JP4962031B2 - Liquid crystal composition and liquid crystal display element - Google Patents

Description

  The present invention relates to a liquid crystal composition suitable mainly for an AM (active matrix) device and the like, and an AM device containing the composition. This composition has a nematic phase and a positive dielectric anisotropy.

  In the liquid crystal display element, the classification based on the operation mode of the liquid crystal includes PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS ( in-plane switching) and VA (vertical alignment). The classification based on the element driving method is PM (passive matrix) and AM (active matrix). PM is classified into static and multiplex, and AM is classified into thin film transistor (TFT), metal insulator metal (MIM), 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.

  These devices contain a liquid crystal composition having appropriate characteristics. This liquid crystal composition has a nematic phase. In order to obtain an AM device having good general characteristics, the general characteristics of the composition are improved. The relationships in the two general characteristics are summarized in Table 1 below. The general 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. The preferable upper limit temperature of the nematic phase is 70 ° C. or higher, and the preferable lower limit temperature of the nematic phase is −10 ° C. or lower. 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. 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. 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. For a device with a mode such as TN, a suitable value is about 0.45 μm. In this case, 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. Generally, the viscosity increases as the dielectric anisotropy increases. Appropriate dielectric anisotropy is required depending on the use of the device. 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 against ultraviolet rays and heat relates to the lifetime of the liquid crystal display element. When their stability is high, the lifetime of the device is long.

Conventional compositions are disclosed in Patent Documents 1 and 2 below.
JP 61-27931 A JP-A-10-114693

  Desirable AM elements have characteristics such as a wide usable temperature range, a short response time, a large contrast ratio, a low threshold voltage, a large voltage holding ratio, and a long lifetime. A shorter response time is desirable even at 1 millisecond. Therefore, desirable properties of the composition include a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a large optical anisotropy, a large dielectric anisotropy, a large specific resistance, a high stability to ultraviolet light, a heat High stability against.

  One of the objects of the present invention is to provide a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a suitable and large optical anisotropy, a suitable dielectric anisotropy, a large specific resistance, ultraviolet light and heat. The object is to provide a liquid crystal composition satisfying a plurality of characteristics in characteristics such as high stability. The object is to provide a liquid crystal composition having an appropriate balance regarding a plurality of characteristics. This object is also to provide a liquid crystal display device containing such a composition. Another object of the present invention is to provide a composition having a small viscosity, an optical anisotropy of 0.10 to 0.17, etc., and a short response time, a large voltage holding ratio, a large contrast ratio, a long It is to provide an AM device having a lifetime.

  At least one compound selected from the group of compounds represented by formula (1) as the first component, and selected from the group of compounds represented by formula (2-1) and formula (2-2) as the second component At least one compound selected from the group of compounds represented by formulas (3-1) to (3-3) as a third component and having a nematic phase object.

Here, R ¹ is alkenyl having 2 to 12 carbon atoms, alkadienyl having 4 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms in which arbitrary hydrogen is replaced by fluorine; R ² , R ³ and R ⁵ are Independently alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons or alkenyl having 2 to 12 carbons in which arbitrary hydrogen is replaced by fluorine; R ⁴ is fluorine, alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbon atoms; ^{R 6} is fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbon atoms; ^{Y 1} is fluorine or It is chlorine; ^{Y 2} is fluorine or trifluoromethoxy; ^{X 1} and ^{X 5} is hydrogen or fluorine ^{independently; X} 2, X ³ and ^{X 4} hydrogen also independently Fluorine is. However, at least one of X ² , X ³ and X ⁴ is fluorine.

  The composition of the present invention has a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a suitable and large optical anisotropy, a suitable dielectric anisotropy, a large specific resistance, a high stability against ultraviolet rays and heat. In characteristics such as sex, a plurality of characteristics are satisfied. This composition has an appropriate balance for multiple properties. The device of the present invention contains this composition. Many of these compositions have properties such as low viscosity, optical anisotropy of 0.10 to 0.17, and AM with short response time, large voltage holding ratio, large contrast ratio, long life, etc. Suitable for device.

  Terms used in this specification are as follows. The liquid crystal composition of the present invention or the liquid crystal display device of the present invention may be abbreviated as “composition” or “device”, respectively. A liquid crystal display element is a general term for a liquid crystal display panel and a liquid crystal display module. “Liquid crystal compound” means a compound having a liquid crystal phase such as a nematic phase or a smectic phase, or a compound having no liquid crystal phase but useful as a component of a composition. This useful compound contains a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene and has a linear molecular structure. An optically active compound may be added to the composition. Even if this compound is a liquid crystal compound, it is classified here as an additive. At least one compound selected from the group of compounds represented by formula (1) may be abbreviated as “compound (1)”. A group of compounds represented by formula (1) may also be abbreviated as “compound (1)”. The same applies to compounds represented by other formulas.

  The upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”. The lower limit temperature of the 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 but also at a high temperature in the initial stage, and has a large specific resistance not only at room temperature but also at a high temperature after long-term use. . “High voltage holding ratio” means that the device has a large voltage holding ratio not only at room temperature but also at a high temperature in the initial stage, and has a large voltage holding ratio not only at room temperature but also at a high temperature after long use. means. When describing characteristics such as optical anisotropy, values measured by the methods described in the examples are used. The “ratio of the first component” means a percentage by weight (% by weight) based on the total weight of the liquid crystal composition. The same applies to the ratio of the second component. The ratio of the additive mixed with the composition means a weight percentage (% by weight) based on the total weight of the liquid crystal composition.

  The following compound (1) has a large optical anisotropy, a large dielectric anisotropy, and a small viscosity. Accordingly, the present composition is selected from compound (2-1) to compound (2-2) and compound (3-1) to compound (3-3) so as to satisfy high reliability and a balance of various properties. Completed the thing. The compound (2-1) to the compound (2-2) have remarkably large dielectric anisotropy, and the compound (3-1) to the compound (3-3) have appropriate optical anisotropy and high maximum temperature. , Low minimum temperature and low viscosity. A composition is prepared based on such an idea, and a composition having characteristics such as appropriate optical anisotropy, appropriate dielectric anisotropy, small viscosity, high reliability, and high maximum temperature and low minimum temperature. I found it. The present invention was completed by further studying component compounds that can finely adjust the properties of the composition.

ここで、Ｒ^１は炭素数２〜１２のアルケニル、炭素数４〜１２のアルカジエニルまたは任意の水素がフッ素で置き換えられた炭素数２〜１２のアルケニルであり、Ｙ^１はフッ素または塩素である。

Here, R ¹ is alkenyl having 2 to 12 carbon atoms, alkadienyl having 4 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms in which arbitrary hydrogen is replaced by fluorine, and Y ¹ is fluorine or chlorine.

