing this composition and having a mode such as IPS, VA, FFS, FPA. The present invention also relates to a polymer-supported alignment type liquid crystal display element.

  In the liquid crystal display element, the classification based on the operation mode of liquid crystal molecules is as follows: PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS. (In-plane switching), VA (vertical alignment), FFS (Fringe Field Switching), FPA (field-induced photo-reactive alignment) and other modes. The classification based on the element driving method is PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into TFT (thin film transistor), MIM (metal insulator metal), and the like. TFTs are classified into amorphous silicon and polycrystalline silicon. The latter is classified into a high temperature type and a low temperature type according to the manufacturing process. The classification based on the light source includes a reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both natural light and backlight.

  The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the characteristics of the composition, an AM device having good characteristics can be obtained. The relationship between the two characteristics is summarized in Table 1 below. The characteristics of the composition will be further described based on a commercially available AM device. The temperature range of the nematic phase is related to the temperature range in which the device can be used. A preferred upper limit temperature of the nematic phase is about 70 ° C. or more, and a preferred lower limit temperature of the nematic phase is about 10 ° C. or less. The viscosity of the composition is related to the response time of the device. A short response time is preferred for displaying moving images on the device. A shorter response time is desirable even at 1 millisecond. Therefore, a small viscosity in the composition is preferred. Small viscosities at low temperatures are more preferred.

  The optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large optical anisotropy or a small optical anisotropy, ie an appropriate optical anisotropy is required. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate product value depends on the type of operation mode. This value is in the range of about 0.30 μm to about 0.40 μm for the VA mode element and in the range of about 0.20 μm to about 0.30 μm for the IPS mode or FFS mode element. In these cases, a composition having a large optical anisotropy is preferable for a device having a small cell gap. A large dielectric anisotropy in the composition contributes to a low threshold voltage, a small power consumption and a large contrast ratio in the device. Therefore, a large dielectric anisotropy is preferable. A large specific resistance in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a large specific resistance not only at room temperature but also at a high temperature in the initial stage is preferable. A composition having a large specific resistance not only at room temperature but also at a high temperature after being used for a long time is preferable. The stability of the composition to ultraviolet light and heat is related to the lifetime of the device. When this stability is high, the lifetime of the device is long. Such characteristics are preferable for an AM device used in a liquid crystal projector, a liquid crystal television, and the like.

The elastic constant of the composition is related to the response speed and threshold voltage of the liquid crystal display element. The elastic constants of the liquid crystal composition are classified into K ₁₁ (spray), K ₂₂ (twist), K ₃₃ (bend), etc. according to the deformation of the liquid crystal. In particular, the elastic constant is greatly related to the response speed when OFF, and the response speed when the liquid crystal display element is OFF is slower than when it is ON. Therefore, the response speed of the entire liquid crystal display element increases as the elastic constant increases. The appropriate value depends on the operation mode of the liquid crystal display element. For example, in the case of a VA mode element, K ₃₃ is greatly related.

  Attempts to improve the elastic constant of the liquid crystal composition are disclosed in Patent Document 1, for example. However, what is disclosed in the Examples and the like is that a compound having an azo group or a hydroxyl group is added, and these chemical structures are extremely inferior in light resistance. Therefore, when these compounds are added to the liquid crystal composition, the light resistance of the liquid crystal composition itself is greatly deteriorated, which may impair the weather resistance and long-term reliability of the liquid crystal display element itself.

  Further, Non-Patent Document 1 discloses an attempt to add a compound having an interaction to a liquid crystal. However, it is a disclosure only about a 1: 1 mixture, there is no description about a composition composed of a compound of three or more components generally used in a liquid crystal display device, and only a description about liquid crystal properties such as a clearing point. There is no disclosure of physical property values of liquid crystal mixtures related to liquid crystal display elements such as elastic constants.

  In a polymer sustained alignment (PSA) type liquid crystal display element, a liquid crystal composition containing a polymer is used. First, a composition to which a small amount of a polymerizable compound is added is injected into the device. Next, the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of the device. The polymerizable compound polymerizes to form a polymer network in the composition. In this composition, since the alignment of liquid crystal molecules can be controlled by the polymer, the response time of the device is shortened, and image burn-in is improved. Such an effect of the polymer can be expected for a device having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

  In an AM device having a TN mode, a composition having a positive dielectric anisotropy is used. A composition having a negative dielectric anisotropy is used in an AM device having a VA mode. In an AM device having an IPS mode or an FFS mode, a composition having a positive or negative dielectric anisotropy is used. In a polymer sustained alignment (PSA) type AM device, a composition having positive or negative dielectric anisotropy is used. An example of a liquid crystal composition having a negative dielectric anisotropy is disclosed in the following Patent Document 2.

JP 2013-185110 A International Publication No. 2012205323

K. Kishikawa et al., Chemistry Letters., 2012, Vol.41, 1465.

  One object of the present invention is to improve the elastic constant without impairing the light resistance and long-term reliability of the liquid crystal composition. The next object is a liquid crystal composition having an appropriate balance between at least two properties. Furthermore, the next object is to provide a liquid crystal display device containing such a composition. Still another object is an AM device having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime.

  As a result of intensive studies to achieve the above object, the present inventor has obtained at least one compound selected from the group of liquid crystalline compounds represented by formula (1) or formula (2) having a polyfluorinated benzene ring. It has been found that the liquid crystal composition contained exhibits excellent characteristics, and as a result, an excellent liquid crystal display element can be obtained by using the liquid crystal composition of the present invention.

式（１）において、Ｒ¹は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素で置き換えられた炭素数２から１２のアルケニルであり；環Ａは独立して１，４−フェニレンまたは少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレンであり、ｐは１または２であり；Ｘ¹〜Ｘ⁵は独立して水素またはフッ素であり、Ｘ¹〜Ｘ⁵のうちの少なくとも１つはフッ素であり；
式（２）において、Ｓｐ¹は炭素数８〜２０のアルキレン、炭素数８〜２０のアルケニレンまたは炭素数８〜２０のアルキニレンであり；
Ｘ^aおよびＸ^bは独立して、水素またはフッ素である。

In the formula (1), R ¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 1 to 12 carbons in which at least one hydrogen is replaced by fluorine. Alkyl, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine; ring A is independently 1,4-phenylene or 1,4 in which at least one hydrogen is replaced by fluorine or chlorine -Phenylene, p is 1 or 2, X ^{1 to} X ⁵ are independently hydrogen or fluorine, and at least one of X ^{1 to} X ⁵ is fluorine;
In the formula (2), Sp ¹ is alkylene having 8 to 20 carbons, alkenylene having 8 to 20 carbons or alkynylene having 8 to 20 carbons;
X ^a and X ^b are independently hydrogen or fluorine.

  The advantage of the present invention is a liquid crystal composition to which a high elastic constant is imparted by adding the compound represented by the formula (1) or the formula (2) of the present invention. Another advantage is the low minimum temperature of nematic phase, small viscosity, appropriate optical anisotropy, negatively large dielectric anisotropy, large specific resistance, high stability against ultraviolet rays, high stability against heat, etc. A liquid crystal composition satisfying at least one characteristic. Another advantage is a liquid crystal composition having an appropriate balance between at least two properties. Another advantage is a liquid crystal display device containing such a composition. Another advantage is an AM device having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime.

  First, the compound (1) and compound (2) of the present invention will be further described. The effect of the compound (1) and the compound (2) is that a high elastic constant can be imparted to the liquid crystal composition by adding. This increase in elastic constant is thought to be due to the interaction of the fluorinated aromatic rings of compound (1) and compound (2). Therefore, from the viewpoint of increasing the elastic constant and compatibility, the compound (1) and the compound (2) are preferably added to a composition having a fluorinated compound as at least one component. In particular, addition to a composition having a fluorinated compound exhibiting a negative dielectric anisotropy value is preferred.

  Compound (1) is a compound having a rod-like structure having a fluorinated benzene ring. This compound is physically and chemically stable under 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 if this composition is stored at a low temperature, even if a large amount of compound (1) is added, it does not precipitate as crystals (or a smectic phase), so it is excellent when a large proportion is desired to be added to the liquid crystal composition. Yes.

  Compound (2) is a compound having a structure in which fluorinated benzene rings are bonded by a carbon chain. This compound is physically and chemically stable under 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). Since the compound (2) has an effect of increasing the elastic constant when added in a small amount, it is excellent when it is desired to add a small proportion to the liquid crystal composition.

  Terms used in this specification are as follows. The terms “liquid crystal composition” and “liquid crystal display element” may be abbreviated as “composition” and “element”, respectively. A liquid crystal display element is a general term for a liquid crystal display panel and a liquid crystal display module. A liquid crystalline compound is a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and does not have a liquid crystal phase. A generic term for compounds to be mixed. This compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-like. The polymerizable compound is a compound added for the purpose of forming a polymer in the composition.

  The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. The ratio (content) of the liquid crystal compound is expressed as a percentage by weight (% by weight) based on the weight of the liquid crystal composition. If necessary, additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, and a polymerization inhibitor are added to the composition. The ratio (addition amount) of the additive is represented by a weight percentage (% by weight) based on the weight of the liquid crystal composition, similarly to the ratio of the liquid crystal compound. Weight parts per million (ppm) may be used. The ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.

  “Maximum temperature of nematic phase” may be abbreviated as “maximum temperature”. “Lower limit temperature of nematic phase” may be abbreviated as “lower limit temperature”. "High specific resistance" means that the composition has a large specific resistance not only at room temperature in the initial stage but also at a temperature close to the upper limit temperature of the nematic phase. It means having a large specific resistance even at a close temperature. "High voltage holding ratio" means that the device has a large voltage holding ratio not only at room temperature in the initial stage but also at a temperature close to the upper limit temperature of the nematic phase. It means having a large voltage holding ratio even at a temperature close to. The expression “increasing dielectric anisotropy” means that when the composition has a positive dielectric anisotropy, the value increases positively, and the composition having a negative dielectric anisotropy When it is a thing, it means that the value increases negatively.

  The expression “at least one‘ A ’may be replaced with‘ B ’” means that the number of ‘A’ is arbitrary. When the number of ‘A’ is one, the position of ‘A’ is arbitrary, and when the number of ‘A’ is two or more, the positions can be selected without limitation. This rule also applies to the expression “at least one 'A' is replaced by 'B'".

In formulas (1) to (5) and formulas (I) and (II), symbols such as A, B, and C surrounded by hexagons correspond to ring A, ring B, and ring C, respectively. In formula (5), the diagonal line across the hexagon of ring K means that the bonding position on the ring can be arbitrarily selected for the P ¹ -Sp ¹ group. This rule also applies to P ² -Sp ² groups such as ring L. A subscript such as h represents the number of groups bonded to ring K or the like. When h is 2, there are two P ¹ -Sp ¹ groups on ring K. The two groups represented by P ¹ -Sp ¹ may be the same or different. This rule also applies to any two when h is greater than 2. This rule also applies to other groups. The compound represented by Formula (1) may be abbreviated as Compound (1). This abbreviation also applies to compounds represented by formula (2) and the like. Compound (1) means one compound or two or more compounds represented by formula (1). In the chemical formulas of the component compounds, the symbol of the terminal group R ² is used for a plurality of compounds. In these compounds, two groups represented by any two R ² may be the same or different. For example, there is a case where R ^{2 of} the compound (3-1) is ethyl and R ² of the compound (3-2) is ethyl. In some cases, R ^{2 of the} compound (3-1) is ethyl and R ² of the compound (3-2) is propyl. This rule also applies to symbols such as other end groups. In formula (2), when b is 2, there are two rings A. In this compound, the two rings represented by the two rings A may be the same or different. This rule also applies to any two rings A when b is greater than 2. This rule also applies to symbols such as Z ¹ and ring D.

  2-Fluoro-1,4-phenylene means the following two divalent groups. In the chemical formula, fluorine may be leftward (L) or rightward (R). This rule also applies to asymmetric ring divalent groups such as tetrahydropyran-2,5-diyl.

本発明は、下記の項などである。
項１．
第一成分として式（１）で表される化合物の群から選択された少なくとも１つの化合物を含有し、それ以外に少なくとも１つの含フッ素液晶性化合物を含有する液晶組成物。

The present invention includes the following items.
Item 1.
A liquid crystal composition containing at least one compound selected from the group of compounds represented by formula (1) as a first component and further containing at least one fluorine-containing liquid crystal compound.

式（１）において、Ｒ¹は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素で置き換えられた炭素数２から１２のアルケニルであり；環Ａは、１，４−フェニレン、または少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレンであり、ｎは１または２であり；Ｘ¹〜Ｘ⁵は独立して水素またはフッ素であり、Ｘ¹〜Ｘ⁵のうちの少なくとも１つはフッ素である。

In the formula (1), R ¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 1 to 12 carbons in which at least one hydrogen is replaced by fluorine. Alkyl, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine; ring A is 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine Phenylene, n is 1 or 2, X ^{1 to} X ⁵ are independently hydrogen or fluorine, and at least one of X ^{1 to} X ⁵ is fluorine.

Item 2.
A liquid crystal composition containing at least one compound selected from the group of compounds represented by formula (2) as the first component, and further containing at least one fluorine-containing liquid crystal compound.

式（２）において、Ｓｐ¹は炭素数２〜２０のアルキレン、炭素数２〜２０のアルケニレンまたは炭素数２〜２０のアルキニレンであり；Ｘ^aおよびＸ^bは独立して、水素またはフッ素である。

In Formula (2), Sp ¹ is alkylene having 2 to 20 carbons, alkenylene having 2 to 20 carbons or alkynylene having 2 to 20 carbons; X ^a and X ^b are independently hydrogen or fluorine. .

Item 3.
Item 2. The liquid crystal composition according to item 1, comprising at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-10) as a first component.

式（１−１）〜式（１−１０）において、Ｒ¹は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素で置き換えられた炭素数２から１２のアルケニルである。

In formula (1-1) to formula (1-10), R ¹ is independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen. Is alkyl having 1 to 12 carbon atoms replaced with fluorine, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine.

Item 4.
Item 3. The liquid crystal composition according to item 2, comprising at least one compound selected from the group of compounds represented by formula (2-1) or formula (2-2) as a first component.

