JP2020084021A - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

To provide a liquid crystal composition satisfying at least one of demands for characteristics such as a high maximum temperature, low minimum temperature, small viscosity, suitable optical anisotropy, positively large dielectric anisotropy, large resistivity, high stability against ultraviolet rays, high stability against heat, and large elastic constant, or having a suitable balance in at least two of the characteristics, and an AM element comprising the above composition.SOLUTION: The liquid crystal composition contains a specific liquid crystal compound having large optical anisotropy and a low minimum temperature as a first component, and may contain a specific liquid crystal compound having a high maximum temperature or a small viscosity as a second component, a specific liquid crystal compound having positive dielectric anisotropy as a third component, and a specific liquid crystal compound having negative dielectric anisotropy as a fourth component.SELECTED DRAWING: None

Description

The present invention relates to a liquid crystal composition, a liquid crystal display device containing this composition, and the like. In particular, the present invention relates to a liquid crystal composition having a positive dielectric anisotropy, and an AM (active matrix) device containing this composition and having a mode of TN, ECB, OCB, IPS, FFS, or FPA.

In a liquid crystal display device, classification based on the operation mode of liquid crystal molecules is performed by PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS. The modes include (in-plane switching), VA (vertical alignment), FFS (fringe field switching), and FPA (field-induced photo-reactive alignment). The classification based on the driving method of the element is PM (passive matrix) and AM (active matrix). PM is classified into static and multiplex, and AM is classified into TFT (thin film transistor) and MIM (metal insulator metal). TFTs are classified into amorphous silicon and polycrystal silicon. The latter is classified into a high temperature type and a low temperature type according to the manufacturing process. The light source-based classification is a reflective type that uses natural light, a transmissive type that uses a backlight, and a semi-transmissive type that uses both natural light and a backlight.

The liquid crystal display device contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the properties of this composition, an AM device having good properties can be obtained. The relationships in these properties are 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. The preferred maximum temperature of the nematic phase is about 70°C or higher, and the preferred minimum temperature of the nematic phase is about -10°C or lower. The viscosity of the composition is related to the response time of the device. A short response time is preferable for displaying a moving image on the device. Response times as short as 1 millisecond are desirable. Therefore, a low viscosity in the composition is preferred. Small viscosities at low temperatures are even more preferred. The elastic constant of the composition is related to the contrast of the device. In order to increase the contrast in the device, a large elastic constant in the composition is preferable.

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, that is, a suitable 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 value of the product depends on the type of operating mode. For a TN-like mode device, 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. Therefore, large dielectric anisotropy is preferable. The 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 in the initial stage is preferable. A composition having a large specific resistance after being used for a long time is preferable. The stability of the composition against ultraviolet rays and heat is related to the life of the liquid crystal display device. When their stability is high, the lifetime of this device is long. Such characteristics are preferable for AM devices used for liquid crystal monitors, liquid crystal televisions, and the like.

A composition having a positive dielectric anisotropy is used in an AM device having a TN mode. A composition having a negative dielectric anisotropy is used in an AM device having a VA mode. A composition having a positive or negative dielectric anisotropy is used in an AM device having an IPS mode or an FFS mode. In a polymer sustained alignment (PSA) type AM device, a composition having a positive or negative dielectric anisotropy is used.

International Publication No. 2004/106460

The subject of the present invention is a high maximum temperature of a nematic phase, a low minimum temperature of a nematic phase, a small viscosity, a suitable optical anisotropy, a positively large dielectric anisotropy, a large specific resistance, a high stability against ultraviolet rays, a heat It is to provide a liquid crystal composition satisfying at least one of properties such as high stability and high elastic constant. Another object is to provide a liquid crystal composition having a suitable balance between at least two of these properties. Another object is to provide a liquid crystal display device containing such a composition. Another problem is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long life.

式（１）において、Ｒ^１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、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炭素数２から１２のアルケニルであり；Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５、およびＸ^６は、水素またはフッ素であり；Ｙ^１は、フッ素、塩素、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炭素数１から１２のアルキル、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つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルオキシであり；Ｚ^１、Ｚ^２、およびＺ^３は、単結合、エチレン、ビニレン、メチレンオキシ、またはカルボニルオキシであり、Ｚ^１、Ｚ^２、およびＺ^３の少なくとも１つはエチレンである。 The present invention contains, as a first component, at least one compound selected from compounds represented by formula (1), and a liquid crystal composition having a positive dielectric anisotropy, and this composition. A liquid crystal display device.

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 2 carbons in which at least one hydrogen is replaced by fluorine or chlorine. To 12 alkenyl; X ¹ , X ² , X ³ , X ⁴ , X ⁵ , and X ⁶ are hydrogen or fluorine; Y ¹ is fluorine, chlorine, at least one hydrogen is fluorine or chlorine. A substituted alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or an alkyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine Alkenyloxy; Z ¹ , Z ² , and Z ³ are single bonds, ethylene, vinylene, methyleneoxy, or carbonyloxy, and at least one of Z ¹ , Z ² , and Z ³ is ethylene.

The advantages of the present invention include a high maximum temperature of a nematic phase, a low minimum temperature of a nematic phase, a small viscosity, a suitable optical anisotropy, a large positive dielectric anisotropy, a large specific resistance, a high stability against ultraviolet rays, and a high thermal stability. It is to provide a liquid crystal composition satisfying at least one of properties such as high stability and high elastic constant. Another advantage is to provide a liquid crystal composition having a suitable balance between at least two of these properties. Another advantage is to provide a liquid crystal display device containing such a composition. Another advantage is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long life.