The details of the present invention are as follows.
[1] At least one compound selected from the group of compounds represented by formula (1) as the first component, and compounds represented by formula (2-1) and formula (2-2) as the second component At least one compound selected from the group, and at least one compound selected from the group of compounds represented by formula (3-1), formula (3-2) and formula (3-3) as the third component And a liquid crystal composition having a nematic phase.

Here, R ¹ is alkenyl having 2 to 12 carbon atoms, alkadienyl having 4 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms in which arbitrary hydrogen is replaced by fluorine; R ² , R ³ and R ⁵ are Independently alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons or alkenyl having 2 to 12 carbons in which arbitrary hydrogen is replaced by fluorine; R ⁴ is fluorine, alkyl having 1 to 12 carbons Or R ⁶ is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons; Y ¹ is fluorine or chlorine by and; ^{Y 2} is fluorine or trifluoromethoxy; ^{X 1} and ^{X 5} is hydrogen or fluorine ^{independently; X} 2, X ³ and ^{X 4} are independently hydrogen or A ^{Tsu-containing,} among X 2, ^{X 3} and ^{X 4,} at least one is fluorine.

[2] The second component is at least one compound selected from the group of compounds represented by formula (2-1), and the third component is selected from the group of compounds represented by formula (3-1) The liquid crystal composition according to item [1], wherein the liquid crystal composition is at least one compound.

[3] Based on the total weight of the liquid crystal composition, the proportion of the first component is in the range of 5 wt% to 20 wt%, the proportion of the second component is in the range of 10 wt% to 35 wt%, and Item 3. The liquid crystal composition according to item [1] or [2], wherein the ratio of the third component is in the range of 10 wt% to 55 wt%.

[4] At least one compound selected from the group of compounds represented by formula (1) as the first component, and compounds represented by formula (2-1) and formula (2-2) as the second component At least one compound selected from the group, at least one compound selected from the group of compounds represented by formula (3-1), formula (3-2) and formula (3-3) as a third component; And a liquid crystal composition containing at least one compound selected from the group of compounds represented by formula (4) as a fourth component and having a nematic phase.

Here, R ¹ is alkenyl having 2 to 12 carbon atoms, alkadienyl having 4 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms in which arbitrary hydrogen is replaced by fluorine; R ² , R ³ and R ⁵ are Independently alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons or alkenyl having 2 to 12 carbons in which arbitrary hydrogen is replaced by fluorine; R ⁴ is fluorine, alkyl having 1 to 12 carbons Or R 2 is alkenyl having 2 to 12 carbons; R ⁶ is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons; R ⁷ and R ⁸ are Independently alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons or alkenyl having 2 to 12 carbons in which arbitrary hydrogen is replaced by fluorine; Y ¹ represents fluorine or Y ² is fluorine or trifluoromethoxy; X ¹ and X ⁵ are independently hydrogen or fluorine; X ² , X ³ and X ⁴ are independently hydrogen or fluorine, X ² , X ³ and X ⁴ are at least one fluorine.

[5] The liquid crystal composition according to item [4], wherein the second component is at least one compound selected from the group of compounds represented by formula (2-1).

[6] The fourth component is at least one compound selected from the group of compounds represented by formula (4), R ⁷ is alkenyl having 2 to 12 carbons, and R ⁸ is 1 to 12 carbons. The liquid crystal composition according to item [4] or [5], wherein

[7] The third component is at least one compound selected from the group of compounds represented by formula (3-1), X ² is fluorine, X ³ and X ⁴ are hydrogen, The liquid crystal composition according to [5] or [6].

[8] The liquid crystal composition according to any one of items [1] to [7], wherein Y ¹ in formula (1) is fluorine.

[9] Based on the total weight of the liquid crystal composition, the proportion of the first component is in the range of 5 wt% to 20 wt%, the proportion of the second component is in the range of 10 wt% to 35 wt%, Item [4] to [8], wherein the proportion of the three components is in the range of 10% to 55% by weight and the proportion of the fourth component is in the range of 10% to 40% by weight. Liquid crystal composition.

[10] The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy at a wavelength of 589 nm at 25 ° C. is in the range of 0.11 to 0.17, and the rotational viscosity coefficient at 25 ° C. is 30 mPa · s. Item 10. The liquid crystal composition according to any one of Items [1] to [9], in a range of from 100 to 100 mPa · s.

[11] A liquid crystal display device comprising the liquid crystal composition according to any one of items [1] to [10].

  The present invention also includes the following items. 1) The above-described composition further containing an optically active compound, 2) the above-mentioned composition further containing additives such as an antioxidant, an ultraviolet absorber, and an antifoaming agent. 3) an AM device containing the above composition, 4) a device containing the above composition and having a mode of TN, ECB, OCB, or IPS, 5) a transmissive device containing the above composition 6) Use of the above composition as a composition having a nematic phase, 7) Use of the above composition 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 preferred ratio of the component compounds and the basis thereof will be described. Fourth, a preferred form of the component compound will be described. Fifth, specific examples of component compounds are shown. Sixth, a method for synthesizing the component compounds will be described. Seventh, additives that may be mixed into the composition 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. The composition A may further contain other liquid crystal compounds, additives, impurities and the like. “Other liquid crystal compounds” include compound (1), compound (2-1), compound (2-2), compound (3-1), compound (3-2), compound (3-3) and compound. It is a liquid crystal compound different from (4). Such compounds are mixed into the composition for the purpose of further adjusting the properties. Additives include optically active compounds, dyes, antioxidants, ultraviolet absorbers and the like. Impurities are compounds mixed in processes such as synthesis of component compounds

  Composition B is substantially composed of Compound (1), Compound (2-1), Compound (2-2), Compound (3-1), Compound (3-2), Compound (3-3) and Compound ( It consists only of the compound selected from 4). “Substantially” means that the composition does not contain a liquid crystal compound different from these compounds. “Substantially” also means that the composition may further contain additives, impurities and the like. Composition B has fewer components than composition A. Composition B is preferred over Composition A because it reduces costs. Since the physical properties can be further adjusted by mixing other liquid crystal compounds, the composition A is preferable to the composition B.

  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 properties of the component compounds are summarized in Table 2 according to the purpose of the present invention. In the symbols in Table 2, L means large or high, M means moderate, and S means small or low.

  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) increases the dielectric anisotropy, increases the optical anisotropy, decreases the minimum temperature, and decreases the viscosity. Compound (2-1) and compound (2-2) greatly increase the dielectric anisotropy. From compound (3-1) to compound (3-3), the maximum temperature is increased, the minimum temperature is decreased, the viscosity is decreased, and the value of optical anisotropy is adjusted to an appropriate value. Compound (4) greatly reduces the viscosity of the composition.

  Third, the preferred ratio of the component compounds and the basis thereof will be described. A desirable ratio of the first component is 5% or more for increasing the dielectric anisotropy, increasing the optical anisotropy, decreasing the minimum temperature and decreasing the viscosity, and increasing the maximum temperature and decreasing the minimum temperature. 30% or less. A more desirable ratio is in the range of 5% to 25%. A particularly desirable ratio is in the range of 6% to 20%.