式（２−１）および式（２−２）において、ｌは独立して、２から１５の整数である。

In Formula (2-1) and Formula (2-2), l is independently an integer of 2 to 15.

Item 5.
Item 5. The liquid crystal composition according to any one of items 1 to 4, wherein the ratio of the first component is in the range of 1% by weight to 30% by weight based on the weight of the liquid crystal composition.

Item 6.
Item 6. The liquid crystal composition according to any one of items 1 to 5, comprising at least one compound selected from the group of compounds represented by formula (3) as the second component.

式（３）において、Ｒ³およびＲ⁴は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から１２のアルキルであり；環Ｄおよび環Ｆは独立して、１，４−シクロへキシレン、１，４−シクロへキセニレン、１，４−フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレン、またはテトラヒドロピラン−２，５−ジイルであり；環Ｅは、２，３−ジフルオロ−１，４−フェニレン、２−クロロ−３−フルオロ−１，４−フェニレン、２，３−ジフルオロ−５−メチル−１，４−フェニレン、３，４，５−トリフルオロナフタレン−２，６−ジイル、または７，８−ジフルオロクロマン−２，６−ジイルであり；Ｚ¹およびＺ²は独立して、単結合、エチレン、カルボニルオキシ、またはメチレンオキシであり；ａは、１、２、または３であり、ｂは、０または１であり；ａとｂとの和は３以下である。

In Formula (3), R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or 1 to 12 carbon atoms in which at least one hydrogen is replaced by halogen; ring D and ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4- Phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, or tetrahydropyran-2,5-diyl; ring E is 2,3-difluoro-1,4-phenylene, 2- Chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-di , Or 7,8-difluorochroman-2,6-diyl; Z ¹ and Z ² are independently a single bond, ethylene, carbonyloxy, or methyleneoxy; a is 1, 2, or 3 and b is 0 or 1; the sum of a and b is 3 or less.

Item 7.
Item 7. The liquid crystal composition according to any one of items 1 to 6, comprising at least one compound selected from the group of compounds represented by formulas (3-1) to (3-19) as a second component: object.

式（３−１）から式（３−１９）において、Ｒ³およびＲ⁴は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から１２のアルキルである。

In the formulas (3-1) to (3-19), R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon The alkenyloxy having 2 to 12 carbon atoms or the alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by halogen.

Item 8.
Item 8. The liquid crystal composition according to item 6 or 7, wherein the ratio of the second component is in the range of 5% by weight to 70% by weight based on the weight of the liquid crystal composition.

Item 9.
Item 9. The liquid crystal composition according to any one of items 1 to 8, comprising at least one compound selected from the group of compounds represented by formula (4) as a third component.

式（４）において、Ｒ⁵およびＲ⁶は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がハロゲンで置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数２から１２のアルケニルであり；環Ｇおよび環Ｊは独立して、１，４−シクロへキシレン、１，４−フェニレン、２−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；Ｚ³は、単結合、エチレンまたはカルボニルオキシであり；ｎは、１、２、または３である。

In the formula (4), R ⁵ and R ⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least one hydrogen is replaced by halogen. Alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by halogen; ring G and ring J are independently 1,4-cyclohexylene, 1,4 -Phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ³ is a single bond, ethylene or carbonyloxy; n is 1, 2, or 3.

Item 10.
Item 10. The liquid crystal composition according to any one of items 1 to 9, comprising at least one compound selected from the group of compounds represented by formulas (4-1) to (4-13) as a third component: object.

式（４−１）から式（４−１３）において、Ｒ⁵およびＲ⁶は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素で置き換えられた炭素数２から１２のアルケニルである。

In formulas (4-1) to (4-13), R ⁵ and R ⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, It is alkyl having 1 to 12 carbons in which one hydrogen is replaced with fluorine, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced with fluorine.

Item 11.
Item 11. The liquid crystal composition according to item 9 or 10, wherein the ratio of the third component is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition.

Item 12.
Item 12. The liquid crystal composition according to any one of items 1 to 11, comprising at least one polymerizable compound selected from the group of compounds represented by formula (5) as an additive component.

式（５）において、環Ｋおよび環Ｍは独立して、シクロヘキシル、シクロヘキセニル、フェニル、１−ナフチル、２−ナフチル、テトラヒドロピラン−２−イル、１，３−ジオキサン−２−イル、ピリミジン−２−イル、またはピリジン−２−イルであり、これらの環において、少なくとも１つの水素は、ハロゲン、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；環Ｌは、１，４−シクロへキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、ナフタレン−１，２−ジイル、ナフタレン−１，３−ジイル、ナフタレン−１，４−ジイル、ナフタレン−１，５−ジイル、ナフタレン−１，６−ジイル、ナフタレン−１，７−ジイル、ナフタレン−１，８−ジイル、ナフタレン−２，３−ジイル、ナフタレン−２，６−ジイル、ナフタレン−２，７−ジイル、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、またはピリジン−２，５−ジイルであり、これらの環において、少なくとも１つの水素は、ハロゲン、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；Ｚ⁴およびＺ⁵は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ₂−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ₂−ＣＨ₂−は、−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ₃）＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ₃）−、または−Ｃ（ＣＨ₃）＝Ｃ（ＣＨ₃）−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｐ¹、Ｐ²、およびＰ³は独立して、重合性基であり；Ｓｐ²、Ｓｐ³、およびＳｐ⁴は独立して、単結合、または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ₂−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ₂−ＣＨ₂−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ｇは、０、１、または２であり；ｈ、ｊ、およびｋは独立して、０、１、２、３、または４であり；そしてｈ、ｊ、およびｋの和は１以上である。

In formula (5), ring K and ring M are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine- 2-yl or pyridin-2-yl, and in these rings, at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen being halogen. May be substituted with substituted alkyl having 1 to 12 carbons; ring L is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl Naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, Phthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1 , 3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in which at least one hydrogen is halogen, alkyl having 1 to 12 carbons , Alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by halogen; Z ⁴ and Z ⁵ are independently a single bond or 1 carbon atom. from alkylene of 10, in the alkylene, at least one of -CH ₂ -, -O -, - CO -, - COO-, or -OCO- in May be replaced come, at least one -CH ₂ -CH ₂ - is, -CH = CH -, - C (CH 3) = CH -, - CH = C (CH 3) -, or -C (CH ₃ ) = C (CH ₃ ) —, in which at least one hydrogen may be replaced by fluorine or chlorine; P ¹ , P ² , and P ³ are independently Sp ² , Sp ³ , and Sp ⁴ are each independently a single bond or alkylene having 1 to 10 carbons, in which at least one —CH ₂ — is —O —, —COO—, —OCO—, or —OCOO— may be substituted, and at least one —CH ₂ —CH ₂ — may be substituted with —CH═CH— or —C≡C—. At least one hydrogen in these groups , Fluorine or chlorine; g is 0, 1, or 2; h, j, and k are independently 0, 1, 2, 3, or 4; and h, The sum of j and k is 1 or more.

Item 13.
In the formula (5) according to item 12, P ¹ , P ² and P ³ are independently selected from the group of groups represented by formula (P-1) to formula (P-6) The liquid crystal composition according to claim 12, which is a functional group.

式（Ｐ−１）から式（Ｐ−６）において、Ｍ¹、Ｍ²、およびＭ³は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から５のアルキルであり；ｈ個のＰ¹およびｋ個のＰ³のすべてが、式（Ｐ−４）で表される基であるとき、式（５）において、ｈ個のＳｐ¹およびｋ個のＳｐ³のうちの少なくとも１つは、少なくとも１つの−ＣＨ₂−が、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられたアルキレンである。

In formula (P-1) to formula (P-6), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced by halogen In formula (5), when all of h P ¹ and k P ³ are groups represented by formula (P-4), At least one of Sp ¹ and k Sp ³ is alkylene in which at least one —CH ₂ — is replaced by —O—, —COO—, —OCO—, or —OCOO—.

Item 14.
Item 14. The item according to any one of items 1 to 13, comprising at least one polymerizable compound selected from the group of compounds represented by formula (5-1) to formula (5-27) as an additive component: Liquid crystal composition.

式（５−１）から式（５−２７）において、Ｐ⁴、Ｐ⁵、およびＰ⁶は独立して、式（Ｐ−１）から式（Ｐ−３）で表される基の群から選択された重合性基であり；

In formula (5-1) to formula (5-27), P ⁴ , P ⁵ and P ⁶ are independently from the group of groups represented by formula (P-1) to formula (P-3). A selected polymerizable group;

式（Ｐ−１）から式（Ｐ−３）において、Ｍ¹、Ｍ²、およびＭ³は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から５のアルキルであり；式（５−１）から式（５−２７）において、Ｓｐ¹、Ｓｐ²、およびＳｐ³は独立して、単結合、または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ₂−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ₂−ＣＨ₂−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。

In formula (P-1) to formula (P-3), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced by halogen In formula (5-1) to formula (5-27), Sp ¹ , Sp ² , and Sp ³ are each independently a single bond or a carbon number of 1 to 10 In which at least one —CH ₂ — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, and at least one —CH ₂ —CH ₂ -May be replaced by -CH = CH- or -C≡C-, in which at least one hydrogen may be replaced by fluorine or chlorine.

Item 15.
Item 15. The liquid crystal composition according to any one of items 12 to 14, wherein the addition ratio of the additive component is in the range of 0.03% by weight to 10% by weight based on the weight of the liquid crystal composition.

Item 16.
Item 16. A liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 15.

Item 17.
Item 18. The liquid crystal display element according to item 16, wherein the operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and the driving method of the liquid crystal display element is an active matrix method.

Item 18.
Item 16. A polymer-supported alignment type liquid crystal display element comprising the liquid crystal composition according to any one of items 12 to 15, wherein a polymerizable compound in the liquid crystal composition is polymerized.

Item 19.
Item 16. Use of the liquid crystal composition according to any one of items 1 to 15 in a liquid crystal display device.

Item 20.
Item 16. Use of the liquid crystal composition according to any one of items 12 to 15 in a polymer-supported alignment type liquid crystal display device.

Item 21.
A compound represented by formula (I).

式（Ｉ）において、Ｒ²は、炭素数２から１２のアルキル、炭素数１から１２のアルコキシ、炭素数３から１２のアルケニル、少なくとも１つの水素がフッ素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素で置き換えられた炭素数２から１２のアルケニルであり；環Ｂは、１，４−フェニレン、または少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレンであり；Ｘ⁶〜Ｘ¹⁰は独立して水素またはフッ素であり、Ｘ⁶〜Ｘ¹⁰のうちの少なくとも１つはフッ素であり；ｍは２である。

In the formula (I), R ² is alkyl having 2 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 3 to 12 carbons, or 1 to 12 carbons in which at least one hydrogen is replaced by fluorine. Alkyl, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine; ring B is 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine X ^{6 to} X ¹⁰ are independently hydrogen or fluorine, at least one of X ^{6 to} X ¹⁰ is fluorine; m is 2.

Item 22.
A compound represented by the formula (II).

式（ＩＩ）において、Ｓｐ⁵は、炭素数８〜２０のアルキレン、炭素数８〜２０のアルケニレン、または炭素数８〜２０のアルキニレンであり；Ｘ^cおよびＸ^dは独立して、水素またはフッ素である。

In the formula (II), Sp ⁵ is alkylene having 8 to 20 carbon atoms, alkenylene having 8 to 20 carbon atoms, or alkynylene having 8 to 20 carbon atoms; X ^c and X ^d are independently hydrogen or fluorine. It is.

  The present invention also includes the following items. (A) The above composition further containing at least one of additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, and a polymerization inhibitor. (B) An AM device containing the above composition. (C) The above-mentioned composition further containing a polymerizable compound, and a polymer-supported orientation (PSA) type AM device containing this composition. (D) A polymer-supported orientation (PSA) type AM device comprising the above-described composition, wherein the polymerizable compound in the composition is polymerized. (E) A device containing the above composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA. (F) A transmissive device containing the above composition. (G) Use of the above composition as a composition having a nematic phase. (H) Use as an optically active composition by adding an optically active compound to the above composition.

  The composition of the present invention will be described in the following order. First, the constitution of component compounds in the composition will be described. Second, the main characteristics of the component compounds and the main effects of the compounds on the composition will be explained. Third, the combination of components in the composition, the preferred ratio of the components, and the basis thereof will be described. Fourth, a preferred form of the component compound will be described. Fifth, preferred component compounds are shown. Sixth, additives that may be added to the composition will be described. Seventh, a method for synthesizing the component compounds will be described. Finally, the use of the composition will be described.

  First, the constitution of component compounds in the composition will be described. The composition of the present invention is classified into Composition A and Composition B. In addition to the compound selected from the compound (1), the compound (2), the compound (3), the compound (4), and the compound (5), the composition A further includes other liquid crystal compounds, additives, and the like. You may contain. The “other liquid crystal compound” is a liquid crystal compound different from the compound (1), the compound (2), the compound (3), and the compound (4). Such compounds are mixed into the composition for the purpose of further adjusting the properties. Additives include optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, and the like.

  Composition B consists essentially of a compound selected from compound (1), compound (2), compound (3), compound (4), and compound (5). “Substantially” means that the composition may contain an additive but no other liquid crystal compound. Composition B has fewer components than composition A. From the viewpoint of reducing the cost, the composition B is preferable to the composition A. The composition A is preferable to the composition B from the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds.

  Second, the main characteristics of the component compounds and the main effects of the compounds on the characteristics of the composition will be explained. The main characteristics of the component compounds are summarized in Table 2 based on the effects of the present invention. In the symbols in Table 2, L means large or high, M means moderate, and S means small or low. The symbols L, M, and S are classifications based on a qualitative comparison among the component compounds, and 0 (zero) means that the value is almost zero.

成分化合物を組成物に混合したとき、成分化合物が組成物の特性に及ぼす主要な効果は次のとおりである。化合物（１）または化合物（２）は弾性定数を上げる。化合物（３）は誘電率異方性を上げ、そして下限温度を下げる。化合物（４）は、粘度を下げる、または上限温度を上げる。化合物（５）は、重合によって重合体を与え、この重合体は、素子の応答時間を短縮し、そして画像の焼き付きを改善する。

When component compounds are mixed into the composition, the main effects of the component compounds on the properties of the composition are as follows. Compound (1) or compound (2) increases the elastic constant. Compound (3) increases the dielectric anisotropy and decreases the minimum temperature. Compound (4) decreases the viscosity or increases the maximum temperature. Compound (5) gives a polymer by polymerization, and this polymer shortens the response time of the device and improves image burn-in.