The usage of terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display device" may be abbreviated as "composition" and "device", respectively. “Liquid crystal display element” is a general term for liquid crystal display panels and liquid crystal display modules. The “liquid crystalline compound” is a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and does not have a liquid crystal phase, but for the purpose of adjusting properties such as temperature range, viscosity and dielectric anisotropy of the nematic phase. It is a general term for the compounds mixed in the composition. This compound has a 6-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecule (liquid crystal molecule) is rod-like. The “polymerizable compound” is a compound added for the purpose of forming a polymer in the composition. Liquid crystal compounds having alkenyl are not classified as polymerizable compounds in that sense.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as an optically active compound and a polymerizable compound are added to the liquid crystal composition as needed. The proportion of the liquid crystal compound is represented by a mass percentage (mass %) based on the mass of the liquid crystal composition containing no additive even when the additive is added. The ratio of the additive is represented by a mass percentage (mass %) based on the mass of the liquid crystal composition containing no additive. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total mass of the liquid crystal compound. The ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the mass of the polymerizable compound.

The "maximum temperature of the nematic phase" may be abbreviated as "maximum temperature". The "minimum temperature of the nematic phase" may be abbreviated as "minimum temperature". The expression “increasing the dielectric anisotropy” means that, in the case of a composition having a positive dielectric anisotropy, that value increases positively, and a composition having a negative dielectric anisotropy. When it is a thing, it means that its value increases negatively. “High voltage retention” means that the device has a large voltage retention not only at room temperature but also at a temperature close to the upper limit temperature at the initial stage, and after a long time use, it has a large voltage not only at room temperature but also at a temperature close to the upper limit temperature. Means to have a retention rate. The properties of the compositions and devices may be examined by aging tests.

上記の化合物（１ｚ）を例にして説明する。式（１ｚ）において、六角形で囲んだαおよびβの記号はそれぞれ環αおよび環βに対応し、六員環、縮合環のような環を表す。添え字‘ｘ’が２のとき、２つの環αが存在する。２つの環αが表す２つの基は、同一であってもよく、または異なってもよい。このルールは、添え字‘ｘ’が２より大きいとき、任意の２つの環αに適用される。このルールは、結合基Ｚのような、他の記号にも適用される。環βの一辺を横切る斜線は、環β上の任意の水素が置換基（−Ｓｐ−Ｐ）で置き換えられてもよいことを表す。添え字‘ｙ’は置き換えられた置換基の数を示す。添え字‘ｙ’が０のとき、そのような置き換えはない。添え字‘ｙ’が２以上のとき、環β上には複数の置換基（−Ｓｐ−Ｐ）が存在する。この場合にも、「同一であってもよく、または異なってもよい」のルールが適用される。なお、このルールは、Ｒａの記号を複数の化合物に用いた場合にも適用される。

The above compound (1z) will be described as an example. In formula (1z), symbols α and β surrounded by hexagons correspond to ring α and ring β, respectively, and represent rings such as a 6-membered ring and a condensed ring. When the subscript'x' is 2, there are two rings α. The two groups represented by the two rings α may be the same or different. This rule applies to any two rings α when the subscript'x' is greater than 2. This rule also applies to other symbols, such as the linking group Z. A diagonal line that crosses one side of the ring β indicates that any hydrogen on the ring β may be replaced with a substituent (—Sp-P). The subscript'y' indicates the number of substituents replaced. When the subscript'y' is 0, there is no such replacement. When the subscript'y' is 2 or more, a plurality of substituents (-Sp-P) are present on the ring β. In this case as well, the rule of "may be the same or different" applies. Note that this rule is also applied when the Ra symbol is used for a plurality of compounds.

In formula (1z), for example, an expression such as "Ra and Rb are alkyl, alkoxy, or alkenyl" means that Ra and Rb are independently selected from the group of alkyl, alkoxy, and alkenyl. Means Here, the group represented by Ra and the group represented by Rb may be the same or different.

At least one compound selected from the compounds represented by formula (1z) may be abbreviated as “compound (1z)”. “Compound (1z)” means one compound represented by formula (1z), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas. The expression "at least one compound selected from the compounds represented by formula (1z) and formula (2z)" means at least one compound selected from the group consisting of compound (1z) and compound (2z). ..

The expression "at least one'A'" means that the number of'A's is arbitrary. The expression "at least one'A' may be replaced by'B'" means that when the number of'A' is one, the position of'A' is arbitrary and the number of'A' is two. If there are more than one, those positions can be selected without restriction. The phrase “at least one —CH ₂ — may be replaced with —O—” is sometimes used. In this _case, -CH ₂ -CH ₂ -CH ₂ - it is, -CH ₂ nonadjacent - may be converted _-O-CH 2 -O- to by is replaced by -O-. However, adjacent -CH ₂ - is not replaced by -O-. This is because this replacement produces —O—O—CH ₂ — (peroxide).

テトラヒドロピラン−２，５−ジイルのような二価基においても同様である。カルボニルオキシのような結合基（−ＣＯＯ−または−ＯＣＯ−）も同様である。 The alkyl of the liquid crystal compound is linear or branched and does not include cyclic alkyl. Straight-chain alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. Regarding the configuration of 1,4-cyclohexylene, trans is preferable to cis for increasing the maximum temperature. Since 2-fluoro-1,4-phenylene is asymmetrical to the left and right, there are leftward (L) and rightward (R) directions.