  A desirable ratio of the second component is 10% or more for increasing the dielectric anisotropy, and 35% or less for decreasing the minimum temperature. A more desirable ratio is in the range of 15% to 35%. A particularly desirable ratio is in the range of 15% to 30%.

  A desirable ratio of the third component is 10% or more for increasing the maximum temperature, decreasing the minimum temperature, and decreasing the viscosity, and is 60% or less for decreasing the minimum temperature and increasing the dielectric anisotropy. . A more desirable ratio is in the range of 10% to 55%. A particularly desirable ratio is in the range of 15% to 55%.

  The fourth component is an optional component and is particularly suitable for preparing a composition having a small viscosity. A desirable ratio of this component is 45% or less for decreasing the minimum temperature. A more desirable ratio is 40% or less. A particularly desirable ratio is 35% or less.

  In the composition A, the preferable ratio of the total of the first component, the second component, the third component, and the fourth component is 70% or more in order to obtain good characteristics. A more desirable ratio is 90% or more. The sum of the four components in composition B is 100%.

  Fourth, a preferred form of the component compound will be described.

R ¹ is alkenyl having 2 to 12 carbons, alkadienyl having 4 to 12 carbons, or alkenyl having 2 to 12 carbons in which any hydrogen is replaced by fluorine. Desirable R ¹ is alkenyl having 2 to 8 carbon atoms, alkadienyl having 4 to 8 carbon atoms or alkenyl having 2 to 8 carbon atoms in which arbitrary hydrogen is replaced by fluorine from the viewpoint of lowering the minimum temperature and decreasing the viscosity. is there. More desirable R ¹ is alkenyl having 2 to 5 carbon atoms. R ² , R ³ and R ⁵ are independently alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons or alkenyl having 2 to 12 carbons in which any hydrogen is replaced by fluorine. Desirable R ² , R ³ and R ⁵ are alkyl having 1 to 8 carbons or alkenyl having 2 to 8 carbons from the viewpoint of lowering the minimum temperature and lowering the viscosity. More desirable R ² , R ³ and R ⁵ are alkyl having 1 to 5 carbons or alkenyl having 2 to 5 carbons. R ⁴ is fluorine, alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons. Desirable R ⁴ is fluorine, alkyl having 1 to 8 carbons or alkenyl having 2 to 8 carbons from the viewpoint of lowering the minimum temperature and decreasing the viscosity. More desirable R ⁴ is fluorine, alkyl having 1 to 5 carbons or alkenyl having 2 to 5 carbons. Particularly preferred R ⁴ is fluorine. R ⁶ is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons. Preferred R ⁶ is fluorine, chlorine, alkyl having 1 to 8 carbons or alkenyl having 2 to 8 carbons from the viewpoint of lowering the minimum temperature and lowering the viscosity. More desirable R ⁶ is fluorine, chlorine, alkyl having 1 to 5 carbons or alkenyl having 2 to 5 carbons. R ⁷ and R ⁸ are alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which any hydrogen is replaced by fluorine. Desirable R ⁷ and R ⁸ are alkyl having 1 to 8 carbons, alkenyl having 2 to 8 carbons or arbitrary hydrogen having 2 to 8 carbons substituted with fluorine from the viewpoint of lowering the viscosity and lowering the minimum temperature. Of alkenyl. More preferably ^{R 7} and ^{R 8} are, ^{R 7} is alkenyl or arbitrary hydrogen alkenyl having 2 to 8 carbon atoms which is replaced by fluorine having from 2 to 8 carbon atoms, the alkyl ^{R 8} is 1 to 8 carbon atoms, The alkenyl having 2 to 8 carbon atoms or the alkenyl having 2 to 8 carbon atoms in which arbitrary hydrogen is replaced by fluorine. Particularly preferred R ⁷ and R ⁸ are those in which R ⁷ is alkenyl having 2 to 8 carbons, and R ⁸ is alkyl having 1 to 8 carbons, alkenyl having 2 to 8 carbons or any hydrogen is replaced by fluorine C2-C8 alkenyl.

  Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. More preferable alkyl is ethyl, propyl, butyl, pentyl, or heptyl from the viewpoint of small 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. Further preferred alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl from the viewpoint of small 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. Cis is preferable in alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl. In these alkenyl, linear alkenyl is preferable to branching.

  Preferred examples of alkenyl in which any hydrogen is replaced by fluorine include 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro-4- Pentenyl, or 6,6-difluoro-5-hexenyl. A more preferred example is 2,2-difluorovinyl for decreasing the viscosity.

  The configuration of 1,4-cyclohexylene in the compound is preferably trans rather than cis from the viewpoint of a high maximum temperature.

X ¹ is hydrogen or fluorine. X ⁵ is hydrogen or fluorine. Particularly preferred X ⁵ is hydrogen from the viewpoint of lowering the minimum temperature. X ² , X ³ and X ⁴ are independently hydrogen or fluorine. Preferred X ² , X ³ and X ⁴ of the compound (3-1) are fluorine, hydrogen and hydrogen, or hydrogen, hydrogen and fluorine or fluorine, fluorine and hydrogen in order from the viewpoint of lowering the minimum temperature and lowering the viscosity, etc. It is. Further preferred X ² , X ³ and X ⁴ are fluorine, hydrogen and hydrogen in this order.

Y ¹ is fluorine or chlorine. Particularly preferred Y ¹ is fluorine from the viewpoint of lowering the minimum temperature. Y ² is fluorine or trifluoromethoxy.

Fifth, specific examples of component compounds are shown. In the following preferred compounds, R ² and R ³ are independently alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons or alkenyl having 2 to 12 carbons in which any hydrogen is replaced by fluorine, R ⁹ is alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons, R ¹⁰ is alkyl having 1 to 12 carbons or alkoxy having 1 to 12 carbons, and R ¹¹ is alkyl having 1 to 12 carbons. Of alkyl. In these compounds, trans is preferable to cis for the configuration of 1,4-cyclohexylene from the viewpoint of a high maximum temperature.

In the chemical formulas of the component compounds, for example, the symbol R ² is used for a plurality of compounds. In these compounds, the meanings of R ² may be the same or different. For example, there is a case where R ^{2 of} the compound (2-2-1) is ethyl and R ² of the compound (3-1-1) is ethyl. In some cases, R ^{2 of the} compound (2-2-1) is ethyl and R ² of the compound (3-1-1) is propyl. This rule also applies to R ³ , R ⁹ , R ¹⁰ , R ^{11 and the} like.

  Desirable compounds (1) are the compounds (1-1) to (1-40). More desirable compounds (1) are the compounds (1-1), (1-5), the compound (1-20), and the compound (1-24) from the viewpoint of a lower minimum temperature and a small viscosity. Particularly preferred compound (1) is compound (1-5).