  Third, the combination of components in the composition, the preferred ratio of the component compounds, and the basis thereof will be described. The preferred combinations of the components in the composition are: first component + second component, first component + third component, first component + second component + third component, first component + second component + additive component, first component One component + third component + additive component, or first component + second component + third component + additive component. Further preferred combinations are first component + second component + third component or first component + second component + third component + additive component.

  A desirable ratio of the first component is approximately 1% by weight or more and approximately 30% by weight or less for increasing the elastic constant. A more desirable ratio is in the range of approximately 3% by weight to approximately 25% by weight. A particularly preferred ratio is in the range of approximately 5% by weight to approximately 20% by weight.

  A desirable ratio of the second component is approximately 5% by weight or more for increasing the dielectric anisotropy, and approximately 70% by weight or less for decreasing the minimum temperature. A more desirable ratio is in the range of approximately 10% by weight to approximately 65% by weight. A particularly preferred ratio is in the range of approximately 15% by weight to approximately 60% by weight.

  A desirable ratio of the third component is approximately 10% by weight or more for increasing the maximum temperature or decreasing the viscosity, and approximately 90% by weight or less for increasing the dielectric anisotropy. A more desirable ratio is in the range of approximately 20% by weight to approximately 80% by weight. A particularly desirable ratio is in the range of approximately 30% by weight to approximately 70% by weight.

  The compound (5) is added to the composition for the purpose of adapting to a polymer-supported orientation type device. A preferable addition ratio of this additive is about 0.03% by weight or more for aligning liquid crystal molecules based on the weight of the liquid crystal composition, and about 10% by weight or less for preventing display defects of the device. A more preferred addition ratio is in the range of approximately 0.1% by weight to approximately 2% by weight. A particularly preferred addition ratio is in the range of about 0.2% by weight to about 1.0% by weight.

Next, the preferable form of each component compound is demonstrated. In Formula (1), Formula (2), Formula (3), Formula (4), Formula (I), and Formula (II), R ¹ is alkyl having 1 to 12 carbons and having 1 to 12 carbons Alkoxy, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine. Desirable R ¹ is alkyl having 1 to 12 carbons for increasing the chemical stability. R ¹ is alkyl having 2 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine. Desirable R ² is alkyl having 2 to 12 carbons for increasing the chemical stability. R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, and at least one hydrogen is fluorine. It is substituted alkyl having 1 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine. Desirable R ³ or R ⁴ is alkyl having 1 to 12 carbons for increasing the stability, and alkoxy having 1 to 12 carbons for increasing the dielectric anisotropy. R ⁵ and R ⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 1 to 12 carbons in which at least one hydrogen is replaced by fluorine. Alkyl or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine. Desirable R ⁵ or R ⁶ is alkenyl having 2 to 12 carbons for decreasing the viscosity, and alkyl having 1 to 12 carbons for increasing the stability.

  Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. More desirable alkyl is ethyl, propyl, butyl, pentyl, or heptyl for decreasing the viscosity.

  Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. More desirable alkoxy is methoxy or ethoxy for decreasing the viscosity.

  Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More desirable alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for decreasing the viscosity. The preferred configuration of —CH═CH— in these alkenyls depends on the position of the double bond. Trans is preferable in alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity. In alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl, cis is preferable. In these alkenyl, linear alkenyl is preferable to branching.

  Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. More preferable alkenyloxy is allyloxy or 3-butenyloxy for decreasing the viscosity.

  Preferred examples of alkenyl in which at least one hydrogen is replaced by fluorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro-4 -Pentenyl, or 6,6-difluoro-5-hexenyl. Further preferred examples include 2,2-difluorovinyl or 4,4-difluoro-3-butenyl for decreasing the viscosity.

In the formula (2), Sp ¹ is alkylene having 2 to 20 carbons, alkenylene having 2 to 20 carbons, or alkynylene having 2 to 20 carbons. Preferred Sp ¹ is alkylene having 2 to 20 carbons for increasing chemical stability, and alkenylene having 2 to 20 carbons for increasing the clearing point of the liquid crystal composition.

In the formula (II), Sp ⁵ is alkylene having 8 to 20 carbon atoms, alkenylene having 1 to 20 carbon atoms, or alkynylene having 8 to 20 carbon atoms. Preferred Sp ⁵ is alkylene having 8 to 20 carbon atoms for increasing chemical stability, and alkenylene having 8 to 20 carbon atoms for increasing the clearing point of the liquid crystal composition.

  Preferred alkylenes are 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9. -Nonylene, 1,10-decanylene, 1,11-undecanylene, 1,12-dodecanylene, 1,13-tridecanylene, 1,14-tetradecanylene, 1,15-pentadecanylene, 1,16-hexadecanylene, 1,17 -Heptadecanylene or 1,18-octadecanylene. More preferred alkyls are 1,8-octylene, 1,9-nonylene, 1,10-decanylene, 1,11-undecanylene, 1,12-dodecanylene, 1,13-tridecanylene, 1,14-tetradecanylene, , 15-pentadecanylene, or 1,16-hexadecanylene.

  Preferred alkenylenes are ethene-1,2-diyl, 2-propene-1,3-diyl, 2-butene-1,4-diyl, 2-pentene-1,5-diyl, 3-hexene-1,6- Diyl, 2-hexene-1,6-diyl, 3-heptene-1,7-diyl, 2-heptene-1,7-diyl, 3-octene-1,8-diyl, 2-octene-1,8- Diyl, 4-nonene-1,9-diyl, 3-nonene-1,9-diyl, 2-nonene-1,9-diyl, 5-decene-1,10-diyl, 4-decene-1,10- Diyl, 3-decene-1,10-diyl, 2-decene-1,10-diyl, 5-undecene-1,11-diyl, 4-undecene-1,11-diyl, 3-undecene-1,11- Diyl, 2-undecen-1,11-diyl, 6-dode -1,12-diyl, 5-dodecene-1,12-diyl, 4-dodecene-1,12-diyl, 3-dodecene-1,12-diyl, 2-dodecene-1,12-diyl, 6-tridecene -1,13-diyl, 5-tridecene-1,13-diyl, 4-tridecene-1,13-diyl, 3-tridecene-1,13-diyl, 2-tridecene-1,13-diyl, 7-tetradecene -1,14-diyl, 6-tetradecene-1,14-diyl, 5-tetradecene-1,14-diyl, 4-tetradecene-1,14-diyl, 3-tetradecene-1,14-diyl, 2-tetradecene -1,14-diyl, 7-pentadecene-1,15-diyl, 6-pentadecene-1,15-diyl, 5-pentadecene-1,15-diyl, 4-pentadecene-1, 5-diyl, 3-pentadecene-1,15-diyl, 2-pentadecene-1,15-diyl, 8-hexadecene-1,16-diyl, 7-hexadecene-1,16-diyl, 6-hexadecene-1, 16-diyl, 5-hexadecene-1,16-diyl, 4-hexadecene-1,16-diyl, 3-hexadecene-1,16-diyl, 2-hexadecene-1,16-diyl, 8-heptadecene-1, 17-diyl, 7-heptadecene-1,17-diyl, 6-heptadecene-1,17-diyl, 5-heptadecene-1,17-diyl, 4-heptadecene-1,17-diyl, 3-heptadecene-1, 17-diyl, 2-heptadecene-1,17-diyl, 9-octadecene-1,18-diyl, 8-octadecene-1,18-diyl, 7-o Kutadecene-1,18-diyl, 6-octadecene-1,18-diyl, 5-octadecene-1,18-diyl, 4-octadecene-1,18-diyl, 3-octadecene-1,18-diyl or 2- Octadecene-1,18-diyl. The preferred configuration of —CH═CH— in these alkenyls depends on the position of the double bond. From the viewpoint of improving the clearing point when added to the composition, the double bond is preferably located inside the carbon chain such as 4-octene-1,8-diyl or 4-nonene-1,9-diyl. In the case of alkenylene such as 3-octene-1,8-diyl, 3-nonene-1,9-diyl and 3-decene-1,10-diyl from the viewpoint of improving the clearing point when added to the composition, Trans is preferred. In alkenylene such as 2-octene-1,8-diyl, 2-nonene-1,9-diyl and 2-decene-1,10-diyl, cis may be used. In these alkenyl, linear alkenyl is preferable to branching.

  Ring A and ring B are independently 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine. Preferred examples of “1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine” are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, or 2-chloro. -3-fluoro-1,4-phenylene and 2,3,5,6-tetrafluoro-1,4-phenylene.

  Ring D and Ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, Preferred examples of tetrahydropyran-2,5-diyl and “1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine” include 2-fluoro-1,4-phenylene, 2,3-difluoro -1,4-phenylene or 2-chloro-3-fluoro-1,4-phenylene. Preferred ring D or ring F is 1,4-cyclohexylene for decreasing the viscosity, and 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4 for increasing the dielectric anisotropy. -Phenylene or tetrahydropyran-2,5-diyl, and 1,4-phenylene for increasing optical anisotropy. The configuration of 1,4-cyclohexylene is preferably trans rather than cis for increasing the maximum temperature. Tetrahydropyran-2,5-diyl is

環Ｅは、２，３−ジフルオロ−１，４−フェニレン、２−クロロ−３−フルオロ−１，４−フェニレン、２，３−ジフルオロ−５−メチル−１，４−フェニレン、３，４，５−トリフルオロナフタレン−２，６−ジイル、または７，８−ジフルオロクロマン−２，６−ジイルである。好ましい環Ｅは、粘度を下げるために２，３−ジフルオロ−１，４−フェニレンであり、光学異方性を下げるために２−クロロ−３−フルオロ−１，４−フェニレンであり、誘電率異方性を上げるために７，８−ジフルオロクロマン−２，６−ジイルである。

Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4, 5-trifluoronaphthalene-2,6-diyl or 7,8-difluorochroman-2,6-diyl. Preferred ring E is 2,3-difluoro-1,4-phenylene for decreasing the viscosity and 2-chloro-3-fluoro-1,4-phenylene for decreasing the optical anisotropy. In order to increase anisotropy, it is 7,8-difluorochroman-2,6-diyl.

  Ring G and ring J are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. Desirable ring D, ring E, or ring F is 1,4-cyclohexylene for decreasing the viscosity or increasing the maximum temperature, and 1,4-phenylene for decreasing the minimum temperature.

Z ¹ and Z ² are independently a single bond, ethylene, carbonyloxy, or methyleneoxy. Desirable Z ¹ or Z ² is a single bond for increasing the stability, and oxymethylene for increasing the dielectric anisotropy. Z ³ is a single bond, ethylene, or carbonyloxy. Desirable Z ³ is a single bond for decreasing the viscosity, and ethylene for decreasing the minimum temperature.

a is 1, 2, or 3. Preferred b is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature. b is 0 or 1; Preferred b is 0 for decreasing the viscosity, and 1 for decreasing the minimum temperature. The sum of a and b is 3 or less.
n is 1, 2 or 3. Preferred n is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.

In the compound (5), P ¹ , P ² and P ³ are polymerizable groups. Preferred P ¹ , P ² , or P ³ is a polymerizable group selected from the group of groups represented by formula (P-1) to formula (P-6). Further preferred P ¹ , P ² or P ³ is a group (P-1) or a group (P-2). Particularly preferred group (P-1) is —OCO—CH═CH ₂ or —OCO—C (CH ₃ ) ═CH ₂ . The wavy line from the group (P-1) to the group (P-6) indicates a site to be bonded.

ｈ個のＰ¹、ｊ個のＰ²、およびｋ個のＰ³のすべてが、基（Ｐ−１）であるとき、Ｐ¹のＭ¹（またはＭ²またはＭ³）、Ｐ²のＭ¹、またはＰ³のＭ¹が同一であってもよいし、または異なってもよい。基（Ｐ−１）から基（Ｐ−６）において、Ｍ¹、Ｍ²およびＭ³は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から５のアルキルである。好ましいＭ¹、Ｍ²またはＭ³は、反応性を上げるために水素またはメチルである。さらに好ましいＭ¹はメチルであり、さらに好ましいＭ²またはＭ³は水素である。

When all of the h of P ^1, j-number of P ^2, and the k P ³ is a group ^{(P-1), M 1} ( or M ² or M ³⁾ of P ^1, the P ² M ¹ or M ^{1 of} P ³ may be the same or different. In groups (P-1) to (P-6), M ¹ , M ² and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced by halogen. And alkyl having 1 to 5 carbon atoms. Preferred M ¹ , M ² or M ³ is hydrogen or methyl for increasing the reactivity. More preferred M ¹ is methyl, and more preferred M ² or M ³ is hydrogen.

When all of h P ¹ and k P ³ are groups (P-4), at least one of h Sp ¹ and k Sp ³ is at least one —CH ₂ -Is alkylene substituted with -O-, -COO-, -OCO-, or -OCOO-. That is, not all of h P ¹ and k P ³ are alkenyl such as 1-propenyl.

P ⁴ , P ⁵ , and P ⁶ are each independently a group represented by Formula (P-1) to Formula (P-3). Preferred P ⁴ , P ⁵ or P ⁶ is group (P-1) or group (P-2). Further preferred group (P-1) is —OCO—CH═CH ₂ or —OCO—C (CH ₃ ) ═CH ₂ . The wavy line from the group (P-1) to the group (P-3) indicates a site to be bonded.

Ｐ⁴、Ｐ⁵、およびＰ⁶のすべてが、基（Ｐ−１）であるとき、Ｐ⁴のＭ¹（またはＭ²またはＭ³）、Ｐ⁵のＭ¹、またはＰ⁶のＭ¹が同一であってもよいし、または異なってもよい。

P ^4, all P ^5, and P ⁶ are, when a group (P-1), M ¹ of P ⁴ (or M ² or M ^3), the M ¹ of M ¹ or P ^6, the P ⁵ They may be the same or different.

Sp ¹ , Sp ² , and Sp ³ are each independently a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, —COO—, —OCO. -, or it may be replaced by -OCOO-, at least one -CH ₂ -CH ₂ - may be replaced by -CH = CH- or -C≡C-, and in the groups, at least 1 One hydrogen may be replaced with fluorine or chlorine. When hydrogen is replaced with —C≡N, the total number of carbon atoms of alkylene substituted with cyano is preferably up to 10. Preferred Sp ¹ , Sp ² or Sp ³ is a single bond.