The same applies to divalent groups such as tetrahydropyran-2,5-diyl. The same applies to a linking group (-COO- or -OCO-) such as carbonyloxy.

The present invention includes the following items.

式（１）において、Ｒ^１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、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炭素数２から１２のアルケニルであり；Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５、およびＸ^６は、水素またはフッ素であり；Ｙ^１は、フッ素、塩素、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炭素数１から１２のアルキル、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つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルオキシであり；Ｚ^１、Ｚ^２、およびＺ^３は、単結合、エチレン、ビニレン、メチレンオキシ、またはカルボニルオキシであり、Ｚ^１、Ｚ^２、およびＺ^３の少なくとも１つはエチレンである。 Item 1. A liquid crystal composition containing as a first component at least one compound selected from the compounds represented by formula (1).

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 2 carbons in which at least one hydrogen is replaced by fluorine or chlorine. To 12 alkenyl; X ¹ , X ² , X ³ , X ⁴ , X ⁵ , and X ⁶ are hydrogen or fluorine; Y ¹ is fluorine, chlorine, at least one hydrogen is fluorine or chlorine. A substituted alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or an alkyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine Alkenyloxy; Z ¹ , Z ² , and Z ³ are single bonds, ethylene, vinylene, methyleneoxy, or carbonyloxy, and at least one of Z ¹ , Z ² , and Z ³ is ethylene.

式（１−１）から式（１−３）において、Ｒ^１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、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炭素数２から１２のアルケニルであり；Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５、およびＸ^６は、水素またはフッ素であり；Ｙ^１は、フッ素、塩素、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炭素数１から１２のアルキル、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つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルオキシである。 Item 2. Item 2. The liquid crystal composition according to item 1, containing at least one compound selected from compounds represented by formulas (1-1) to (1-3) as a first component.

In formulas (1-1) to (1-3), R ¹ represents alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen being fluorine. Or alkenyl having 2 to 12 carbon atoms substituted with chlorine; X ¹ , X ² , X ³ , X ⁴ , X ⁵ , and X ⁶ are hydrogen or fluorine; Y ¹ is fluorine, chlorine, Alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen being fluorine or chlorine. It is a substituted alkenyloxy having 2 to 12 carbons.

Item 3. Item 3. The liquid crystal composition according to item 1 or 2, wherein the ratio of the first component is in the range of 5% by mass to 50% by mass.

式（２）において、Ｒ^２およびＲ^３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、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炭素数２から１２のアルケニルであり；環Ａおよび環Ｂは、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、または２，５−ジフルオロ−１，４−フェニレンであり；Ｚ^４は、単結合、エチレン、ビニレン、メチレンオキシ、またはカルボニルオキシであり；ａは、１、２、または３である。 Item 4. Item 4. The liquid crystal composition according to any one of items 1 to 3, containing at least one compound selected from the compounds represented by formula (2) as the second component.

In formula (2), R ² and R ³ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen is replaced with fluorine or chlorine. C2-C12 alkenyl; Ring A and Ring B are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4. - be a phenylene; ^{Z 4} is a single bond, ethylene, vinylene, methyleneoxy or carbonyloxy,; a is 1, 2 or 3.

式（２−１）から式（２−１３）において、Ｒ^２およびＲ^３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、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炭素数２から１２のアルケニルである。 Item 5. Item 5. The liquid crystal composition according to any one of items 1 to 4, containing at least one compound selected from compounds represented by formulas (2-1) to (2-13) as a second component.

In formulas (2-1) to (2-13), R ² and R ³ are each alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one. It is alkenyl having 2 to 12 carbons in which hydrogen is replaced by fluorine or chlorine.

Item 6. Item 6. The liquid crystal composition according to item 4 or 5, wherein the ratio of the second component is in the range of 10% by mass to 80% by mass.

式（３）において、Ｒ^４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、または炭素数２から１２のアルケニルであり；環Ｃは、１，４−シクロヘキシレン、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、ピリミジン−２，５−ジイル、または１，３−ジオキサン−２，５−ジイルであり；Ｚ^５は、単結合、エチレン、ビニレン、メチレンオキシ、カルボニルオキシ、またはジフルオロメチレンオキシであり；Ｘ^７およびＸ^８は、水素またはフッ素であり；Ｙ^２は、フッ素、塩素、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炭素数１から１２のアルキル、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つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルオキシであり；ｂは、１、２、３、または４である。 Item 7. Item 7. The liquid crystal composition according to any one of items 1 to 6, containing at least one compound selected from the compounds represented by formula (3) as the third component.

In formula (3), R ⁴ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons; ring C is 1,4-cyclohexylene, 1, 4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, pyrimidine-2,5-diyl, or 1,3-dioxane-2,5-diyl; Z ⁵ is a single A bond, ethylene, vinylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy; X ⁷ and X ⁸ are hydrogen or fluorine; Y ² is fluorine, chlorine, at least one hydrogen is replaced by fluorine or chlorine. An alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or an alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Is oxy; b is 1, 2, 3, or 4.

Item 8. Item 8. The liquid crystal composition according to any one of items 1 to 7, containing at least one compound selected from compounds represented by formulas (3-1) to (3-34) as a third component.

式（３−１）から式（３−３４）において、Ｒ^４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、または炭素数２から１２のアルケニルである。

In formulas (3-1) to (3-34), R ⁴ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons.

Item 9. Item 9. The liquid crystal composition according to item 7 or 8, wherein the ratio of the third component is in the range of 10% by mass to 70% by mass.