  Desirable compounds (2-1) are the compounds (2-1-1) to (2-1-4). More desirable compounds (2-1) are the compound (2-1-2) and the compound (2-1-3) from the viewpoint of a lower minimum temperature.

  Desirable compounds (2-2) are the compound (2-2-1) and the compound (2-2-2). More desirable compound (2-2) is compound (2-2-1).

  Desirable compounds (3-1) are the compounds (3-1-1) to (3-1-3). A more desirable compound (3-1) is the compound (3-1-1) from the viewpoints of a lower minimum temperature and a small viscosity. Desirable compounds (3-2) are the compound (3-2-1) and the compound (3-2-2). More desirable compound (3-2) is the compound (3-2-2) from the viewpoint of a lower minimum temperature. Desirable compounds (3-3) are the compounds (3-3-1) to (3-3-3). More desirable compounds (3-3) are the compound (3-3-1) and the compound (3-3-3) from the viewpoint of a lower minimum temperature.

  Desirable compounds (4) are from the compound (4-1) to the compound (4-8). More desirable compounds (4) are the compound (4-2), the compound (4-3) and the compound (4-8) from the viewpoints of a lower minimum temperature and a small viscosity. Particularly preferred compounds (4) are the compound (4-2) and the compound (4-3).

  Sixth, a method for synthesizing the component compounds will be described. These compounds can be synthesized by known methods. The synthesis method is illustrated. Compound (1-1), compound (1-5), compound (1-20) and compound (1-24) are synthesized by the method described in JP-A No. 61-27931. Compound (2-1-2) and compound (2-1-3) are synthesized by the method described in JP-A-10-251186. Compound (3-1-1) is synthesized by the method described in JP-A-60-51135. Compound (3-3-1) is synthesized by the method described in JP-A-57-165328. Compound (3-3-3) is synthesized by the method described in JP-A-57-114531. Compound (4-7) is synthesized by the method described in JP-A-61-27928. Compound (4-8) is synthesized by the method described in JP-A-1-308239.

  Compounds that have not been described as synthetic methods include Organic Syntheses (John Wiley & Sons, Inc), Organic Reactions (John Wiley & Sons, Inc), Comprehensive Organic Synthesis (Comprehensive Organic Synthesis) Synthesis, Pergamon Press) and new experimental chemistry course (Maruzen).

  Seventh, additives that may be mixed into the composition will be described. Such additives are optically active compounds, dyes, antioxidants, ultraviolet absorbers and the like. An optically active compound is mixed with the composition for the purpose of inducing a helical structure of liquid crystal to give a twist angle. Examples of such compounds are compound (5-1) to compound (5-4). A desirable ratio of the optically active compound is 5% or less. A more desirable ratio is in the range of 0.01% to 2%.

  A dichroic dye such as an azo dye or an anthraquinone dye is mixed with the composition in order to adapt to a GH (Guest host) mode element. A preferred proportion of the dye is in the range of 0.01% to 10%. 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 high temperature after using the device for a long time, an antioxidant is added to the composition. Mixed. A desirable ratio of the antioxidant is 50 ppm or more for achieving its effect, and is 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 100 ppm to 300 ppm.

  Preferable examples of the antioxidant include compound (6) where k is an integer of 1 to 9. In the compound (6), preferred k is 1, 3, 5, 7, or 9. Further preferred k is 1 or 7. Since the compound (6) in which k is 1 has high volatility, it is effective in preventing a decrease in specific resistance due to heating in the atmosphere. Since the compound (6) in which k is 7 has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a high temperature after the device has been used for a long time.

  Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. A desirable ratio of the ultraviolet absorber is 50 ppm or more for obtaining the effect thereof, and is 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 100 ppm to 1000 ppm.

  Finally, the use of the composition will be described. Most compositions have a minimum temperature of −20 ° C. or lower, a maximum temperature of 70 ° C. or higher, and an optical anisotropy of 0.10 to 0.17. 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 of 0.10 to 0.17 by controlling the ratio of component compounds or by mixing other liquid crystal compounds, and further an optical of 0.08 to 0.30 A composition having anisotropy 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 also be used for devices having modes such as PC, TN, STN, ECB, OCB, IPS, and VA. It is particularly preferable to use the device for a fast response element having a TN or OCB mode. 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. NCAP (nematic curvilinear aligned phase) elements produced by microencapsulating this composition, and PD (polymer dispersed) elements in which a three-dimensional network polymer is formed in the composition, for example, PN (polymer network) elements Can also be used.

The present invention will be described in detail by examples. The present invention is not limited by the following examples. The compounds in Comparative Examples and Examples were represented by symbols based on the definitions in Table 3 below.
In Table 3, the configuration regarding 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl is trans. The configuration regarding the bonding group of —CH═CH— is trans. In the examples, the number in parentheses after the symbol corresponds to the number of the preferred compound. The symbol (−) means other liquid crystal compounds. The ratio (percentage) of the liquid crystal composition is a weight percentage (% by weight) based on the total weight of the liquid crystal composition. The composition is prepared by measuring the weight of components such as a liquid crystal compound and then mixing them. Therefore, it is easy to calculate the weight percentage of the component.

  When the sample was a composition, it was measured as it was and the obtained value was described. When the sample was a compound, the sample was prepared by mixing 15% by weight compound and 85% by weight mother liquid crystals. The characteristic value of the compound was calculated by extrapolation from the value obtained by the measurement. 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 composition of the mother liquid crystals is as follows.

  The characteristic values were measured according to the following method. Many of them are the method described in the Standard of Electric Industries Association of Japan EIAJ ED-2521A or a modified method thereof. No TFT was attached to the TN device used for measurement.

  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”.

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

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

  Rotational viscosity (γ1; measured at 25 ° C .; mPa · s): Measurement was according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was put in a TN device having a twist angle of 0 ° and a distance (cell gap) between two glass substrates of 5 μm. The voltage was applied to the TN device in steps of 0.5V in the range of 16V to 19.5V. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. The value of rotational viscosity was obtained from these measured values and the paper by M. Imai et al., Formula (8) on page 40. The value of dielectric anisotropy necessary for this calculation was obtained by the following dielectric anisotropy measurement method using the element used for the measurement of the rotational viscosity.

  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⊥.

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

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

  Voltage holding ratio (VHR-1; 25 ° C .;%, VHR-2; 80 ° C .;%): The TN device used for the measurement has a polyimide alignment film, and the distance between two glass substrates (cell gap) is 5 μm. This element was sealed with an adhesive polymerized by ultraviolet rays after putting a sample. The TN device was charged by applying a pulse voltage (60 μs at 5 V). The decaying voltage was measured for 16.7 ms with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined. The area B is an area when it is not attenuated. The voltage holding ratio is a percentage of the area A with respect to the area B.