  Ring K and Ring M are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl, or pyridine In these rings, at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 1 carbon in which at least one hydrogen is replaced by halogen. To 12 alkyls. Preferred ring K or ring M is phenyl. Ring L is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene- 2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings , At least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or carbon in which at least one hydrogen is replaced by halogen It may be replaced by alkyl having having 1 12. Preferred ring L is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁵ and Z ⁶ are each independently a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, —CO—, —COO—, or — may be replaced by OCO-, at least one -CH ₂ -CH ₂ - is, -CH = CH -, - C (CH 3) = CH -, - CH = C (CH 3) -, or -C (CH ₃ ) ═C (CH ₃ ) — may be replaced, and in these groups at least one hydrogen may be replaced with fluorine or chlorine. Preferred Z ⁵ or Z ⁶ is a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, or —OCO—. Further preferred Z ⁵ or Z ⁶ is a single bond.

  g is 1 or 2. Preferred g is 1. h, j, and k are each independently an integer of 1 to 4, provided that one j when g is 2 may be 0. Preferred h, j, or k is 1 or 2.

  Fifth, preferred component compounds are shown. Preferred compound (1) is from compound (1-1) to compound (1-10) according to item 3, and preferred compound (2) is (2-1) and (2-2). In these compounds, at least one of the first components is the compound (1-3), the compound (1-5), the compound (1-8), the compound (1-10), or the compound (2-1). It is preferable.

  Desirable compound (3) is the compound (3-1) to the compound (3-19) according to item 7. In these compounds, at least one of the second components is a compound (3-1), a compound (3-2), a compound (3-6), a compound (3-7), a compound (3-10), a compound ( 3-11) or compound (3-13) is preferred. It is preferable that at least two of the second components are the compound (3-1) and the compound (3-6), or the combination of the compound (3-1) and the compound (3-13).

  Desirable compound (4) is the compound (4-1) to the compound (4-13) according to item 10. In these compounds, at least one of the third components is the compound (4-1), the compound (4-3), the compound (4-5), the compound (4-7), or the compound (4-8). It is preferable. It is preferable that at least two of the third components are a combination of the compound (4-1) and the compound (4-3), the compound (4-1) and the compound (4-5).

Desirable compound (5) is the compound (5-1) to the compound (5-27) according to item 14. In these compounds, at least one of the additive components is compound (5-1), compound (5-2), compound (5-24), compound (5-25), compound (5-26), or compound (5-27) is preferred. At least two of the additive components are compound (5-1) and compound (5-2), compound (5-1) and compound (5-18), compound (5-2) and compound (5-24), Compound (5-2) and Compound (5-25), Compound (5-2) and Compound (5-26), Compound (5-25) and Compound (5-26), or Compound (5-18) and A combination of compounds (5-24) is preferred. In the group (P-1) to the group (P-3), preferred M ¹ , M ² , or M ³ is hydrogen or methyl. Preferred Sp ¹ , Sp ² , or Sp ³ is a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CO—CH═CH—, or -CH = CH-CO-.

  In addition, in the composition in which the compound (1) and the compound (2) are added to a fluorinated compound having a positive dielectric anisotropy value, the same addition to the compound having a negative dielectric anisotropy value is performed. Show the effect. As examples of such fluorinated compounds exhibiting a positive dielectric anisotropy value, (PSI-1) to (PSI-3) are shown below. In addition, the fluorinated compound which shows the positive dielectric constant anisotropy value which can add a compound (1) and a compound (2) is not necessarily limited to the following compound.

式（ＰＳＩ−１）〜（ＰＳＩ−３）において、Ｒ⁷は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から１２のアルキルである。

In formulas (PSI-1) to (PSI-3), R ⁷ is independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 to 12 carbons. Or an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by a halogen.

  Sixth, additives that may be added to the composition will be described. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, and the like. An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal to give a twist angle. Examples of such compounds are compound (6-1) to compound (6-5). A desirable ratio of the optically active compound is approximately 5% by weight or less. A more desirable ratio is in the range of approximately 0.01% by weight to approximately 2% by weight.

大気中での加熱による比抵抗の低下を防止するために、または素子を長時間使用したあと、室温だけではなく上限温度に近い温度でも大きな電圧保持率を維持するために、酸化防止剤が組成物に添加される。酸化防止剤の好ましい例は、ｎが１から９の整数である化合物（７）などである。

In order to prevent a decrease in specific resistance due to heating in the atmosphere or to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after using the device for a long time, an antioxidant is composed. Added to the product. A preferred example of the antioxidant is a compound (7) wherein n is an integer of 1 to 9.

化合物（７）において、好ましいｎは、１、３、５、７、または９である。さらに好ましいｎは７である。ｎが７である化合物（７）は、揮発性が小さいので、素子を長時間使用したあと、室温だけではなく上限温度に近い温度でも大きな電圧保持率を維持するのに有効である。酸化防止剤の好ましい割合は、その効果を得るために約５０ｐｐｍ以上であり、上限温度を下げないように、または下限温度を上げないように約６００ｐｐｍ以下である。さらに好ましい割合は、約１００ｐｐｍから約３００ｐｐｍの範囲である。

In the compound (7), preferred n is 1, 3, 5, 7, or 9. Further preferred n is 7. Since the compound (7) in which n is 7 has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after the device has been used for a long time. A desirable ratio of the antioxidant is approximately 50 ppm or more for achieving its effect, and is approximately 600 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 300 ppm.

  Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Also preferred are light stabilizers such as sterically hindered amines. A desirable ratio of these absorbers and stabilizers is approximately 50 ppm or more for achieving the effect thereof, and approximately 10,000 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 10,000 ppm.

  A dichroic dye such as an azo dye or an anthraquinone dye is added to the composition in order to adapt to a GH (guest host) mode device. A preferred ratio of the dye is in the range of approximately 0.01% by weight to approximately 10% by weight. In order to prevent foaming, an antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is added to the composition. A desirable ratio of the antifoaming agent is approximately 1 ppm or more for obtaining the effect thereof, and approximately 1000 ppm or less for preventing a display defect. A more desirable ratio is in the range of approximately 1 ppm to approximately 500 ppm.

  A polymerizable compound is used to adapt to a polymer support alignment (PSA) type device. Compound (5) is suitable for this purpose. A polymerizable compound different from the compound (5) may be added to the composition together with the compound (5). Preferable examples of such a polymerizable compound are compounds such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. Further preferred examples are acrylate or methacrylate derivatives. A desirable ratio of compound (5) is 10% by weight or more based on the total weight of the polymerizable compound. A more desirable ratio is 50% by weight or more. A particularly desirable ratio is 80% by weight or more. The most preferred ratio is 100% by weight.

  A polymerizable compound such as compound (5) is polymerized by ultraviolet irradiation. The polymerization may be performed in the presence of a suitable initiator such as a photopolymerization initiator. Appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those skilled in the art and are described in the literature. For example, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF), which are photoinitiators, are suitable for radical polymerization. A desirable ratio of the photopolymerization initiator is in the range of approximately 0.1% by weight to approximately 5% by weight based on the total weight of the polymerizable compound. A more desirable ratio is in the range of approximately 1% by weight to approximately 3% by weight.

  When storing a polymerizable compound such as compound (5), a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of the polymerization inhibitor are hydroquinone derivatives such as hydroquinone and methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine and the like.

  Seventh, a method for synthesizing the component compounds will be described. An example of a method for synthesizing compound (1), compound (2), compound (I) and compound (II) of the present invention is shown in the following scheme. However, the synthesis method of these compounds is not limited to the following scheme.

例えば、本願発明の化合物（１）、化合物（２）、化合物（Ｉ）および化合物（ＩＩ）は、対応する安息香酸［化合物（ｒ−１）、化合物（ｒ−３）、化合物（ｒ−５）、化合物（ｒ−７）］と対応するフェノール［化合物（ｒ−２）、化合物（ｒ−６）］またはジオール［化合物（ｒ−４）、化合物（ｒ−８）］とを４−ジメチルアミノピリジン＜ＤＭＡＰ＞存在下、脱水剤（例：Ｎ，Ｎ−ジシクロヘキシルカルボジイミド＜ＤＣＣ＞）を作用させることで合成することが出来る。

For example, the compound (1), the compound (2), the compound (I) and the compound (II) of the invention of the present application are represented by the corresponding benzoic acid [compound (r-1), compound (r-3), compound (r-5). ), Compound (r-7)] and the corresponding phenol [compound (r-2), compound (r-6)] or diol [compound (r-4), compound (r-8)] It can be synthesized by reacting a dehydrating agent (eg, N, N-dicyclohexylcarbodiimide <DCC>) in the presence of aminopyridine <DMAP>.

  In addition, from the corresponding benzoic acid [compound (r-1), compound (r-3), compound (r-5), compound (r-7)] in the presence of a tertiary amine (eg, pyridine, triethylamine, etc.). It is also synthesized by reacting an inducible acid halide with the corresponding phenol [compound (r-2), compound (r-6)] or diol [compound (r-4), compound (r-8)]. I can do it.

  Other compounds can be synthesized by known methods. The synthesis method is illustrated. Compound (3-1) and compound (3-2) are synthesized by the method described in JP-T-2-503441. Compound (3-6) is synthesized by the method described in JP-T-2-503443. Compound (4-1) is synthesized by the method described in JP-A-59-176221. Compound (4-13) is synthesized by the method described in JP-A No. 02-237799. Compounds of formula (7) where n is 1 are available from Sigma-Aldrich Corporation. Compound (7) etc. in which n is 7 is synthesized by the method described in US Pat. No. 3,660,505.

  Compounds that have not been described synthetic methods and intermediates disclosed in the synthetic route are Organic Syntheses (John Wiley & Sons, Inc), Organic Reactions (Organic Reactions, John Wiley & Sons, Inc), Comple It can be synthesized by methods described in books such as Comprehensive Organic Synthesis (Pergamon Press) and New Experimental Chemistry Course (Maruzen). The composition is prepared from the compound thus obtained by known methods. For example, the component compounds are mixed and dissolved in each other by heating.

  Finally, the use of the composition will be described. The composition mainly has a minimum temperature of about −10 ° C. or lower, a maximum temperature of about 70 ° C. or higher, and an optical anisotropy in the range of about 0.07 to about 0.20. A device containing this composition has a large voltage holding ratio. This composition is suitable for an AM device. This composition is particularly suitable for a transmissive AM device. A composition having an optical anisotropy in the range of about 0.08 to about 0.25 by controlling the proportion of the component compounds or by mixing other liquid crystal compounds, and further from about 0.10 Compositions having optical anisotropy in the range of about 0.30 may be prepared. This composition can be used as a composition having a nematic phase, or can be used as an optically active composition by adding an optically active compound.

  This composition can be used for an AM device. Further, it can be used for PM elements. This composition can be used for an AM device and a PM device having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, and FPA. Use for an AM device having a TN, OCB, IPS mode or FFS mode is particularly preferable. In an AM device having an IPS mode or an FFS mode, when no voltage is applied, the alignment of liquid crystal molecules may be parallel to or perpendicular to the glass substrate. These elements may be reflective, transmissive, or transflective. Use in a transmissive element is preferred. It can also be used for an amorphous silicon-TFT device or a polycrystalline silicon-TFT device. It can also be used for an NCAP (nematic curvilinear aligned phase) type device produced by microencapsulating this composition, or a PD (polymer dispersed) type device in which a three-dimensional network polymer is formed in the composition.

  The invention is explained in more detail by means of examples. The invention is not limited by these examples. The synthesized compound was identified by a method such as NMR analysis. The properties of the compounds and compositions were measured by the methods described below.

NMR analysis: For measurement, DRX-500 manufactured by Bruker BioSpin Corporation was used. ^In the measurement of ¹ H-NMR, the sample was dissolved in a deuterated solvent such as CDCl _3, and the measurement was performed at room temperature under conditions of 500 MHz and 16 integrations. Tetramethylsilane was used as an internal standard. ^{In the 19} F-NMR measurement, CFCl ₃ was used as an internal standard and the number of integrations was 24. In the description of the nuclear magnetic resonance spectrum, s is a singlet, d is a doublet, t is a triplet, q is a quartet, quint is a quintet, sex is a sextet, m is a multiplet, and br is broad.

  Gas chromatographic analysis: A GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for measurement. The carrier gas is helium (2 mL / min). The sample vaporization chamber was set at 280 ° C, and the detector (FID) was set at 300 ° C. For separation of the component compounds, capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm; stationary liquid phase is dimethylpolysiloxane; nonpolar) manufactured by Agilent Technologies Inc. was used. The column was held at 200 ° C. for 2 minutes and then heated to 280 ° C. at a rate of 5 ° C./min. A sample was prepared in an acetone solution (0.1% by weight), and 1 μL thereof was injected into the sample vaporization chamber. The recorder is a C-R5A type Chromatopac manufactured by Shimadzu Corporation or an equivalent thereof. The obtained gas chromatogram showed the peak retention time and peak area corresponding to the component compounds.

  As a solvent for diluting the sample, chloroform, hexane or the like may be used. In order to separate the component compounds, the following capillary column may be used. HP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc., Rtx-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Restek Corporation, BP-1 made by SGE International Pty. Ltd (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm). In order to prevent compound peaks from overlapping, a capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Shimadzu Corporation may be used.

  The ratio of the liquid crystal compound contained in the composition may be calculated by the following method. A mixture of liquid crystal compounds is detected by a gas chromatograph (FID). The area ratio of peaks in the gas chromatogram corresponds to the ratio (weight ratio) of liquid crystal compounds. When the capillary column described above is used, the correction coefficient of each liquid crystal compound may be regarded as 1. Therefore, the ratio (% by weight) of the liquid crystal compound can be calculated from the peak area ratio.

  Measurement sample: When measuring the characteristics of the composition, the composition was used as it was as a sample. When measuring the characteristics of the compound, a sample for measurement was prepared by mixing this compound (15% by weight) with mother liquid crystals (85% by weight). The characteristic value of the compound was calculated from the value obtained by the measurement by extrapolation. (Extrapolated value) = {(Measured value of sample) −0.85 × (Measured value of mother liquid crystal)} / 0.15. When the smectic phase (or crystal) is precipitated at 25 ° C. at this ratio, the ratio of the 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 this order changed. By this extrapolation method, the maximum temperature, optical anisotropy, viscosity, and dielectric anisotropy values for the compound were determined.