式（４）において、Ｒ^５およびＲ^６は、水素、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、または炭素数２から１２のアルケニルオキシであり；環Ｄおよび環Ｆは、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、テトラヒドロピラン−２，５−ジイル、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、ナフタレン−２，６−ジイル、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ナフタレン−２，６−ジイル、クロマン−２，６−ジイル、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クロマン−２，６−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、７，８−ジフルオロクロマン−２，６−ジイル、３，４，５，６−テトラフルオロフルオレン−２，７−ジイル、４，６−ジフルオロジベンゾフラン−３，７−ジイル、４，６−ジフルオロジベンゾチオフェン−３，７−ジイル、または１，１，６，７−テトラフルオロインダン−２，５−ジイルであり；Ｚ^６およびＺ^７は、単結合、エチレン、ビニレン、メチレンオキシ、またはカルボニルオキシであり；ｃは、０、１、２、または３であり、ｄは、０または１であり、そしてｃおよびｄの和は、３以下である。 Item 10. Item 10. The liquid crystal composition according to any one of items 1 to 9, containing at least one compound selected from the compounds represented by formula (4) as the fourth component.

In formula (4), R ⁵ and R ⁶ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons. Ring D and ring F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen being replaced by fluorine or chlorine. 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen is fluorine or Chroman-2,6-diyl substituted with chlorine; 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, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluoro Fluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2, 5-diyl; Z ⁶ and Z ⁷ are single bonds, ethylene, vinylene, methyleneoxy, or carbonyloxy; c is 0, 1, 2, or 3, and d is 0 or 1. And the sum of c and d is 3 or less.

Item 11. Item 11. The liquid crystal composition according to any one of items 1 to 10, containing at least one compound selected from compounds represented by formulas (4-1) to (4-35) as a fourth component.

式（４−１）から式（４−３５）において、Ｒ^５およびＲ^６は、水素、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、または炭素数２から１２のアルケニルオキシである。

In formulas (4-1) to (4-35), R ⁵ and R ⁶ represent hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon. It is an alkenyloxy of the numbers 2 to 12.

Item 12. Item 12. The liquid crystal composition according to item 10 or 11, wherein the ratio of the fourth component is in the range of 3% by mass to 50% by mass.

Item 13. The maximum temperature of the nematic phase is 70° C. or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25° C.) is 0.07 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25° C.) is 2 13. The liquid crystal composition according to any one of items 1 to 12, which is the above.

Item 14. Item 14. A liquid crystal display device containing the liquid crystal composition according to any one of items 1 to 13.

Item 15. Item 15. The liquid crystal display element according to item 14, wherein an operation mode of the liquid crystal display element is a TN mode, an ECB mode, an OCB mode, an IPS mode, an FFS mode, or an FPA mode, and a driving method of the liquid crystal display element is an active matrix method. ..

Item 16. Item 14. Use of the liquid crystal composition according to any one of items 1 to 13 in a liquid crystal display device.

The present invention also includes the following items. (A) One compound selected from additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a quencher, a dye, a defoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound. A composition as described above containing two compounds, or more than two compounds. (B) An AM device containing the above composition. (C) The above composition further containing a polymerizable compound, and a polymer-supported alignment (PSA) type AM device containing this composition. (D) A polymer-supported alignment (PSA) type AM device containing the composition described above and in which 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 element containing the above composition. (G) Use of the above composition as a composition having a nematic phase. (H) Use of an optically active composition obtained by adding an optically active compound to the above composition.

The present invention also includes the following items. Composition containing at least one compound selected from compounds represented by formula (1) and at least one compound selected from compounds represented by formula (2-1), and AM containing this composition element.

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

First, the composition of the composition will be described. This composition contains a plurality of liquid crystal compounds. The composition may contain additives. Additives are optically active compounds, antioxidants, ultraviolet absorbers, quenchers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. This composition is classified into composition A and composition B from the viewpoint of the liquid crystal compound. The composition A further contains other liquid crystal compounds, additives and the like in addition to the liquid crystal compounds selected from the compound (1), the compound (2), the compound (3) and the compound (4). Good. 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.

The composition B consists essentially of the liquid crystal compound selected from the compound (1), the compound (2), the compound (3), and the compound (4). “Substantially” means that the composition B may contain an additive but does not contain any other liquid crystal compound. Composition B has fewer components than composition A. From the viewpoint of cost reduction, 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 the other liquid crystal compounds.

Second, the main characteristics of the component compounds and the main effects of the compounds on the compositions and devices will be explained. The main characteristics of the component compounds are summarized in Table 2. In the symbols in Table 2, L means large or high, M means medium, and S means small or low. The symbols L, M and S are classifications based on a qualitative comparison among the component compounds, and the symbol 0 (zero) means smaller than S.

The main effects of the component compounds are as follows. The compound (1) increases the optical anisotropy and lowers the minimum temperature. The compound (2) lowers the viscosity or raises the maximum temperature. The compound (3) increases the dielectric anisotropy and lowers the minimum temperature. The compound (4) increases the dielectric constant in the minor axis direction.

Thirdly, the combination of the component compounds in the composition, the preferable ratio, and the basis thereof will be described. Preferred combinations of the component compounds in the composition are compound (1)+compound (2), compound (1)+compound (2)+compound (3), compound (1)+compound (2)+compound (4), Alternatively, compound (1)+compound (2)+compound (3)+compound (4). A more preferred combination is compound (1)+compound (2) or compound (1)+compound (2)+compound (3).