  Voltage holding ratio (VHR-3; 25 ° C .;%): After irradiation with ultraviolet rays, the voltage holding ratio (VHR-3; 25 ° C .;%) was measured to evaluate the stability against ultraviolet rays. A composition having a large VHR-3 has a large stability to ultraviolet light. The TN device used for measurement has a polyimide alignment film, and the cell gap is 5 μm. A sample was injected into this element and irradiated with light for 20 minutes. The light source is an ultra high pressure mercury lamp USH-500D (manufactured by USHIO), and the distance between the element and the light source is 20 cm. In the measurement of VHR-3, the decreasing voltage was measured for 1667 milliseconds.

  Response time (τ; measured at 25 ° C .; ms (millisecond)): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source is a halogen lamp. The low-pass filter was set to 5 kHz. A sample was placed in a normally white mode TN device in which the distance between two glass substrates (cell gap) was about 0.45 / Δn (μm) and the twist angle was 80 degrees. A rectangular wave (60 Hz, 5 V, 0.5 seconds) was applied to this element. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. The transmittance is 100% when the light amount is maximum, and the transmittance is 0% when the light amount is minimum. The rise time (τr: rise time) is the time required for the transmittance to change from 90% to 10%. The fall time (τf: fall time) is the time required to change the transmittance from 10% to 90%. The response time is the sum of the rise time and the fall time thus obtained.

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

[Comparative Example 1]
Example 4 was selected from the compositions disclosed in Patent Document 2 (Japanese Patent Laid-Open No. 10-114693). The reason is that this composition contains the compound (1-3). The components and properties of this composition are as follows. The composition was prepared and the physical property values were measured.
V2-BB-F (1-3) 20%
V-HHB (F) -F (-) 40%
V2-HHB (F) -F (-) 40%
NI = 74.8 ° C .; Tc ≦ 0 ° C .; Δn = 0.098; Δε = 3.4; γ1 = 70.5 mPa · s; VHR-1 = 99.1%; VHR-2 = 98.2%.

[Example 1]
1V2-BB-F (1-5) 8%
3-BB (F, F) XB (F, F) -F (2-1-2) 19%
2-BB (F) B-3 (3-1-1) 10%
2-BB (F) B-5 (3-1-1) 14%
3-BB (F) B-5 (3-1-1) 16%
V-HH-3 (4-2) 23%
1V-HH-3 (4-3) 6%
5-HBB (F) B-2 (-) 4%
NI = 74.9 ° C .; Tc ≦ −20 ° C .; Δn = 0.159; Δε = 3.8; γ1 = 60.8 mPa · s; Vth = 2.39 V; VHR-1 = 98.9%; VHR− 2 = 98.0%; τ = 25.7 msec.
The composition of Example 1 had substantially the same upper limit temperature, lower lower limit temperature, large dielectric anisotropy, large optical anisotropy and small rotational viscosity as compared to the composition of Comparative Example 1.

[Example 2]
1V2-BB-F (1-5) 13%
3-BB (F, F) XB (F, F) -F (2-1-2) 24%
2-BB (F) B-3 (3-1-1) 3%
2-HBB-F (3-2-2) 7%
3-HBB-F (3-2-2) 7%
5-HBB-F (3-2-2) 7%
3-HHB-1 (3-3-1) 8%
3-HHB-CL (3-3-3) 8%
5-HHB-CL (3-3-3) 7%
V-HH-3 (4-2) 12%
V-HH-5 (4-2) 4%
NI = 73.4 ° C .; Tc ≦ −20 ° C .; Δn = 0.124; Δε = 6.3; γ1 = 66.4 mPa · s; Vth = 1.71 V; VHR-1 = 99.0%; VHR− 2 = 98.0%
Τ = 21.8 ms.

[Example 3]
1V2-BB-CL (1-24) 8%
3-BB (F, F) XB (F, F) -F (2-1-2) 20%
2-BB (F) B-3 (3-1-1) 8%
2-BB (F) B-5 (3-1-1) 14%
3-BB (F) B-5 (3-1-1) 16%
V-HH-3 (4-2) 31%
5-HBB (F) B-2 (-) 3%
NI = 72.2 ° C .; Tc ≦ −20 ° C .; Δn = 0.157; Δε = 4.0; γ1 = 56.9 mPa · s; Vth = 2.25 V; VHR-1 = 98.7%; VHR− 2 = 98.1%; τ = 22.8 ms.

[Example 4]
V2-BB-CL (1-22) 13%
3-BB (F, F) XB (F, F) -F (2-1-2) 22%
2-BB (F) B-3 (3-1-1) 2%
2-HBB-F (3-2-2) 7%
3-HBB-F (3-2-2) 7%
5-HBB-F (3-2-2) 7%
3-HHB-1 (3-3-1) 8%
3-HHB-CL (3-3-3) 8%
5-HHB-CL (3-3-3) 7%
V-HH-3 (4-2) 12%
V-HH-5 (4-2) 7%
NI = 75.3 ° C .; Tc ≦ −10 ° C .; Δn = 0.124; Δε = 5.9; γ1 = 62.0 mPa · s; Vth = 1.73 V; VHR-1 = 98.5%; VHR− 2 = 97.9%; τ = 20.8 ms.

[Example 5]
V4-BB-F (1-10) 13%
3-BB (F, F) XB (F, F) -F (2-1-2) 21%
2-BB (F) B-3 (3-1-1) 7%
2-HBB-F (3-2-2) 7%
3-HBB-F (3-2-2) 7%
5-HBB-F (3-2-2) 7%
3-HHB-1 (3-3-1) 6%
3-HHB-3 (3-3-1) 3%
3-HHB-CL (3-3-3) 8%
5-HHB-CL (3-3-3) 7%
V-HH-3 (4-2) 9%
V-HH-5 (4-2) 5%
NI = 74.1 ° C .; Tc ≦ −20 ° C .; Δn = 0.124; Δε = 5.6; γ1 = 65.0 mPa · s; Vth = 1.89 V; VHR-1 = 98.2%; VHR− 2 = 97.9%; τ = 22.2 ms.

[Example 6]
V2V2-BB-F (1-19) 13%
3-BB (F, F) XB (F, F) -F (2-1-2) 21%
2-BB (F) B-3 (3-1-1) 7%
2-HBB-F (3-2-2) 7%
3-HBB-F (3-2-2) 7%
5-HBB-F (3-2-2) 7%
3-HHB-1 (3-3-1) 8%
3-HHB-CL (3-3-3) 8%
5-HHB-CL (3-3-3) 7%
V-HH-3 (4-2) 12%
V-HH-5 (4-2) 3%
NI = 74.7 ° C .; Tc ≦ −20 ° C .; Δn = 0.125; Δε = 5.6; γ1 = 66.7 mPa · s; Vth = 1.77 V; VHR-1 = 98.2%; VHR− 2 = 97.9%; τ = 22.7 ms.