  The following mother liquid crystals were used. The ratio of the component compounds is shown by weight%.

測定方法：特性の測定は下記の方法で行った。これらの多くは、社団法人電子情報技術産業協会（Japan Electronics and Information Technology Industries Association；以下ＪＥＩＴＡという）で審議制定されるＪＥＩＴＡ規格（ＪＥＩＴＡ・ＥＤ−２５２１Ｂ）に記載された方法、またはこれを修飾した方法であった。測定に用いたＴＮ素子には、薄膜トランジスター（ＴＦＴ）を取り付けなかった。

Measuring method: The characteristics were measured by the following method. Many of these methods are modified by a method described in the JEITA standard (JEITA ED-2521B) established by the Japan Electronics and Information Technology Industries Association (hereinafter referred to as JEITA), or a modification thereof. It was a method. No thin film transistor (TFT) was attached to the TN device used for measurement.

(1) Maximum temperature of nematic phase (NI; ° C.): A sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when a part of the sample changed from a nematic phase to an isotropic liquid. The upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”.

(2) Minimum temperature of nematic phase (T _C ; ° C.): A sample having a nematic phase is placed in a glass bottle and placed in a freezer at 0 ° C., −10 ° C., −20 ° C., −30 ° C., and −40 ° C. for 10 days. After storage, 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., T _C was described as <−20 ° C. The lower limit temperature of the nematic phase may be abbreviated as “lower limit temperature”.

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

(4) Viscosity (rotational viscosity; γ1; measured at 25 ° C .; mPa · s): The measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). I followed. A sample was put in a VA device having a distance (cell gap) between two glass substrates of 20 μm. This element was applied stepwise in increments of 1 volt within a range of 39 to 50 volts. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. These measurements and M.I. The value of rotational viscosity was obtained from the paper by Imai et al., Calculation formula (8) on page 40. The dielectric anisotropy necessary for this calculation was measured in the item (6).

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

(6) Dielectric anisotropy (Δε; measured at NI-35 ° C.): The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥. The dielectric constants (ε‖ and ε⊥) were measured as follows.
1) Measurement of dielectric constant (ε‖): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a well-cleaned glass substrate. The glass substrate was rotated with a spinner and then heated at 150 ° C. for 1 hour. A sample was put in a VA element in which the distance between two glass substrates (cell gap) was 4 μm, and the element was sealed with an adhesive that was cured with ultraviolet rays. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε‖) in the major axis direction of the liquid crystal molecules was measured.
2) Measurement of dielectric constant (ε⊥): A polyimide solution was applied to a well-cleaned glass substrate. After baking this glass substrate, the obtained alignment film was rubbed. A sample was put in a TN device in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured.

(7) Threshold voltage (Vth; measured at NI-35 ° C .; V): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. A sample is placed in a normally black mode VA element in which the distance between two glass substrates (cell gap) is 4 μm and the rubbing direction is anti-parallel, and an adhesive that cures the element with ultraviolet rays is used. And sealed. The voltage (60 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 20V by 0.02V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount reached the maximum and the transmittance was 0% when the light amount was the minimum. The threshold voltage was expressed as a voltage when the transmittance reached 10%.

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

(9) Voltage holding ratio (VHR-2; measured at 80 ° C .;%): The voltage holding ratio was measured in the same procedure as above except that it was measured at 80 ° C. instead of 25 ° C. The obtained value was represented by VHR-2.

(10) Voltage holding ratio (VHR-3; measured at 25 ° C .;%): After irradiation with ultraviolet rays, the voltage holding ratio was measured to evaluate the stability against ultraviolet rays. The TN device used for the measurement had a polyimide alignment film, and the cell gap was 5 μm. A sample was injected into this element and irradiated with light for 20 minutes. The light source was an ultra-high pressure mercury lamp USH-500D (made by USHIO Inc.), and the distance between the element and the light source was 20 cm. In the measurement of VHR-3, a decaying voltage was measured for 16.7 milliseconds. A composition having a large VHR-3 has a large stability to ultraviolet light. VHR-3 is preferably 90% or more, and more preferably 95% or more.

(11) Voltage holding ratio (VHR-4; measured at 25 ° C .;%): The TN device into which the sample was injected was heated in a thermostatic bath at 80 ° C. for 500 hours, and then the voltage holding ratio was measured and stability against heat. Evaluated. In the measurement of VHR-4, a decaying voltage was measured for 16.7 milliseconds. A composition having a large VHR-4 has a large stability to heat.

(12) Response time (τ; measured at 25 ° C .; ms): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. The low-pass filter was set to 5 kHz. A sample was put in a normally black mode VA device in which the distance between two glass substrates (cell gap) was 4 μm and the rubbing direction was anti-parallel. The device was sealed using an adhesive that was cured with ultraviolet light. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to this element. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. It was considered that the transmittance was 100% when the light amount was the maximum, and the transmittance was 0% when the light amount was the minimum. The response time was expressed as the time required for the change in transmittance from 90% to 10% (fall time; millisecond).

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

(14) Elastic constant (K ₁₁ , K ₃₃ ; measured at NI-35 ° C.)
An EC-1 type elastic constant measuring instrument manufactured by Toyo Corporation was used for the measurement. A sample was put in a vertical alignment cell in which the distance between two glass substrates (cell gap) was 20 μm. A 20 to 0 volt charge was applied to the cell, and the capacitance and applied voltage were measured. Fitting the measured values of capacitance (C) and applied voltage (V) using “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun), formulas (2.98) and (2.101) on page 75 The value of the elastic constant was obtained from the formula (2.100).

[Example A1]
According to the synthesis method described above, 4-methylphenyl 3-fluorobenzoate [compound (1-1-1)] was synthesized.
¹ H-NMR (CDCl ₃ δ [ppm]); 7.99 (td, 1H), 7.87 (td, 1H), 7.48 (td, 1H), 7.32 (td, 1H), 7 .22 (d, 2H), 7.09 (d, 2H), 2.37 (s, 3H).

The transition temperature is a measured value of the compound itself, and the upper limit temperature (T _NI ), the dielectric anisotropy (Δε), and the optical anisotropy (Δn) are the measured values of the sample in which the compound is mixed with the mother liquid crystal. Extrapolated values converted according to the extrapolation method. The physical property values of the compound (1-1-1) were as follows.
Transition temperature: Cr 43.7 Iso.
T _NI = −63.6 ° C., Δε = 3.23, Δn = 0.060.

[Example A2]
According to the synthesis method described above, 4-methylphenyl 3,4-difluorobenzoate [Compound (1-2-1)] was synthesized.
¹ H-NMR (CDCl ₃ δ [ppm]); 8.04-7.97 (m, 2H), 7.28 (dq, 1H), 7.22 (d, 2H), 7.07 (td, 2H), 2.37 (s, 3H).

The transition temperature is a measured value of the compound itself, and the upper limit temperature (T _NI ), the dielectric anisotropy (Δε), and the optical anisotropy (Δn) are the measured values of the sample in which the compound is mixed with the mother liquid crystal. Extrapolated values converted according to the extrapolation method. The physical properties of compound (1-2-1) were as follows.
Transition temperature: Cr 56.8 Iso.
T _NI = −45.0 ° C., Δε = 6.57, Δn = 0.057.

[Example A3]
According to the synthesis method described above, 4-methylphenyl 2,3,4-trifluorobenzoate [compound (1-3-1)] was synthesized.
¹ H-NMR (CDCl ₃ δ [ppm]); 7.90-7.86 (m, 1H), 7.22 (d, 2H), 7.11-7.07 (m, 3H), 2. 37 (s, 3H).

The transition temperature is a measured value of the compound itself, and the upper limit temperature (T _NI ), the dielectric anisotropy (Δε), and the optical anisotropy (Δn) are the measured values of the sample in which the compound is mixed with the mother liquid crystal. Extrapolated values converted according to the extrapolation method. The physical property values of the compound (1-3-1) were as follows.
Transition temperature: Cr 85.9 Iso.
T _NI = −36.3 ° C., Δε = 7.23, Δn = 0.070.

[Example A4]
According to the synthesis method described above, 4-methylphenyl 2,3,4,5-tetrafluorobenzoate [compound (1-4-1)] was synthesized.
¹ H-NMR (CDCl ₃ δ [ppm]); 7.78-7.72 (m, 1H), 7.23 (d, 2H), 7.09 (td, 2H), 2.38 (s, 3H).

The transition temperature is a measured value of the compound itself, and the upper limit temperature (T _NI ), the dielectric anisotropy (Δε), and the optical anisotropy (Δn) are the measured values of the sample in which the compound is mixed with the mother liquid crystal. Extrapolated values converted according to the extrapolation method. The physical property values of the compound (1-4-1) were as follows.
Transition temperature: Cr 85.3 Iso.
T _NI = −48.3 ° C., Δε = 9.90, Δn = 0.077.

[Example A5]
According to the synthesis method described above, 4-methylphenyl 2,3,4,5,6-pentafluorobenzoate [compound (1-5-1)] was synthesized.
¹ H-NMR (CDCl ₃ δ [ppm]); 7.24 (d, 2H), 7.12 (td, 2H), 2.38 (s, 3H).

The transition temperature is a measured value of the compound itself, and the upper limit temperature (T _NI ), the dielectric anisotropy (Δε), and the optical anisotropy (Δn) are the measured values of the sample in which the compound is mixed with the mother liquid crystal. Extrapolated values converted according to the extrapolation method. The physical property values of the compound (1-5-1) were as follows.
Transition temperature: Cr 93.6 Iso.
T _NI = −60.3 ° C., Δε = 7.90, Δn = 0.077.

[Example A6]
According to the synthesis method described above, 4-butylphenyl 3-fluorobenzoate [Compound (1-1-2)] was synthesized.
¹ H-NMR (CDCl ₃ δ [ppm]); 7.99 (td, 1H), 7.87 (td, 1H), 7.48 (td, 1H), 7.32 (td, 1H), 7 .22 (d, 2H), 7.09 (d, 2H), 2.63 (t, 2H), 1.61 (quin, 2H), 1.37 (sex, 2H), 0.936 (t, 3H).

The transition temperature is a measured value of the compound itself, and the upper limit temperature (T _NI ), the dielectric anisotropy (Δε), and the optical anisotropy (Δn) are the measured values of the sample in which the compound is mixed with the mother liquid crystal. Extrapolated values converted according to the extrapolation method. The physical property values of the compound (1-1-2) were as follows.
Transition temperature: Cr 20.0 Iso.
T _NI = −63.6 ° C., Δε = 2.47, Δn = 0.044.

[Example A7]
According to the synthesis method described above, 4-butylphenyl 3,4-difluorobenzoate [Compound (1-2-2)] was synthesized.
¹ H-NMR (CDCl ₃ δ [ppm]); 8.04-7.97 (m, 2H), 7.28 (dq, 1H), 7.22 (d, 2H), 7.07 (td, 2H), 2.63 (t, 2H), 1.61 (quin, 2H), 1.37 (sex, 2H), 0.936 (t, 3H).

The transition temperature is a measured value of the compound itself, and the upper limit temperature (T _NI ), the dielectric anisotropy (Δε), and the optical anisotropy (Δn) are the measured values of the sample in which the compound is mixed with the mother liquid crystal. Extrapolated values converted according to the extrapolation method. The physical properties of compound (1-2-2) were as follows.
Transition temperature: Cr 13.8 Iso.
T _NI = −46.3 ° C., Δε = 5.13, Δn = 0.057.

[Example A8]
According to the synthesis method described above, 4-butylphenyl 2,3,4-trifluorobenzoate [Compound (1-3-2)] was synthesized.
¹ H-NMR (CDCl ₃ δ [ppm]); 7.90-7.86 (m, 1H), 7.22 (d, 2H), 7.11-7.07 (m, 3H), 2. 63 (t, 2H), 1.61 (quin, 2H), 1.37 (sex, 2H), 0.936 (t, 3H).

The transition temperature is a measured value of the compound itself, and the upper limit temperature (T _NI ), the dielectric anisotropy (Δε), and the optical anisotropy (Δn) are the measured values of the sample in which the compound is mixed with the mother liquid crystal. Extrapolated values converted according to the extrapolation method. The physical property values of the compound (1-3-2) were as follows.
Transition _{temperature: Cr 1 -29.9 Cr 2 8.7 Iso} .
T _NI = −41.0 ° C., Δε = 5.13, Δn = 0.050.

[Example A9]
According to the synthesis method described above, 4-butylphenyl 2,3,4,5-tetrafluorobenzoate [compound (1-4-2)] was synthesized.
¹ H-NMR (CDCl ₃ δ [ppm]); 7.78-7.72 (m, 1H), 7.23 (d, 2H), 7.09 (td, 2H), 2.63 (t, 2H), 1.61 (quin, 2H), 1.37 (sex, 2H), 0.936 (t, 3H).

The transition temperature is a measured value of the compound itself, and the upper limit temperature (T _NI ), the dielectric anisotropy (Δε), and the optical anisotropy (Δn) are the measured values of the sample in which the compound is mixed with the mother liquid crystal. Extrapolated values converted according to the extrapolation method. The physical property values of the compound (1-4-2) were as follows.
Transition temperature: Cr 20.6 Iso.
T _NI = −67.0 ° C., Δε = 4.47, Δn = 0.030.

[Example A10]
According to the synthesis method described above, 4-butylphenyl 2,3,4,5,6-pentafluorobenzoate [compound (1-5-2)] was synthesized.
¹ H-NMR (CDCl ₃ δ [ppm]); 7.24 (d, 2H), 7.12 (td, 2H), 2.63 (t, 2H), 1.61 (quin, 2H), 1 .37 (sex, 2H), 0.936 (t, 3H).

The transition temperature is a measured value of the compound itself, and the upper limit temperature (T _NI ), the dielectric anisotropy (Δε), and the optical anisotropy (Δn) Extrapolated values converted according to the extrapolation method. The physical properties of compound (1-5-2) were as follows.
Transition temperature: Cr 46.2 Iso.
T _NI = −90.3 ° C., Δε = 7.83, Δn = 0.004.