A desirable ratio of the compound (1) is about 5% by mass or more for increasing the optical anisotropy and decreasing the minimum temperature, and about 50% by mass or less for decreasing the viscosity. A more desirable ratio is in the range of approximately 10% by mass to approximately 40% by mass. A particularly desirable ratio is in the range of approximately 10% by mass to approximately 35% by mass.

The preferable ratio of the compound (2) is about 10% by mass or more for increasing the maximum temperature or decreasing the viscosity, and about 80% by mass or less for increasing the dielectric anisotropy. A more desirable ratio is in the range of approximately 20% by mass to approximately 70% by mass. A particularly desirable ratio is in the range of approximately 30% by mass to approximately 60% by mass.

A desirable ratio of the compound (3) is about 10% by mass or more for increasing the dielectric anisotropy, and about 70% by mass or less for decreasing the minimum temperature. A more desirable ratio is in the range of approximately 10% by mass to approximately 40% by mass. A particularly desirable ratio is in the range of approximately 10% by mass to approximately 35% by mass.

The preferable ratio of the compound (4) is about 3% by mass or more for increasing the dielectric constant in the minor axis direction and about 50% by mass or less for decreasing the minimum temperature. A more desirable ratio is in the range of approximately 5% by mass to approximately 45% by mass. A particularly desirable ratio is in the range of approximately 5% by mass to approximately 40% by mass.

Fourthly, a preferred form of the component compound will be described. In formula (1), formula (2), formula (3), and formula (4), R ¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, Alternatively, it is alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Desirable R ¹ is alkyl having 1 to 12 carbons for the purpose of increasing stability to ultraviolet rays or heat. R ² and R ³ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. It is alkenyl. Preferred R ² or R ³ is alkenyl having 2 to 12 carbons for decreasing the viscosity, and alkyl having 1 to 12 carbons for increasing the stability to ultraviolet rays or heat. R ⁴ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons. Preferred R ⁴ is alkyl having 1 to 12 carbons for the purpose of increasing stability to ultraviolet rays or heat. R ⁵ and R ⁶ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons. Desirable R ⁵ or R ⁶ is alkyl having 1 to 12 carbons for increasing the stability against ultraviolet rays or heat, and alkoxy having 1 to 12 carbons for increasing the dielectric constant in the minor axis direction.

Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More desirable alkyl is methyl, ethyl, propyl, butyl, or pentyl 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, It is 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 the alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity. Cis is preferable in the alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl.

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

Preferred examples of alkenyl in which at least one hydrogen has been replaced by fluorine or chlorine 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. A more preferred example is 2,2-difluorovinyl or 4,4-difluoro-3-butenyl for decreasing the viscosity.

Ring A and ring B are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. Preferred ring A or ring B is 1,4-cyclohexylene for decreasing the viscosity or increasing the maximum temperature, and 1,4-phenylene for decreasing the minimum temperature.

Ring C is 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, pyrimidine-2,5-diyl, or 1,3-dioxane- It is 2,5-diyl. Preferred examples of 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 2,6-difluoro. It is -1,4-phenylene. Preferred ring C is 1,4-cyclohexylene for increasing the maximum temperature, 1,4-phenylene for increasing optical anisotropy, and 2,6-difluoro for increasing dielectric anisotropy. It is -1,4-phenylene.

Ring D and ring F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1 in which at least one hydrogen is replaced by fluorine or chlorine. , 4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen is fluorine or chlorine Chroman-2,6-diyl substituted with. Preferred examples of 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. A preferred example of naphthalene-2,6-diyl in which at least one hydrogen has been replaced by fluorine or chlorine is 3,4,5-trifluoronaphthalene-2,6-diyl. A preferred example of chroman-2,6-diyl in which at least one hydrogen has been replaced by fluorine or chlorine is 7,8-difluorochroman-2,6-diyl. Preferred ring D or ring F is 1,4-cyclohexylene for decreasing the viscosity, tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and for increasing the optical anisotropy. It is 1,4-phenylene.

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, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl (FLF4), 4,6- Difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2), or 1,1,6,7-tetrafluoroindane-2,5-diyl (InF4) Is.

Preferred ring E is 2,3-difluoro-1,4-phenylene for decreasing the viscosity, 2-chloro-3-fluoro-1,4-phenylene for decreasing the optical anisotropy, and the dielectric constant. It is 7,8-difluorochroman-2,6-diyl for increasing anisotropy.

Z ¹ , Z ² , and Z ³ are single bonds, ethylene, vinylene, methyleneoxy, or carbonyloxy, and at least one of Z ¹ , Z ² , and Z ³ is ethylene. Preferred Z ¹ is ethylene for increasing the optical anisotropy and decreasing the minimum temperature. Preferred Z ² or Z ³ is a single bond for decreasing the viscosity. Z ⁴ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Preferred Z ⁴ is a single bond for decreasing the viscosity. Z ⁵ is a single bond, ethylene, vinylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy. Preferred Z ⁵ is a single bond for decreasing the viscosity, and difluoromethyleneoxy for increasing the dielectric anisotropy. Z ⁶ and Z ⁷ are single bonds, ethylene, vinylene, methyleneoxy, or carbonyloxy. Preferred Z ⁶ or Z ⁷ is a single bond for decreasing the viscosity, ethylene for decreasing the minimum temperature, and methyleneoxy for increasing the dielectric anisotropy.

Divalent groups such as methyleneoxy are asymmetric. In methyleneoxy, _-CH 2 O-is -OCH ₂ - preferred over. In carbonyloxy, -COO- is preferable to -OCO-. In difluoromethyleneoxy, _-CF 2 O-it is -OCF ₂ - preferred over.