[Example 7]
V2-BB-F (1-3) 5%
1V2-BB-F (1-5) 8%
3-BB (F, F) XB (F, F) -F (2-1-2) 10%
3-BB (F, F) XB (F, F) -OCF3 (2-1-4) 12%
2-BB (F) B-3 (3-1-1) 10%
2-BB (F) B-5 (3-1-1) 10%
V-HHB-1 (3-3-1) 10%
V2-HHB-1 (3-3-1) 8%
V-HH-3 (4-2) 15%
V-HH-4 (4-2) 8%
5-HBB (F) B-2 (-) 4%
NI = 73.8 ° C .; Tc ≦ −20 ° C .; Δn = 0.139; Δε = 4.7; γ1 = 59.6 mPa · s; Vth = 2.16 V; VHR-1 = 98.3%; VHR− 2 = 97.9%; τ = 23.4 ms.

[Example 8]
V2-BB-F (1-3) 5%
1V2-BB-F (1-5) 12%
3-BB (F, F) XB (F) -OCF3 (2-1-3) 18%
3-BB (F) B (F, F) -F (2-2-1) 10%
2-BB (F) B-3 (3-1-1) 5%
2-BBB (2F) -3 (3-1-2) 5%
2-BBB (2F) -5 (3-1-2) 5%
2-BB (2F, 5F) B-2 (3-1-3) 5%
3-HHB-1 (3-3-1) 3%
3-HHB-O1 (3-3-1) 3%
V-HHB-1 (3-3-1) 5%
VFF-HHB-1 (3-3-1) 8%
3-HHB-F (3-3-2) 5%
V-HH-3 (4-2) 6%
VFF-HH-3 (4-8) 5%
NI = 70.1 ° C .; Tc ≦ −20 ° C .; Δn = 0.152; Δε = 5.2; γ1 = 77.5 mPa · s; Vth = 2.01 V; VHR-1 = 98.0%; VHR− 2 = 97.5%; τ = 27.1 ms.

[Example 9]
V2-BB-F (1-3) 3%
1V2-BB-F (1-5) 7%
V4-BB-F (1-10) 3%
1V2-BB-CL (1-24) 5%
VFF2-BB-F (1-39) 4%
3-BB (F, F) XB (F, F) -F (2-1-2) 10%
3-BB (F, F) XB (F) -F (2-1-1) 5%
3-BB (F, F) XB (F) -OCF3 (2-1-3) 6%
3-HBB-2 (3-2-1) 5%
V2-HBB-2 (3-2-1) 4%
1V2-HBB-2 (3-2-1) 4%
2-HBB-F (3-2-2) 5%
3-HBB-F (3-2-2) 5%
5-HBB-F (3-2-2) 5%
V-HHB-1 (3-3-1) 12%
V2-HHB-1 (3-3-1) 5%
V-HH-3 (4-2) 6%
VFF-HH-3 (4-8) 6%
NI = 71.2 ° C .; Tc ≦ −20 ° C .; Δn = 0.136; Δε = 4.7; γ1 = 55.7 mPa · s; Vth = 2.13 V; VHR-1 = 98.0%; VHR− 2 = 97.7%; τ = 20.7 ms.

[Example 10]
V2-BB-F (1-3) 5%
1V2-BB-F (1-5) 10%
3-BB (F, F) XB (F, F) -F (2-1-2) 10%
3-BB (F) B (F, F) -F (2-2-1) 12%
3-HBB-2 (3-2-1) 5%
5-HBB-2 (3-2-1) 3%
V2-HBB-2 (3-2-1) 5%
2-HBB-F (3-2-2) 7%
3-HBB-F (3-2-2) 7%
5-HBB-F (3-2-2) 7%
V-HH-3 (4-2) 10%
V-HH-4 (4-2) 5%
V-HH-5 (4-2) 5%
1V-HH-3 (4-3) 5%
5-HBB (F) B-2 (-) 4%
NI = 72.7 ° C .; Tc ≦ −20 ° C .; Δn = 0.135; Δε = 4.0; γ1 = 52.4 mPa · s; Vth = 2.32 V; VHR-1 = 98.3%; VHR− 2 = 97.9%; τ = 21.1 ms.

[Example 11]
1V2-BB-F (1-5) 10%
1V2-BB-CL (1-24) 7%
3-BB (F, F) XB (F, F) -F (2-1-2) 10%
3-BB (F, F) XB (F, F) -OCF3 (2-1-4) 5%
3-BB (F, F) XB (F) -OCF3 (2-1-3) 10%
3-HHB-1 (3-3-1) 5%
3-HHB-3 (3-3-1) 5%
3-HHB-O1 (3-3-1) 5%
V-HHB-1 (3-3-1) 7%
V2-HHB-1 (3-3-1) 5%
VFF-HHB-1 (3-3-1) 5%
3-HHB-CL (3-3-3) 5%
5-HHB-CL (3-3-3) 5%
V-HH-3 (4-2) 16%
NI = 82.1 ° C .; Tc ≦ −20 ° C .; Δn = 0.125; Δε = 5.1; γ1 = 65.9 mPa · s; Vth = 2.12 V; VHR-1 = 98.2%; VHR− 2 = 97.7%; τ = 23.7 ms.

[Example 12]
1V2-BB-F (1-5) 4%
V4-BB-F (1-10) 4%
V2V2-BB-F (1-19) 3%
3-BB (F, F) XB (F, F) -F (2-1-2) 4%
3-BB (F, F) XB (F, F) -OCF3 (2-1-4) 7%
3-BB (F) B (F, F) -F (2-2-1) 6%
5-BB (F) B (F, F) -F (2-2-1) 6%
2-BB (F) B-3 (3-1-1) 5%
2-BB (F) B-5 (3-1-1) 5%
2-BBB (2F) -3 (3-1-2) 5%
2-BB (2F, 5F) B-2 (3-1-3) 4%
3-BB (2F, 5F) B-3 (3-1-3) 4%
1V2-HBB-2 (3-2-1) 10%
3-HBB-2 (3-2-1) 5%
2-HBB-F (3-2-2) 4%
3-HBB-F (3-2-2) 4%
5-HBB-F (3-2-2) 4%
V-HH-3 (4-2) 16%
NI = 74.8 ° C .; Tc ≦ −20 ° C .; Δn = 0.162; Δε = 4.7; γ1 = 93.7 mPa · s; Vth = 2.16 V; VHR-1 = 98.3%; VHR− 2 = 97.8%; τ = 35.0 ms.