[Example A11]
According to the synthesis method described above, octane-1,8-diyl bis (2,3,4,5,6-pentafluorobenzoate [compound (2-1-1)] was synthesized.
¹ H-NMR (CDCl ₃ δ [ppm]); 4.38 (t, 4H), 1.76 (quin, 4H), 1.39 (br, 8H).

The transition temperature is a measured value of the compound itself, and the upper limit temperature (T _NI ), the dielectric anisotropy (Δε), and the optical anisotropy (Δn) Extrapolated values converted according to the extrapolation method. The physical property values of the compound (2-1-1) were as follows.
Transition temperature: Cr ₁ -3.2 Cr ₂ 25.5 Iso.
T _NI = −152.3 ° C., Δε = 0.80, Δn = −0.023.

[Example A12]
In accordance with the synthesis method described above, decane-1,10-diyl bis (2,3,4,5,6-pentafluorobenzoate [compound (2-1-2)] was synthesized.
¹ H-NMR (CDCl ₃ δ [ppm]); 4.38 (t, 4H), 1.76 (quin, 4H), 1.31 (br, 12H).

The transition temperature is a measured value of the compound itself, and the upper limit temperature (T _NI ), the dielectric anisotropy (Δε), and the optical anisotropy (Δn) Extrapolated values converted according to the extrapolation method. The physical property values of the compound (2-1-2) were as follows.
Transition temperature: Cr 40.0 Iso.
T _NI = −184.3 ° C., Δε = −1.90, Δn = −0.043.

[Example A13]
According to the synthesis method described above, dodecane-1,12-diyl bis (2,3,4,5,6-pentafluorobenzoate [compound (2-1-3)] was synthesized.
¹ H-NMR (CDCl ₃ δ [ppm]); 4.39 (t, 4H), 1.75 (quin, 4H), 1.29 (br, 16H).

The transition temperature is a measured value of the compound itself, and the upper limit temperature (T _NI ), the dielectric anisotropy (Δε), and the optical anisotropy (Δn) Extrapolated values converted according to the extrapolation method. The physical property values of the compound (2-1-3) were as follows.
Transition temperature: Cr 51.1 Iso.
T _NI = −113.3 ° C., Δε = 0.10, Δn = −0.003.

[Example A14]
Tridecane-1,13-diyl bis (2,3,4,5,6-pentafluorobenzoate [compound (2-1-4)] was synthesized according to the synthesis method described above.
¹ H-NMR (CDCl ₃ δ [ppm]); 4.38 (t, 4H), 1.75 (quin, 4H), 1.28 (br, 18H).

The transition temperature is a measured value of the compound itself, and the upper limit temperature (T _NI ), the dielectric anisotropy (Δε), and the optical anisotropy (Δn) Extrapolated values converted according to the extrapolation method. The physical properties of compound (2-1-4) were as follows.
Transition temperature: Cr 23.5 Iso.
T _NI = −185.6 ° C., Δε = −2.57, Δn = −0.043.

[Example A15]
According to the synthesis method described above, 2,3,4,5,6-pentafluorobenzoic acid 4- (4-propyloxyphenyl) phenyl [compound (1-10-1)] was synthesized.
¹ H-NMR (CDCl ₃ δ [ppm]); 7.60 (d, 2H), 7.51 (d, 2H), 7.29 (d, 2H), 6.98 (d, 2H), 3 97 (t, 2H), 1.84 (quin., 2H), 1.06 (t, 3H).

The transition temperature of the compound itself was as follows.
Transition temperature: Cr 119 SmA 140 N 165 Iso.

[Example A16]
According to the synthesis method described above, octane-1,8-diyl bis (2,3,4-trifluorobenzoate [compound (2-2-1)]] was synthesized.
¹ H-NMR (CDCl ₃ δ [ppm]); 7.77-7.69 (m, 2H), 7.08-6.99 (m, 2H), 4.34 (t, 4H), 1. 77 (quin, 4H), 1.57-1.40 (m, 8H).

The transition temperature is a measured value of the compound itself, and the upper limit temperature (T _NI ), the dielectric anisotropy (Δε), and the optical anisotropy (Δn) Extrapolated values converted according to the extrapolation method. The physical properties of compound (2-2-1) were as follows.
Transition temperature: Cr 77.2 Iso.
T _NI = −71.6 ° C., Δε = 5.43, Δn = 0.037.

[Example A17]
Nonane-1,9-diylbis (2,3,4-trifluorobenzoate [compound (2-2-2)]] was synthesized according to the synthesis method described above.
¹ H-NMR (CDCl ₃ δ [ppm]); 7.78-7.70 (m, 2H), 7.08-7.00 (m, 2H), 4.34 (t, 4H), 1. 76 (quin, 4H), 1.4-1.35 (m, 10H).

The transition temperature is a measured value of the compound itself, and the upper limit temperature (T _NI ), the dielectric anisotropy (Δε), and the optical anisotropy (Δn) Extrapolated values converted according to the extrapolation method. The physical properties of compound (2-2-2) were as follows.
Transition temperature: Cr 62.5 Iso.
T _NI = −84.3 ° C., Δε = 12.1, Δn = 0.017.

[Example A18]
In accordance with the synthesis method described above, decane-1,10-diyl bis (2,3,4-trifluorobenzoate [compound (2-2-3)] was synthesized.
¹ H-NMR (CDCl ₃ δ [ppm]); 7.77-7.69 (m, 2H), 7.08-6.99 (m, 2H), 4.34 (t, 4H), 1. 76 (quin, 4H), 1.43-1.32 (m, 12H).

The transition temperature of the compound itself was as follows.
Transition temperature: Cr 83.5 Iso.

[Example A19]
According to the synthesis method described above, undecane-1,11-diyl bis (2,3,4-trifluorobenzoate [compound (2-2-4)] was synthesized according to the synthesis method described above.
¹ H-NMR (CDCl ₃ δ [ppm]); 7.77-7.69 (m, 2H), 7.08-6.99 (m, 2H), 4.34 (t, 4H), 1. 76 (quin, 4H), 1.43-1.31 (m, 14H).

The transition temperature of the compound itself was as follows.
Transition temperature: Cr 68.4 Iso.

[Example A20]
According to the synthesis method described above, dodecane-1,12-diyl bis (2,3,4-trifluorobenzoate [compound (2-2-5)]] was synthesized according to the synthesis method described above.
¹ H-NMR (CDCl ₃ δ [ppm]); 7.78-7.70 (m, 2H), 7.08-6.99 (m, 2H), 4.34 (t, 4H), 1. 76 (quin, 4H), 1.43-1.29 (m, 16H).

The transition temperature of the compound itself was as follows.
Transition temperature: Cr 87.2 Iso.

[Example A21]
According to the synthesis method described above, tridecane-1,13-diyl bis (2,3,4-trifluorobenzoate [compound (2-2-6)] was synthesized according to the synthesis method described above.
¹ H-NMR (CDCl ₃ δ [ppm]); 7.78-7.70 (m, 2H), 7.08-6.99 (m, 2H), 4.34 (t, 4H), 1. 76 (quin, 4H), 1.43-1.27 (m, 18H).

The transition temperature of the compound itself was as follows.
Transition temperature: Cr 72.6 Iso.

  The compound in Example A was represented by a symbol based on the definition in Table 3 below. In Table 3, the configuration regarding 1,4-cyclohexylene is trans. The number in parentheses after the symbol corresponds to the compound number. The symbol (−) means other liquid crystal compounds.

Using the liquid crystal compound of Example A described above, a liquid crystal composition having the following ratio (percentage) was prepared, and the characteristic values were evaluated. All are weight percentages (% by weight) based on the weight of the liquid crystal composition.
[Example B1]
H-B (2F) EB-1 (1-1-1) 10%
3-H2B (2F, 3F) -O2 (3-2) 6%
3-HBB (2F, 3F) -O2 (3-13) 11%
4-HBB (2F, 3F) -O2 (3-13) 6%
5-HBB (2F, 3F) -O2 (3-13) 9%
V-HHB (2F, 3F) -O2 (3-6) 15%
V-HHB (2F, 3F) -O4 (3-6) 15%
3-HH-4 (4-1) 6%
3-HHB-1 (4-5) 4%
3-HHB-3 (4-5) 3%
3-HHB-O1 (4-5) 3%
5-HB-O2 (4-2) 3%
3-HHEBH-3 (4-10) 3%
3-HHEBH-4 (4-10) 3%
3-HHEBH-5 (4-10) 3%
NI = 61.8 ° C .; Tc <−20 ° C .; Δε = −3.79; Vth = 1.67 V; K11 = 8.90; K33 = 9.47.

[Example B2]
FB (2F) EB-1 (1-2-1) 10%
3-H2B (2F, 3F) -O2 (3-2) 6%
3-HBB (2F, 3F) -O2 (3-13) 11%
4-HBB (2F, 3F) -O2 (3-13) 6%
5-HBB (2F, 3F) -O2 (3-13) 9%
V-HHB (2F, 3F) -O2 (3-6) 15%
V-HHB (2F, 3F) -O4 (3-6) 15%
3-HH-4 (4-1) 6%
3-HHB-1 (4-5) 4%
3-HHB-3 (4-5) 3%
3-HHB-O1 (4-5) 3%
5-HB-O2 (4-2) 3%
3-HHEBH-3 (4-10) 3%
3-HHEBH-4 (4-10) 3%
3-HHEBH-5 (4-10) 3%
NI = 69.2 ° C .; Tc <−20 ° C .; Δε = −3.27; Vth = 1.78 V; K11 = 8.47; K33 = 9.22.

[Example B3]
FB (2F3F) EB-1 (1-3-1) 10%
3-H2B (2F, 3F) -O2 (3-2) 6%
3-HBB (2F, 3F) -O2 (3-13) 11%
4-HBB (2F, 3F) -O2 (3-13) 6%
5-HBB (2F, 3F) -O2 (3-13) 9%
V-HHB (2F, 3F) -O2 (3-6) 15%
V-HHB (2F, 3F) -O4 (3-6) 15%
3-HH-4 (4-1) 6%
3-HHB-1 (4-5) 4%
3-HHB-3 (4-5) 3%
3-HHB-O1 (4-5) 3%
5-HB-O2 (4-2) 3%
3-HHEBH-3 (4-10) 3%
3-HHEBH-4 (4-10) 3%
3-HHEBH-5 (4-10) 3%
NI = 72.5 ° C .; Tc <−20 ° C .; Δε = −3.53; Vth = 1.66 V; K11 = 9.42; K33 = 8.94.

[Example B4]
FB (2F3F5F) EB-1 (1-4-1) 10%
3-H2B (2F, 3F) -O2 (3-2) 6%
3-HBB (2F, 3F) -O2 (3-13) 11%
4-HBB (2F, 3F) -O2 (3-13) 6%
5-HBB (2F, 3F) -O2 (3-13) 9%
V-HHB (2F, 3F) -O2 (3-6) 15%
V-HHB (2F, 3F) -O4 (3-6) 15%
3-HH-4 (4-1) 6%
3-HHB-1 (4-5) 4%
3-HHB-3 (4-5) 3%
3-HHB-O1 (4-5) 3%
5-HB-O2 (4-2) 3%
3-HHEBH-3 (4-10) 3%
3-HHEBH-4 (4-10) 3%
3-HHEBH-5 (4-10) 3%
NI = 70.1 ° C .; Tc <−20 ° C .; Δ∈ = −3.53; Vth = 1.79 V; K11 = 9.53; K33 = 9.08.

[Example B5]
FB (F4) EB-1 (1-5-1) 10%
3-H2B (2F, 3F) -O2 (3-2) 6%
3-HBB (2F, 3F) -O2 (3-13) 11%
4-HBB (2F, 3F) -O2 (3-13) 6%
5-HBB (2F, 3F) -O2 (3-13) 9%
V-HHB (2F, 3F) -O2 (3-6) 15%
V-HHB (2F, 3F) -O4 (3-6) 15%
3-HH-4 (4-1) 6%
3-HHB-1 (4-5) 4%
3-HHB-3 (4-5) 3%
3-HHB-O1 (4-5) 3%
5-HB-O2 (4-2) 3%
3-HHEBH-3 (4-10) 3%
3-HHEBH-4 (4-10) 3%
3-HHEBH-5 (4-10) 3%
NI = 71.2 ° C .; Tc <−20 ° C .; Δε = −3.19; Vth = 1.76 V; K11 = 9.57; K33 = 8.95.

[Example B6]
H-B (2F) EB-4 (1-1-2) 20%
3-H2B (2F, 3F) -O2 (3-2) 6%
3-HBB (2F, 3F) -O2 (3-13) 10%
4-HBB (2F, 3F) -O2 (3-13) 6%
5-HBB (2F, 3F) -O2 (3-13) 8%
V-HHB (2F, 3F) -O2 (3-6) 14%
V-HHB (2F, 3F) -O4 (3-6) 14%
3-HH-4 (4-1) 6%
3-HHB-1 (4-5) 4%
3-HHB-3 (4-5) 2%
3-HHB-O1 (4-5) 2%
5-HB-O2 (4-2) 2%
3-HHEBH-3 (4-10) 2%
3-HHEBH-4 (4-10) 2%
3-HHEBH-5 (4-10) 2%
NI = 37.6 ° C .; Tc <−20 ° C .; Δε = −4.25; Vth = 1.60 V; K11 = 9.12; K33 = 9.79.

[Example B7]
FB (2F) EB-4 (1-2-2) 20%
3-H2B (2F, 3F) -O2 (3-2) 6%
3-HBB (2F, 3F) -O2 (3-13) 10%
4-HBB (2F, 3F) -O2 (3-13) 6%
5-HBB (2F, 3F) -O2 (3-13) 8%
V-HHB (2F, 3F) -O2 (3-6) 14%
V-HHB (2F, 3F) -O4 (3-6) 14%
3-HH-4 (4-1) 6%
3-HHB-1 (4-5) 4%
3-HHB-3 (4-5) 2%
3-HHB-O1 (4-5) 2%
5-HB-O2 (4-2) 2%
3-HHEBH-3 (4-10) 2%
3-HHEBH-4 (4-10) 2%
3-HHEBH-5 (4-10) 2%
NI = 52.2 ° C .; Tc <−20 ° C .; Δε = −3.05; Vth = 1.89 V; K11 = 8.69; K33 = 9.76.