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , and X ⁸ are hydrogen or fluorine. Preferred X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , or X ⁸ is fluorine for increasing the dielectric anisotropy.

Y ¹ and Y ² are fluorine, chlorine, an alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or an alkyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. It is alkenyloxy. A preferred example of alkyl in which at least one hydrogen has been replaced by fluorine or chlorine is trifluoromethyl. A preferred example of alkenyloxy in which at least one hydrogen has been replaced with fluorine or chlorine is trifluorovinyloxy. Preferred Y ¹ or Y ² is fluorine for decreasing the minimum temperature.

a is 1, 2, or 3. Preferred a is 1 for decreasing the viscosity and 2 or 3 for increasing the maximum temperature. b is 1, 2, 3, or 4. Preferred b is 2 or 3 for increasing the dielectric anisotropy. c is 0, 1, 2, or 3, d is 0 or 1, and the sum of c and d is 3 or less. Preferred c is 1 for decreasing the viscosity and 2 or 3 for increasing the maximum temperature. Preferred d is 0 for decreasing the viscosity and 1 for decreasing the minimum temperature.

Fifth, preferable component compounds are shown. Preferred compound (1) includes compound (1-1) to compound (1-3) according to item 2. In these compounds, at least one of the first components is preferably the compound (1-1). At least two of the first components are compound (1-1) and compound (1-2), compound (1-1) and compound (1-3), or compound (1-2) and compound (1-3). The combination is preferably.

Preferred compound (2) includes compound (2-1) to compound (2-13) according to item 5. In these compounds, at least one of the second components is compound (2-1), compound (2-3), compound (2-5), compound (2-6), compound (2-8), or compound. It is preferably (2-13). At least two of the second components are compound (2-1) and compound (2-3), compound (2-1) and compound (2-5), compound (2-1) and compound (2-8), Alternatively, a combination of compound (2-3) and compound (2-5) is preferable.

Preferred compound (3) includes compound (3-1) to compound (3-34) according to item 8. In these compounds, at least one of the third components is compound (3-4), compound (3-12), compound (3-14), compound (3-15), compound (3-17), compound ( 3-18), compound (3-23), compound (3-24), compound (3-26), compound (3-28), or compound (3-29) is preferable. At least two of the third components are compound (3-12) and compound (3-15), compound (3-14) and compound (3-26), compound (3-18) and compound (3-24), The compound (3-18) and the compound (3-28), the compound (3-24) and the compound (3-28), or the combination of the compound (3-28) and the compound (3-29) is preferable.

Preferred compound (4) is compound (4-1) to compound (4-35) according to item 11. In these compounds, at least one of the fourth components is compound (4-1), compound (4-3), compound (4-6), compound (4-8), compound (4-10), compound ( 4-14) or the compound (4-34) is preferable. At least two of the fourth components are compound (4-1) and compound (4-8), compound (4-1) and compound (4-14), compound (4-3) and compound (4-8), Compound (4-3) and compound (4-14), compound (4-3) and compound (4-34), compound (4-6) and compound (4-8), compound (4-6) and compound It is preferably (4-10) or a combination of compound (4-6) and compound (4-14).

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

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, the compound (6-1 ) To an antioxidant such as compound (6-3) may be added to the composition.

Since the compound (6-2) 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 using the device for a long time. A preferable ratio of the antioxidant is about 50 ppm or more to obtain the effect, and about 600 ppm or less so as not to lower the upper limit temperature or to raise the lower limit temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 300 ppm.

Preferred examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as sterically hindered amines are also preferred. Preferred examples of the light stabilizer include compound (7-1) to compound (7-16). The preferred ratio of these absorbents and stabilizers is about 50 ppm or more for obtaining the effect, and about 10,000 ppm or less for not lowering the upper limit temperature or for not raising the lower limit temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 10,000 ppm.

The quencher is a compound that receives the light energy absorbed by the liquid crystal compound and converts it into heat energy to prevent the liquid crystal compound from decomposing. Preferable examples of the quencher include the compound (8-1) to the compound (8-7). The preferable ratio of these quenchers is about 50 ppm or more for obtaining the effect, and about 20,000 ppm or less for not raising 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, anthraquinone dye, or the like is added to the composition in order to adapt to a GH (guest host) mode device. The preferred proportion of dye is in the range of about 0.01% to about 10% by weight. An antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is added to the composition to prevent foaming. The preferable ratio of the defoaming agent is about 1 ppm or more to obtain the effect, and about 1000 ppm or less to prevent display defects. A more desirable ratio is in the range of approximately 1 ppm to approximately 500 ppm.

Polymerizable compounds are used to adapt to polymer-supported alignment (PSA) type devices. Preferred 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 is about 10% by mass or more based on the total mass of the polymerizable compound. A more desirable ratio is about 50% by mass or more. A particularly desirable ratio is about 80% by mass or more. The most preferable ratio is 100% by mass.

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

The polar compound is an organic compound having polarity. Here, a compound having an ionic bond is not included. Atoms such as oxygen, sulfur, and nitrogen are more electronegative and tend to have a partial negative charge. Carbon and hydrogen tend to be neutral or have a partial positive charge. Polarity arises from the uneven distribution of partial charges among different atoms in the compound. For example, polar compounds have _{-OH, -COOH, -SH, -NH 2} ,> NH, at least one of the> N-moiety like.