[Example 13]
1V2-BB-F (1-5) 7%
3-BB (F, F) XB (F, F) -F (2-1-2) 10%
3-BB (F, F) XB (F, F) -OCF3 (2-1-4) 10%
2-BB (F) B-3 (3-1-1) 5%
1V2-BB (F) B-2 (3-1-1) 5%
1V2-HBB-2 (3-2-1) 10%
V-HHB-1 (3-3-1) 10%
V-HH-3 (4-2) 10%
1V-HH-3 (4-3) 10%
7-HB-1 (-) 5%
3-HB-CL (-) 10%
5-HBB (F) B-2 (-) 4%
5-HBB (F) B-3 (-) 4%
NI = 77.8 ° C .; Tc ≦ −20 ° C .; Δn = 0.137; Δε = 4.2; γ1 = 68.1 mPa · s; Vth = 2.30 V; VHR-1 = 98.2%; VHR− 2 = 97.9%; τ = 26.8 ms.

[Example 14]
1V2-BB-F (1-5) 5%
1V2-BB-CL (1-24) 4%
V2V2-BB-CL (1-38) 4%
3-BB (F, F) XB (F, F) -F (2-1-2) 20%
2-HBB-F (3-2-2) 6%
3-HBB-F (3-2-2) 5%
5-HBB-F (3-2-2) 5%
3-HHB-CL (3-3-3) 5%
5-HHB-CL (3-3-3) 5%
V-HH-3 (4-2) 20%
3-HHB (F) -F (-) 3%
3-HBB (F) -F (-) 3%
3-H2BB (F) -F (-) 3%
3-HHB (F, F) -F (-) 3%
5-HB (F) BH-3 (-) 3%
1O1-HBBH-3 (-) 3%
1O1-HBBH-4 (-) 3%
NI = 81.5 ° C .; Tc ≦ −20 ° C .; Δn = 0.129; Δε = 5.1; γ1 = 83.6 mPa · s; Vth = 2.12 V; VHR-1 = 98.1%; VHR− 2 = 97.9%; τ = 30.0 ms.

[Example 15]
V2-BB-F (1-3) 6%
1V2-BB-F (1-5) 6%
3-BB (F, F) XB (F, F) -F (2-1-2) 14%
3-BB (F, F) XB (F, F) -OCF3 (2-1-4) 10%
V-HHB-1 (3-3-1) 16%
V2-HHB-1 (3-3-1) 10%
3-HHB-CL (3-3-3) 7%
5-HHB-CL (3-3-3) 2%
V-HH-3 (4-2) 23%
V-HH-5 (4-2) 6%
NI = 72.4 ° C .; Tc ≦ −20 ° C .; Δn = 0.107; Δε = 4.4; γ1 = 44.3 mPa · s; Vth = 2.21 V; VHR-1 = 98.3%; VHR− 2 = 97.9%; τ = 17.0 ms.

[Example 16]
V2-BB-F (1-3) 11%
1V2-BB-F (1-5) 10%
3-BB (F, F) XB (F) -OCF3 (2-1-3) 10%
3-BB (F) B (F, F) -F (2-2-1) 10%
2-BB (F) B-3 (3-1-1) 4%
3-HBB-2 (3-2-1) 4%
1V2-HBB-2 (3-2-1) 5%
2-HBB-F (3-2-2) 7%
3-HBB-F (3-2-2) 7%
5-HBB-F (3-2-2) 7%
V-HHB-1 (3-3-1) 10%
VFF-HHB-1 (3-3-1) 5%
3-HHB-CL (3-3-3) 5%
5-HHB-CL (3-3-3) 5%
NI = 84.6 ° C .; Tc ≦ −20 ° C .; Δn = 0.154; Δε = 4.4; γ1 = 87.6 mPa · s; Vth = 2.32 V; VHR-1 = 98.2%; VHR− 2 = 97.5%; τ = 34.0 ms.

[Example 17]
V2-BB-CL (1-22) 5%
1V2-BB-CL (1-24) 2%
VFF2-BB-CL (1-40) 3%
3-BB (F, F) XB (F, F) -F (2-1-2) 10%
3-BB (F, F) XB (F) -OCF3 (2-1-3) 10%
2-BB (2F, 5F) B-2 (3-1-3) 5%
3-BB (2F, 5F) B-3 (3-1-3) 5%
V2-HBB-2 (3-2-1) 10%
3-HHB-1 (3-3-1) 5%
3-HHB-3 (3-3-1) 5%
V-HHB-1 (3-3-1) 10%
3-HHB-CL (3-3-3) 6%
5-HHB-CL (3-3-3) 6%
3-HB-CL (-) 8%
3-HB-O2 (-) 10%
NI = 81.5 ° C .; Tc ≦ −10 ° C .; Δn = 0.145; Δε = 4.5; γ1 = 86.4 mPa · s; Vth = 2.27 V; VHR-1 = 98.4%; VHR− 2 = 97.6%; τ = 33.2 ms.

[Example 18]
1V2-BB-F (1-5) 12%
3-BB (F, F) XB (F, F) -F (2-1-2) 15%
2-BB (F) B-3 (3-1-1) 10%
2-HBB-F (3-2-2) 6%
3-HBB-F (3-2-2) 6%
5-HBB-F (3-2-2) 6%
2-HH-3 (4-1) 5%
3-HH-4 (4-1) 16%
3-HHXB (F, F) -F (-) 10%
3-HHB (F) -F (-) 14%
NI = 70.6 ° C .; Tc ≦ −20 ° C .; Δn = 0.121; Δε = 5.2; γ1 = 68.1 mPa · s; Vth = 2.02 V; VHR-1 = 98.2%; VHR− 2 = 97.6%; τ = 24.2 ms.

[Example 19]
V2-BB-F (1-3) 3%
1V2-BB-F (1-5) 8%
3-BB (F, F) XB (F, F) -F (2-1-2) 2%
3-BB (F) B (F, F) -F (2-2-1) 18%
2-BB (F) B-3 (3-1-1) 10%
V2-HBB-2 (3-2-1) 5%
2-HBB-F (3-2-2) 5%
3-HBB-F (3-2-2) 5%
5-HBB-F (3-2-2) 5%
V-HH-3 (4-2) 10%
V-HH-5 (4-2) 10%
3-HH-O1 (-) 10%
3-HHEB (F, F) -F (-) 5%
5-HBB (F) B-2 (-) 4%
NI = 71.6 ° C .; Tc ≦ −20 ° C .; Δn = 0.139; Δε = 3.8; γ1 = 91.1 mPa · s; Vth = 2.51 V; VHR-1 = 98.4%; VHR− 2 = 97.7%; τ = 29.9 ms.

[Example 20]
1V2-BB-F (1-5) 8%
1V2-BB-CL (1-24) 5%
3-BB (F, F) XB (F, F) -F (2-1-2) 10%
3-BB (F, F) XB (F, F) -OCF3 (2-1-4) 10%
2-BB (F) B-3 (3-1-1) 10%
3-HBB-2 (3-2-1) 3%
2-HBB-F (3-2-2) 4%
3-HBB-F (3-2-2) 4%
5-HBB-F (3-2-2) 3%
V-HHB-1 (3-3-1) 10%
V2-HHB-1 (3-3-1) 5%
3-HHB-CL (3-3-3) 3%
VFF-HH-3 (4-8) 12%
VFF-HH-5 (4-8) 5%
3-HGB (F, F) -F (-) 4%
3-GHB (F, F) -F (-) 4%
NI = 73.0 ° C .; Tc ≦ −20 ° C .; Δn = 0.136; Δε = 6.6; γ1 = 83.6 mPa · s; Vth = 1.81 V; VHR-1 = 98.0%; VHR− 2 = 97.8%; τ = 26.9 ms.