[Example B8]
FB (2F3F) EB-4 (1-3-2) 20%
3-H2B (2F, 3F) -O2 (3-2) 6%
3-HBB (2F, 3F) -O2 (3-13) 10%
4-HBB (2F, 3F) -O2 (3-13) 6%
5-HBB (2F, 3F) -O2 (3-13) 8%
V-HHB (2F, 3F) -O2 (3-6) 14%
V-HHB (2F, 3F) -O4 (3-6) 14%
3-HH-4 (4-1) 6%
3-HHB-1 (4-5) 4%
3-HHB-3 (4-5) 2%
3-HHB-O1 (4-5) 2%
5-HB-O2 (4-2) 2%
3-HHEBH-3 (4-10) 2%
3-HHEBH-4 (4-10) 2%
3-HHEBH-5 (4-10) 2%
NI = 58.0 ° C .; Tc <−20 ° C .; Δε = −3.56; Vth = 1.71 V; K11 = 8.07; K33 = 9.26.

[Example B9]
FB (2F3F5F) EB-4 (1-4-2) 20%
3-H2B (2F, 3F) -O2 (3-2) 6%
3-HBB (2F, 3F) -O2 (3-13) 10%
4-HBB (2F, 3F) -O2 (3-13) 6%
5-HBB (2F, 3F) -O2 (3-13) 8%
V-HHB (2F, 3F) -O2 (3-6) 14%
V-HHB (2F, 3F) -O4 (3-6) 14%
3-HH-4 (4-1) 6%
3-HHB-1 (4-5) 4%
3-HHB-3 (4-5) 2%
3-HHB-O1 (4-5) 2%
5-HB-O2 (4-2) 2%
3-HHEBH-3 (4-10) 2%
3-HHEBH-4 (4-10) 2%
3-HHEBH-5 (4-10) 2%
NI = 53.2 ° C .; Tc <−20 ° C .; Δ∈ = −2.74; Vth = 1.96 V; K11 = 8.81; K33 = 9.44.

[Example B10]
FB (F4) EB-4 (1-5-2) 20%
3-H2B (2F, 3F) -O2 (3-2) 6%
3-HBB (2F, 3F) -O2 (3-13) 10%
4-HBB (2F, 3F) -O2 (3-13) 6%
5-HBB (2F, 3F) -O2 (3-13) 8%
V-HHB (2F, 3F) -O2 (3-6) 14%
V-HHB (2F, 3F) -O4 (3-6) 14%
3-HH-4 (4-1) 6%
3-HHB-1 (4-5) 4%
3-HHB-3 (4-5) 2%
3-HHB-O1 (4-5) 2%
5-HB-O2 (4-2) 2%
3-HHEBH-3 (4-10) 2%
3-HHEBH-4 (4-10) 2%
3-HHEBH-5 (4-10) 2%
NI = 52.8 ° C .; Tc <−20 ° C .; Δε = −2.95; Vth = 1.88 V; K11 = 8.61; K33 = 9.34.

[Example B11]
FB (4F) E8eB (4F) -F (2-1-1) 10%
3-H2B (2F, 3F) -O2 (3-2) 6%
3-HBB (2F, 3F) -O2 (3-13) 11%
4-HBB (2F, 3F) -O2 (3-13) 6%
5-HBB (2F, 3F) -O2 (3-13) 9%
V-HHB (2F, 3F) -O2 (3-6) 15%
V-HHB (2F, 3F) -O4 (3-6) 15%
3-HH-4 (4-1) 6%
3-HHB-1 (4-5) 4%
3-HHB-3 (4-5) 3%
3-HHB-O1 (4-5) 3%
5-HB-O2 (4-2) 3%
3-HHEBH-3 (4-10) 3%
3-HHEBH-4 (4-10) 3%
3-HHEBH-5 (4-10) 3%
NI = 59.0 ° C .; Tc <−20 ° C .; Δε = −3.82; Vth = 1.75 V; K11 = 9.60; K33 = 10.5.

[Example B12]
FB (4F) E10eB (4F) -F (2-1-2) 10%
3-H2B (2F, 3F) -O2 (3-2) 6%
3-HBB (2F, 3F) -O2 (3-13) 11%
4-HBB (2F, 3F) -O2 (3-13) 6%
5-HBB (2F, 3F) -O2 (3-13) 9%
V-HHB (2F, 3F) -O2 (3-6) 15%
V-HHB (2F, 3F) -O4 (3-6) 15%
3-HH-4 (4-1) 6%
3-HHB-1 (4-5) 4%
3-HHB-3 (4-5) 3%
3-HHB-O1 (4-5) 3%
5-HB-O2 (4-2) 3%
3-HHEBH-3 (4-10) 3%
3-HHEBH-4 (4-10) 3%
3-HHEBH-5 (4-10) 3%
NI = 54.6 ° C .; Tc <−20 ° C .; Δε = −3.86; Vth = 1.74 V; K11 = 10.2; K33 = 10.5.

[Example B13]
FB (4F) E12eB (4F) -F (2-1-3) 10%
3-H2B (2F, 3F) -O2 (3-2) 6%
3-HBB (2F, 3F) -O2 (3-13) 11%
4-HBB (2F, 3F) -O2 (3-13) 6%
5-HBB (2F, 3F) -O2 (3-13) 9%
V-HHB (2F, 3F) -O2 (3-6) 15%
V-HHB (2F, 3F) -O4 (3-6) 15%
3-HH-4 (4-1) 6%
3-HHB-1 (4-5) 4%
3-HHB-3 (4-5) 3%
3-HHB-O1 (4-5) 3%
5-HB-O2 (4-2) 3%
3-HHEBH-3 (4-10) 3%
3-HHEBH-4 (4-10) 3%
3-HHEBH-5 (4-10) 3%
NI = 55.8 ° C .; Tc <−20 ° C .; Δε = −3.84; Vth = 1.78 V; K11 = 10.3; K33 = 10.9.

[Example B14]
FB (4F) E13eB (4F) -F (2-1-4) 10%
3-H2B (2F, 3F) -O2 (3-2) 6%
3-HBB (2F, 3F) -O2 (3-13) 11%
4-HBB (2F, 3F) -O2 (3-13) 6%
5-HBB (2F, 3F) -O2 (3-13) 9%
V-HHB (2F, 3F) -O2 (3-6) 15%
V-HHB (2F, 3F) -O4 (3-6) 15%
3-HH-4 (4-1) 6%
3-HHB-1 (4-5) 4%
3-HHB-3 (4-5) 3%
3-HHB-O1 (4-5) 3%
5-HB-O2 (4-2) 3%
3-HHEBH-3 (4-10) 3%
3-HHEBH-4 (4-10) 3%
3-HHEBH-5 (4-10) 3%
NI = 53.7 ° C .; Tc <−20 ° C .; Δε = −3.69; Vth = 1.75 V; K11 = 9.88; K33 = 10.2.

[Example B15]
H-B (2F) EB-1 (1-1-1) 5%
2-HHB (F) -F (PSI-1) 16%
3-HHB (F) -F (PSI-1) 16%
5-HHB (F) -F (PSI-1) 16%
2-H2HB (F) -F (PSI-2) 10%
3-H2HB (F) -F (PSI-2) 4%
5-H2HB (F) -F (PSI-2) 10%
2-HBB (F) -F (PSI-3) 6%
3-HBB (F) -F (PSI-3) 6%
5-HBB (F) -F (PSI-3) 11%
NI = 91.8 ° C .; Tc <−20 ° C .; K11 = 7.18; K22 = 6.60; K33 = 14.2; k33 / K11 = 1.99; K33 / K22 = 2.16.

[Example B16]
FB (2F) EB-1 (1-2-1) 5%
2-HHB (F) -F (PSI-1) 16%
3-HHB (F) -F (PSI-1) 16%
5-HHB (F) -F (PSI-1) 16%
2-H2HB (F) -F (PSI-2) 10%
3-H2HB (F) -F (PSI-2) 4%
5-H2HB (F) -F (PSI-2) 10%
2-HBB (F) -F (PSI-3) 6%
3-HBB (F) -F (PSI-3) 6%
5-HBB (F) -F (PSI-3) 11%
NI = 92.7 ° C .; Tc <−20 ° C .; K11 = 7.64; K22 = 5.94; K33 = 14.4; K33 / K11 = 1.89; K33 / K22 = 2.46.

[Example B17]
FB (2F3F) EB-1 (1-3-1) 5%
2-HHB (F) -F (PSI-1) 16%
3-HHB (F) -F (PSI-1) 16%
5-HHB (F) -F (PSI-1) 16%
2-H2HB (F) -F (PSI-2) 10%
3-H2HB (F) -F (PSI-2) 4%
5-H2HB (F) -F (PSI-2) 10%
2-HBB (F) -F (PSI-3) 6%
3-HBB (F) -F (PSI-3) 6%
5-HBB (F) -F (PSI-3) 11%
NI = 93.8 ° C .; Tc <−20 ° C .; K11 = 7.55; K22 = 6.18; K33 = 14.7; K33 / K11 = 1.94; K33 / K22 = 2.38.

[Example B18]
FB (2F3F5F) EB-1 (1-4-1) 5%
2-HHB (F) -F (PSI-1) 16%
3-HHB (F) -F (PSI-1) 16%
5-HHB (F) -F (PSI-1) 16%
2-H2HB (F) -F (PSI-2) 10%
3-H2HB (F) -F (PSI-2) 4%
5-H2HB (F) -F (PSI-2) 10%
2-HBB (F) -F (PSI-3) 6%
3-HBB (F) -F (PSI-3) 6%
5-HBB (F) -F (PSI-3) 11%
NI = 92.6 ° C .; Tc <−20 ° C .; K11 = 7.32; K22 = 6.29; K33 = 14.0; K33 / K11 = 2.91; K33 / K22 = 2.29.

[Example B19]
FB (F4) EB-1 (1-5-1) 5%
2-HHB (F) -F (PSI-1) 16%
3-HHB (F) -F (PSI-1) 16%
5-HHB (F) -F (PSI-1) 16%
2-H2HB (F) -F (PSI-2) 10%
3-H2HB (F) -F (PSI-2) 4%
5-H2HB (F) -F (PSI-2) 10%
2-HBB (F) -F (PSI-3) 6%
3-HBB (F) -F (PSI-3) 6%
5-HBB (F) -F (PSI-3) 11%
NI = 92.5 ° C .; Tc <−20 ° C .; K11 = 7.00; K22 = 5.90; K33 = 14.9; K33 / K11 = 2.13; K33 / K22 = 2.54.

[Example B20]
H-B (2F) EB-4 (1-1-2) 20%
2-HHB (F) -F (PSI-1) 13%
3-HHB (F) -F (PSI-1) 13%
5-HHB (F) -F (PSI-1) 13%
2-H2HB (F) -F (PSI-2) 8%
3-H2HB (F) -F (PSI-2) 4%
5-H2HB (F) -F (PSI-2) 8%
2-HBB (F) -F (PSI-3) 5%
3-HBB (F) -F (PSI-3) 5%
5-HBB (F) -F (PSI-3) 11%
NI = 61.7 ° C .; Tc <−20 ° C .; K11 = 6.36; K22 = 4.56; K33 = 11.2; K33 / K11 = 1.77; K33 / K22 = 2.48.

[Example B21]
FB (2F) EB-4 (1-2-2) 20%
2-HHB (F) -F (PSI-1) 13%
3-HHB (F) -F (PSI-1) 13%
5-HHB (F) -F (PSI-1) 13%
2-H2HB (F) -F (PSI-2) 8%
3-H2HB (F) -F (PSI-2) 4%
5-H2HB (F) -F (PSI-2) 8%
2-HBB (F) -F (PSI-3) 5%
3-HBB (F) -F (PSI-3) 5%
5-HBB (F) -F (PSI-3) 11%
NI = 66.3 ° C .; Tc <−20 ° C .; K11 = 6.52; K22 = 0.08; K33 = 12.0; K33 / K11 = 1.84; K33 / K22 = 2.38.

[Example B22]
FB (2F3F) EB-4 (1-3-2) 20%
2-HHB (F) -F (PSI-1) 13%
3-HHB (F) -F (PSI-1) 13%
5-HHB (F) -F (PSI-1) 13%
2-H2HB (F) -F (PSI-2) 8%
3-H2HB (F) -F (PSI-2) 4%
5-H2HB (F) -F (PSI-2) 8%
2-HBB (F) -F (PSI-3) 5%
3-HBB (F) -F (PSI-3) 5%
5-HBB (F) -F (PSI-3) 11%
NI = 70.0 ° C .; Tc <−20 ° C .; K11 = 6.77; K22 = 4.23; K33 = 12.3; K33 / K11 = 1.82; K33 / K22 = 2.94.

[Example B23]
FB (2F3F5F) EB-4 (1-4-2) 20%
2-HHB (F) -F (PSI-1) 13%
3-HHB (F) -F (PSI-1) 13%
5-HHB (F) -F (PSI-1) 13%
2-H2HB (F) -F (PSI-2) 8%
3-H2HB (F) -F (PSI-2) 4%
5-H2HB (F) -F (PSI-2) 8%
2-HBB (F) -F (PSI-3) 5%
3-HBB (F) -F (PSI-3) 5%
5-HBB (F) -F (PSI-3) 11%
NI = 64.1 ° C .; Tc <−20 ° C .; K11 = 5.99; K22 = 4.67; K33 = 10.8; K33 / K11 = 1.81; K33 / K22 = 2.32.

[Example B24]
FB (F4) EB-1 (1-5-2) 20%
2-HHB (F) -F (PSI-1) 13%
3-HHB (F) -F (PSI-1) 13%
5-HHB (F) -F (PSI-1) 13%
2-H2HB (F) -F (PSI-2) 8%
3-H2HB (F) -F (PSI-2) 4%
5-H2HB (F) -F (PSI-2) 8%
2-HBB (F) -F (PSI-3) 5%
3-HBB (F) -F (PSI-3) 5%
5-HBB (F) -F (PSI-3) 11%
NI = 64.5 ° C .; Tc <−20 ° C .; K11 = 6.13; K22 = 4.19; K33 = 10.5; K33 / K11 = 1.71; K33 / K22 = 2.58.