Seventh, a method of synthesizing the component compounds will be described. These compounds can be synthesized by known methods. A synthetic method is illustrated. Compound (1-1) is synthesized by the method described in WO 2004/106460. The compound (2-1) is synthesized by the method described in JP-A-59-176221. The compound (3-8) is synthesized by the method described in JP-A-2-233626. The compound (4-1) and the compound (4-8) are synthesized by the method disclosed in Japanese Patent Publication No. 2-503441. Antioxidants are commercially available. Compound (6-1) is available from Aldrich (Sigma-Aldrich Corporation). Compound (6-2) and the like are synthesized by the method described in US Pat. No. 3,660,505.

Compounds for which no synthetic method is described are Organic Syntheses, John Wiley & Sons, Inc, Organic Reactions, John Wiley & Sons, Inc, Comprehensive Organic Synthesis. Synthesis, Pergamon Press), New Experimental Chemistry Course (Maruzen), etc. The composition is prepared from the compounds thus obtained by known methods. For example, the component compounds are mixed and dissolved by heating.

Finally, the use of the composition will be explained. This 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 composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the ratio of component compounds or by mixing with other liquid crystal compounds. Compositions having optical anisotropy in the range of about 0.10 to about 0.30 may be prepared by trial and error. 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. This composition can be used as a composition having a nematic phase, or 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 a PM element. This composition can be used for AM and PM devices having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA and FPA. The use in AM devices having TN, OCB, IPS mode or FFS mode is particularly preferable. In the AM device having the IPS mode or the FFS mode, when no voltage is applied, the liquid crystal molecules may be aligned in parallel with 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 element produced by microencapsulating this composition and a PD (polymer dispersed) type element in which a three-dimensional network polymer is formed in the composition.

When the liquid crystal display device is used for a long time, flicker may occur on the display screen. Flicker is associated with image burn-in and is presumed to be caused by a difference between the positive frame potential and the negative frame potential when driven by an alternating current. The flicker rate (%) can be represented by (|luminance when a positive voltage is applied-luminance when a negative voltage is applied)/average luminance)×100. The flicker rate is preferably in the range of 0% to 1%. A small flicker rate is preferred. With this composition, the occurrence of flicker can be suppressed.

The present invention will be described in more detail by way of examples. The invention is not limited by these examples. The present invention comprises a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes a mixture of at least two of the example compositions. The synthesized compound was identified by a method such as NMR analysis. The properties of the compounds, compositions, and devices were measured by the methods described below.

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

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

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

The ratio of the liquid crystal compound contained in the composition may be calculated by the following method. The mixture of liquid crystal compounds is analyzed by gas chromatography (FID). The area ratio of the peaks in the gas chromatogram corresponds to the 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 (mass %) of the liquid crystal compound can be calculated from the peak area ratio.

Measurement sample: When measuring the characteristics of the composition or device, the composition was directly used as a sample. When measuring the characteristics of the compound, a sample for measurement was prepared by mixing this compound (15% by mass) with the mother liquid crystal (85% by mass). 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. in this proportion, the proportions of the compound and the mother liquid crystal are 10% by mass: 90% by mass, 5% by mass: 95% by mass, 1% by mass: 99% by mass in this order. changed. Values of the maximum temperature, optical anisotropy, viscosity, and dielectric anisotropy of the compound were obtained by this extrapolation method.

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

Measuring method: The characteristics were measured by the following methods. Most of these are the methods described in the JEITA standard (JEITA/ED-2521B), which is deliberated and established by the Japan Electronics and Information Technology Industries Association (JEITA), or modified methods. Met. No thin film transistor (TFT) was attached to the TN device used for the measurement.

(1) Maximum temperature of the nematic phase (NI; °C): The sample was placed on a hot plate of a melting point measuring device equipped with a polarization 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 maximum temperature of the nematic phase may be abbreviated as “maximum temperature”.

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

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

(4) Viscosity (rotational viscosity; γ1; measured at 25° C.; mPa·s): The method is described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). I obeyed. The sample was put in a TN device having a twist angle of 0° and a distance (cell gap) between two glass substrates of 5 μm. A voltage of 16V to 19.5V was applied to the device in steps of 0.5V. After 0.2 seconds of non-application, application was repeated under the conditions of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and the peak time of the transient current generated by this application were measured. The rotational viscosity value was obtained from these measured values and the calculation formula (10) described on page 40 in the paper by M. Imai et al. The value of the dielectric anisotropy required for this calculation was determined by the method described below using the device whose rotational viscosity was measured.

(5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25° C.): The measurement was carried out using an Abbe refractometer with a polarizing plate attached to the eyepiece, using light having a wavelength of 589 nm. After rubbing the surface of the main prism in one direction, the sample was dropped on the main prism. The refractive index n/| was measured when the direction of polarized light was parallel to the direction of rubbing. The refractive index n⊥ was measured when the direction of polarized light was perpendicular to the direction of rubbing. The value of optical anisotropy was calculated from the formula: Δn=n/-n⊥.

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

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

(8) Voltage holding ratio (VHR-1; measured at 25° C.; %): The TN device used for measurement had a polyimide alignment film, and the distance (cell gap) between two glass substrates was 5 μm. .. This device was sealed with an adhesive which was cured by ultraviolet rays after the sample was put in. A pulse voltage (60 microseconds at 1 V) was applied to the TN device to charge it. The decaying voltage was measured with a high-speed voltmeter for 166.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit cycle was obtained. Area B was the area when it was not attenuated. The voltage holding ratio was expressed as a percentage of the area A with respect to the area B.