[Example 21]
V2-BB-F (1-3) 3%
1V2-BB-F (1-5) 12%
3-BB (F, F) XB (F, F) -F (2-1-2) 15%
3-B (F) B (F) B (F, F) -F (2-2-2) 10%
2-BB (F) B-3 (3-1-1) 4%
2-BB (F) B-5 (3-1-1) 4%
1V2-HBB-2 (3-2-1) 5%
2-HBB-F (3-2-2) 4%
3-HBB-F (3-2-2) 4%
5-HBB-F (3-2-2) 4%
V-HHB-1 (3-3-1) 5%
V-HH-3 (4-2) 22%
5-HBB (F) B-2 (-) 5%
5-HBB (F) B-3 (-) 3%
NI = 70.6 ° C .; Tc ≦ −20 ° C .; Δn = 0.147; Δε = 5.6; γ1 = 67.0 mPa · s; Vth = 1.93 V; VHR-1 = 98.0%; VHR− 2 = 97.8%; τ = 22.0 ms.

[Example 22]
1V2-BB-F (1-5) 12%
3-BB (F) B (F, F) -F (2-2-1) 10%
3-B (F) B (F) B (F, F) -F (2-2-2) 10%
2-BB (F) B-3 (3-1-1) 4%
2-BB (F) B-5 (3-1-1) 4%
2-HBB-F (3-2-2) 5%
3-HBB-F (3-2-2) 5%
5-HBB-F (3-2-2) 5%
3-HHB-F (3-3-2) 4%
3-HHB-CL (3-3-3) 5%
5-HHB-CL (3-3-3) 5%
V-HH-3 (4-2) 20%
V-HH-5 (4-2) 11%
NI = 72.9 ° C .; Tc ≦ −20 ° C .; Δn = 0.136; Δε = 3.9; γ1 = 44.8 mPa · s; Vth = 2.20 V; VHR-1 = 98.0%; VHR− 2 = 97.8%; τ = 19.2 ms.

Claims (11)

At least one compound selected from the group of compounds represented by formula (1) as the first component, and selected from the group of compounds represented by formula (2-1) and formula (2-2) as the second component And at least one compound selected from the group of compounds represented by formula (3-1), formula (3-2) and formula (3-3) as a third component The liquid crystal composition in which the third component contains at least one compound selected from the group of compounds represented by formula (3-1) and has a nematic phase.

Here, R ¹ is alkenyl having 2 to 12 carbon atoms, alkadienyl having 4 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms in which arbitrary hydrogen is replaced by fluorine; R ² , R ³ and R ⁵ are Independently alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons or alkenyl having 2 to 12 carbons in which arbitrary hydrogen is replaced by fluorine; R ⁴ is fluorine, alkyl having 1 to 12 carbons Or R ⁶ is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons; Y ¹ is fluorine or chlorine by and; ^{Y 2} is fluorine or trifluoromethoxy; ^{X 1} and ^{X 5} is hydrogen or fluorine ^{independently; X} 2, X ³ and ^{X 4} are independently hydrogen or A ^{Tsu-containing,} among X 2, ^{X 3} and ^{X 4,} at least one is fluorine.   The second component is at least one compound selected from the group of compounds represented by formula (2-1), and the third component is at least selected from the group of compounds represented by formula (3-1) The liquid crystal composition according to claim 1, which is a single compound.   Based on the total weight of the liquid crystal composition, the proportion of the first component is in the range of 5 wt% to 20 wt%, the proportion of the second component is in the range of 10 wt% to 35 wt%, and the third component The liquid crystal composition according to claim 1 or 2, wherein the ratio of is in the range of 10 wt% to 55 wt%. At least one compound selected from the group of compounds represented by formula (1) as the first component, and selected from the group of compounds represented by formula (2-1) and formula (2-2) as the second component At least one compound selected from the group of compounds represented by formula (3-1), formula (3-2) and formula (3-3) as a third component, and fourth Containing at least one compound selected from the group of compounds represented by formula (4) as a component , and wherein the third component is at least selected from the group of compounds represented by formula (3-1) A liquid crystal composition containing one compound and having a nematic phase.

Here, R ¹ is alkenyl having 2 to 12 carbon atoms, alkadienyl having 4 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms in which arbitrary hydrogen is replaced by fluorine; R ² , R ³ and R ⁵ are Independently alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons or alkenyl having 2 to 12 carbons in which arbitrary hydrogen is replaced by fluorine; R ⁴ is fluorine, alkyl having 1 to 12 carbons Or R 2 is alkenyl having 2 to 12 carbons; R ⁶ is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons; R ⁷ and R ⁸ are Independently alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons or alkenyl having 2 to 12 carbons in which arbitrary hydrogen is replaced by fluorine; Y ¹ represents fluorine or Y ² is fluorine or trifluoromethoxy; X ¹ and X ⁵ are independently hydrogen or fluorine; X ² , X ³ and X ⁴ are independently hydrogen or fluorine, X ² , X ³ and X ⁴ are at least one fluorine.   The liquid crystal composition according to claim 4, wherein the second component is at least one compound selected from the group of compounds represented by formula (2-1). The fourth component is at least one compound selected from the group of compounds represented by formula (4), R ⁷ is alkenyl having 2 to 12 carbons, and R ⁸ is alkyl having 1 to 12 carbons. The liquid crystal composition according to claim 4 or 5, wherein The third component is at least one compound selected from the group of compounds represented by formula (3-1), X ² is fluorine, and X ³ and X ⁴ are hydrogen. The liquid crystal composition described in 1. The liquid crystal composition according to claim 1, wherein Y ¹ in formula (1) is fluorine.   Based on the total weight of the liquid crystal composition, the proportion of the first component is in the range of 5 wt% to 20 wt%, the proportion of the second component is in the range of 10 wt% to 35 wt%, The liquid crystal composition according to any one of claims 4 to 8, wherein the ratio is in the range of 10% to 55% by weight, and the ratio of the fourth component is in the range of 10% to 40% by weight.   The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy at a wavelength of 589 nm at 25 ° C. is in the range of 0.11 to 0.17, and the rotational viscosity coefficient at 25 ° C. is from 30 mPa · s to 100 mPa · s. The liquid crystal composition according to claim 1, which is in the range of s.   The liquid crystal display element containing the liquid-crystal composition of any one of Claim 1 to 10.