[Example B25]
FB (F4) EBB-O3 (1-10-1) 5%
3-H2B (2F, 3F) -O2 (3-2) 6%
3-HBB (2F, 3F) -O2 (3-13) 12%
4-HBB (2F, 3F) -O2 (3-13) 6%
5-HBB (2F, 3F) -O2 (3-13) 10%
V-HHB (2F, 3F) -O2 (3-6) 16%
V-HHB (2F, 3F) -O4 (3-6) 16%
3-HH-4 (4-1) 7%
3-HHB-1 (4-5) 4%
3-HHB-3 (4-5) 3%
3-HHB-O1 (4-5) 3%
5-HB-O2 (4-2) 3%
3-HHEBH-3 (4-10) 3%
3-HHEBH-4 (4-10) 3%
3-HHEBH-5 (4-10) 3%
NI = 88.2 ° C .; Tc <−20 ° C .; Vth = 1.84 V; K11 = 9.15; K33 = 8.64.

[Comparative Example 1]
In order to clarify the effect of the composition of the present application, the physical properties of the composition not containing the first component compound (1), which is a feature of the composition of the present application, were measured. The components and physical properties of the composition are as follows.
3-H2B (2F, 3F) -O2 (3-2) 7%
3-HBB (2F, 3F) -O2 (3-13) 12%
4-HBB (2F, 3F) -O2 (3-13) 7%
5-HBB (2F, 3F) -O2 (3-13) 10%
V-HHB (2F, 3F) -O2 (3-6) 17%
V-HHB (2F, 3F) -O4 (3-6) 17%
3-HH-4 (4-1) 7%
3-HHB-1 (4-5) 5%
3-HHB-3 (4-5) 3%
3-HHB-O1 (4-5) 3%
5-HB-O2 (4-2) 3%
3-HHEBH-3 (4-10) 3%
3-HHEBH-4 (4-10) 3%
3-HHEBH-5 (4-10) 3%
NI = 85.5 ° C .; Tc <−20 ° C .; Δε = −3.28; Vth = 1.75 V; K11 = 10.8; K33 = 8.93.

[Contrast between Examples B1 to 10 and Comparative Example 1]
Table 4 shows the type, content (wt%), and elastic constant K33 of the first component of Example B1 to Example B10.

実施例Ｂ１〜１０と比較例１との物性を対比した結果、実施例Ｂ１から実施例Ｂ１０の組成物は、第一成分を含まない比較例１と比べて大きな弾性定数Ｋ３３を示した。

As a result of comparing the physical properties of Examples B1 to 10 and Comparative Example 1, the compositions of Example B1 to Example B10 exhibited a larger elastic constant K33 than Comparative Example 1 that did not contain the first component.

[Contrast of Examples B11-24 with Comparative Example 1]
Table 5 shows the type, content, Δε, and elastic constant K33 of the first component of Examples B11 to B14.

As a result of comparing the physical properties of Examples B11 to 14 and Comparative Example 1, the compositions of Example B11 to Example B14 showed a large Δε and elastic constant K33 as compared with Comparative Example 1 not including the first component. .
In addition, the compositions of Example B11 to Example B24 showed a larger elastic constant than that of Comparative Example 1. Therefore, it is concluded that the liquid crystal composition of the present invention has excellent characteristics.

[Comparative Example 2]
The physical property values of the composition of Compound 2e and EBBA disclosed in Non-Patent Document 1 K. Kishikawa et al., Chemistry Letters., 2012, Vol. 41, 1465.
(Synthesis of Comparative Compound 2e)
First, hexane-1,6-diyl bis (2,3,4,5,6-pentafluorobenzoate (2e) was synthesized as a comparative compound.

The chemical shift δ (ppm) of ¹ H-NMR analysis is as follows, and the obtained compound was hexane-1,6-diylbis (2,3,4,5,6-pentafluorobenzoate (2e). Was identified.
¹ H-NMR (CDCl ₃ δ [ppm]); 4.39 (t, 4H), 1.79 (quin, 4H), 1.49 (quin, 4H).
The transition temperature of compound (2e) was as follows.
Transition temperature: Cr 42.2 Iso.

(Physical properties of mother liquid crystal EBBA)
Subsequently, physical property values of N- (4-ethoxybenzylidene) 4-butylaniline (EBBA: manufactured by Tokyo Chemical Industry Co., Ltd.) serving as a mother liquid crystal were measured. The physical properties of this mother liquid crystal EBBA were as follows. The viscosity, optical anisotropy, and dielectric anisotropy are measured values at 40 ° C. at which EBBA exhibits a nematic phase.

上限温度（Ｔ_NI）＝８０．０℃；粘度（η₂₀）＝１５．２ｍＰａ・ｓ；光学異方性（Δｎ）＝０．２４１；誘電率異方性（Δε）＝−０．２．

Maximum temperature (T _NI ) = 80.0 ° C .; viscosity (η ₂₀ ) = 15.2 mPa · s; optical anisotropy (Δn) = 0.241; dielectric anisotropy (Δε) = − 0.2.

(Physical properties of liquid crystal composition <Ex-1> comprising compound 2e and mother liquid crystal EBBA)
A liquid crystal composition (Ex-1) in which 5 wt% of 2e was added to the mother liquid crystal EBBA was prepared, and the physical properties thereof were measured. The physical properties of this liquid crystal composition Ex-1 were as follows. The viscosity and optical anisotropy are measured values at 40 ° C. as in the case of the base liquid crystal EBBA.
Maximum temperature (T _NI ) = 70.4 ° C .; viscosity (η ₂₀ ) = 16.5 mPa · s; optical anisotropy (Δn) = 0.236.

(Measurement of dielectric anisotropy value and elastic constant of liquid crystal composition <Ex-1>)
According to the measurement method described above, dielectric anisotropy and elastic constant K33 at 40 ° C. were measured. However, the liquid crystal composition Ex-1 had almost no dielectric anisotropy and could not be calculated as a numerical value. Further, since there was no dielectric anisotropy and no response to applied voltage, the elastic constant of the liquid crystal composition Ex-1 could not be measured.

  From the results of Comparative Example 2, the composition of Compound 2e and EBBA disclosed in Non-Patent Document 1 is unsuitable as a liquid crystal composition used for a liquid crystal element, and can impart a high elastic constant which is an effect of the present application. No effect was seen.

  Therefore, from the result of comparison between Examples B1 to 24 and Comparative Examples 1 and 2, it was found that the liquid crystal composition of the present application is useful as a liquid crystal composition for a liquid crystal element.

  The liquid crystal composition of the present invention has a high maximum temperature, a low minimum temperature, a small viscosity, a suitable optical anisotropy, a large negative dielectric anisotropy, a large specific resistance, a high stability to ultraviolet rays, and a high stability to heat Or the like, satisfying at least one characteristic or having an appropriate balance with respect to at least two characteristics. A liquid crystal display element containing this composition has characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime, and thus can be used for a liquid crystal projector, a liquid crystal television, and the like. .

Claims (19)

Containing at least one compound selected from the group of compounds represented by formula (1) as a first component;

(In the formula (1), R ¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 1 to 12 carbons in which at least one hydrogen is replaced by fluorine. Or an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine;
Ring A is 1,4-phenylene or 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine;
p is 1 or 2; X ^{1 to} X ⁵ are independently hydrogen or fluorine;
At least one of X ^{1 to} X ⁵ is fluorine. )
Further, a liquid crystal composition containing at least one fluorine-containing liquid crystal compound represented by the formula (3) as a second component .

In Formula (3), R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or 1 to 12 carbon alkyls in which at least one hydrogen is replaced by halogen;
Ring D and Ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, Or tetrahydropyran-2,5-diyl;
Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4, 5-trifluoronaphthalene-2,6-diyl or 7,8-difluorochroman-2,6-diyl;
Z ¹ and Z ² are independently a single bond, ethylene, carbonyloxy, or methyleneoxy;
a is 1, 2, or 3, b is 0 or 1, and the sum of a and b is 3 or less. Containing at least one compound selected from the group of compounds represented by formula (2) as a first component;

(In the formula (2), Sp ¹ is alkylene having 2 to 20 carbon atoms, alkenylene having 2 to 20 carbon atoms, or alkynylene having 2 to 20 carbon atoms;
X ^a and X ^b are independently hydrogen or fluorine. Further, a liquid crystal composition containing at least one fluorine-containing liquid crystal compound represented by the formula (3) as a second component .

In Formula (3), R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or 1 to 12 carbon alkyls in which at least one hydrogen is replaced by halogen;
Ring D and Ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, Or tetrahydropyran-2,5-diyl;
Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4, 5-trifluoronaphthalene-2,6-diyl or 7,8-difluorochroman-2,6-diyl;
Z ¹ and Z ² are independently a single bond, ethylene, carbonyloxy, or methyleneoxy;
a is 1, 2, or 3, b is 0 or 1, and the sum of a and b is 3 or less. The liquid crystal composition according to claim 1, comprising at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-10) as a first component.

In formula (1-1) to formula (1-10), R ¹ is independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen. Is alkyl having 1 to 12 carbon atoms replaced with fluorine, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine. The liquid crystal composition according to claim 2, comprising at least one compound selected from the group of compounds represented by formula (2-1) or formula (2-2) as a first component.

In Formula (2-1) and Formula (2-2), l is independently an integer of 2 to 15.   5. The liquid crystal composition according to claim 1, wherein the ratio of the first component is in the range of 1% by weight to 30% by weight based on the weight of the liquid crystal composition. The liquid crystal according to any one of claims 1 to 5 , comprising at least one compound selected from the group of compounds represented by formula (3-1) to formula (3-19) as a second component. Composition.

In the formulas (3-1) to (3-19), R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon The alkenyloxy having 2 to 12 carbon atoms or the alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by halogen. The liquid crystal composition according to any one of claims 1 to 6 , wherein the proportion of the second component is in the range of 5 wt% to 70 wt% based on the weight of the liquid crystal composition. Containing at least one compound selected from the group of compounds represented by formula (4) as a third component, the liquid crystal composition according to any one of claims 1 to 7.

In the formula (4), R ⁵ and R ⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least one hydrogen is replaced by halogen. Alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by halogen; ring G and ring J are independently 1,4-cyclohexylene, 1,4 -Phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ³ is a single bond, ethylene, or carbonyloxy; n is 1, 2, Or 3. The liquid crystal according to any one of claims 1 to 8 , comprising at least one compound selected from the group of compounds represented by formulas (4-1) to (4-13) as a third component. Composition.

In formulas (4-1) to (4-13), R ⁵ and R ⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, It is alkyl having 1 to 12 carbons in which one hydrogen is replaced with fluorine, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced with fluorine. The liquid crystal composition according to any one of claims 1 to 9, wherein the ratio of the third component is in the range of 10 wt% to 90 wt% based on the weight of the liquid crystal composition. Containing at least one polymerizable compound as an additive component selected from the group of compounds represented by formula (5), the liquid crystal composition according to any one of claims 1 to 10.

In formula (5), ring K and ring M are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine- 2-yl or pyridin-2-yl, and in these rings, at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen being halogen. May be substituted with substituted alkyl having 1 to 12 carbons; ring L is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl Naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, Phthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1 , 3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in which at least one hydrogen is halogen, alkyl having 1 to 12 carbons , Alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by halogen; Z ⁴ and Z ⁵ are independently a single bond or 1 carbon atom. from alkylene of 10, in the alkylene, at least one of -CH ₂ -, -O -, - CO -, - COO-, or -OCO- in May be replaced come, at least one -CH ₂ -CH ₂ - is, -CH = CH -, - C (CH 3) = CH -, - CH = C (CH 3) -, or -C (CH ₃ ) = C (CH ₃ ) —, in which at least one hydrogen may be replaced by fluorine or chlorine; P ¹ , P ² , and P ³ are independently Sp ² , Sp ³ , and Sp ⁴ are each independently a single bond or alkylene having 1 to 10 carbons, in which at least one —CH ₂ — is —O —, —COO—, —OCO—, or —OCOO— may be substituted, and at least one —CH ₂ —CH ₂ — may be substituted with —CH═CH— or —C≡C—. At least one hydrogen in these groups , Fluorine or chlorine; g is 0, 1, or 2; h, j, and k are independently 0, 1, 2, 3, or 4; and h, The sum of j and k is 1 or more. In formula (5) according to claim 11, P ¹ , P ² and P ³ are independently selected from the group of groups represented by formula (P-1) to formula (P-6). The liquid crystal composition according to claim 11, which is a polymerizable group.

In formula (P-1) to formula (P-6), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced by halogen In the formula (5), when all of the h P ¹ and k P ³ are groups represented by the formula (P-4), At least one of Sp ¹ and k Sp ³ is alkylene in which at least one —CH ₂ — is replaced by —O—, —COO—, —OCO—, or —OCOO—. The additive component according to any one of claims 1 to 12 , comprising at least one polymerizable compound selected from the group of compounds represented by formula (5-1) to formula (5-27). Liquid crystal composition.

In formula (5-1) to formula (5-27), P ⁴ , P ⁵ and P ⁶ are independently from the group of groups represented by formula (P-1) to formula (P-3). A selected polymerizable group;

In formula (P-1) to formula (P-3), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced by halogen In formula (5-1) to formula (5-27), Sp ¹ , Sp ² , and Sp ³ are each independently a single bond or a carbon number of 1 to 10 In which at least one —CH ₂ — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, and at least one —CH ₂ —CH ₂ -May be replaced by -CH = CH- or -C≡C-, in which at least one hydrogen may be replaced by fluorine or chlorine. The liquid crystal composition according to any one of claims 11 to 13 , wherein an addition ratio of the additive component is in the range of 0.03% by weight to 10% by weight based on the weight of the liquid crystal composition. The liquid crystal display element containing the liquid-crystal composition of any one of Claim 1 to 14 . The liquid crystal display element according to claim 15 , wherein an operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and a driving method of the liquid crystal display element is an active matrix method. A liquid crystal display element of a polymer-supported alignment type, comprising the liquid crystal composition according to any one of claims 11 to 14 , wherein a polymerizable compound in the liquid crystal composition is polymerized. Use of the liquid crystal composition according to claim 1 in a liquid crystal display device. Use of the liquid crystal composition according to any one of claims 11 to 14 in a polymer supported alignment type liquid crystal display element.