(9) Voltage holding ratio (VHR-2; measured at 60°C; %): The voltage holding ratio was measured by the same procedure as above except that the temperature was measured at 60°C instead of 25°C. The obtained value was represented by VHR-2.

(10) Voltage holding ratio (VHR-3; measured at 60° C.; %): After irradiation with ultraviolet rays, the voltage holding ratio was measured to evaluate 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 device and was irradiated with 5 mW/cm ² ultraviolet rays for 167 minutes. The light source was a black light manufactured by Eye Graphics Co., Ltd., F40T10/BL (peak wavelength 369 nm), and the distance between the element and the light source was 5 mm. The VHR-3 measurement measured the decaying voltage during 166.7 milliseconds. Compositions with large VHR-3 have great stability to UV light.

(11) Voltage holding ratio (VHR-4; measured at 60° C.; %): The TN device injecting the sample was heated in a constant temperature bath at 120° C. for 20 hours, and then the voltage holding ratio was measured to determine the stability to heat. Was evaluated. In the VHR-4 measurement, a voltage that decays for 166.7 milliseconds was measured. Compositions with large VHR-4 have great stability to heat.

(12) Voltage holding ratio (VHR-5; measured at 60° C.; %): The TN device injecting the sample was heated in a thermostatic chamber at 100° C. for 3 weeks, then the voltage holding ratio was measured, and the stability against heat was measured. Was evaluated. In the VHR-5 measurement, the voltage that decays for 166.7 milliseconds was measured. Compositions with large VHR-5 have great heat stability.

(13) Response time (τ; measured at 25° C.; ms): Measurement was carried out with LCD Evaluation System Model LCD-5100 made by Otsuka Electronics Co., Ltd. The light source was a halogen lamp. The low-pass filter (Low-pass filter) was set to 5 kHz. The sample was put into a normally white mode TN device in which a distance (cell gap) between two glass substrates was 5.0 μm and a twist angle was 80 degrees. A rectangular wave (60 Hz, 5 V, 0.5 seconds) was applied to this device. 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 maximum, and the transmittance was 0% when the light amount was minimum. The rise time (τr: rise time; millisecond) is the time required for the transmittance to change from 90% to 10%. The fall time (τf: fall time; millisecond) is the time required to change the transmittance from 10% to 90%. The response time was represented by the sum of the rise time and fall time thus obtained.

(14) Elastic constant (K; measured at 25° C.; pN): An HP4284A LCR meter manufactured by Yokogawa-Hewlett Packard Co. was used for the measurement. The sample was placed in a horizontal alignment device in which the distance (cell gap) between two glass substrates was 20 μm. A charge of 0 V to 20 V was applied to this device, and the electrostatic capacity and the applied voltage were measured. Fitting the measured capacitance (C) and applied voltage (V) values using the formula (2.98) and formula (2.101) on page 75 of "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun). Then, the values of K11 and K33 were obtained from the formula (2.99). Next, K22 was calculated by using the values of K11 and K33 obtained earlier in the equation (3.18) on page 171. The elastic constant was represented by the average value of K11, K22, and K33 thus obtained.

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

(16) Helical pitch (P; measured at room temperature; μm): The helical pitch was measured by the wedge method. See "Liquid Crystal Handbook", page 196 (issued in 2000, Maruzen). The sample was poured into a wedge-shaped cell and allowed to stand at room temperature for 2 hours, after which the spacing (d2-d1) of the disclination line was observed with a polarizing microscope (Nikon Corporation, trade name MM40/60 series). The spiral pitch (P) was calculated from the following equation in which the angle of the wedge cell was represented by θ. P=2×(d2-d1)×tan θ.

(17) Dielectric constant in short axis direction (ε⊥; measured at 25° C.): A sample was put in a TN device in which a distance (cell gap) between two glass substrates was 9 μm and a twist angle was 80 degrees. .. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the dielectric constant (ε⊥) in the short axis direction of the liquid crystal molecule was measured.

(18) Flicker rate (measured at 25° C.; %): Yokogawa Electric Co., Ltd. multimedia display tester 3298F was used for measurement. The light source was an LED. The sample was put in a normally black mode FFS device in which the distance between two glass substrates (cell gap) was 3.5 μm and the rubbing direction was antiparallel. The device was sealed with an adhesive that was cured with ultraviolet light. A voltage was applied to this element, and the voltage at which the amount of light transmitted through the element was maximized was measured. While applying this voltage to the element, the sensor part was brought close to the element and the displayed flicker rate was read.

Examples of compositions are given below. The component compounds are represented by symbols based on the definitions in Table 3 below. In Table 3, the configuration of 1,4-cyclohexylene is trans. The number in parentheses after the symbolized compound represents the chemical formula to which the compound belongs. The symbol (−) means other liquid crystal compound. The ratio (percentage) of the liquid crystal compound is a mass percentage (mass %) based on the mass of the liquid crystal composition containing no additive. Finally, the characteristic values of the composition are summarized.

この化合物は、１つのテトラヒドロピラン環と３つのベンゼン環とを有する点で化合物（１）に類似している。 [Comparative Example 1]
Mixture example 1 described on page 61 of WO 2004/106460 was chosen for comparison. The rationale is that this mixture contains APGU-3-F (10.0%) having the structure: This compound is designated 3-dhBB(F)B(F,F)-F according to the nomenclature of Table 3.

This compound is similar to compound (1) in that it has one tetrahydropyran ring and three benzene rings.

The ingredients and properties of Mixture Example 1 were as follows: There was no description of viscosity. Then, when the viscosity (η) was measured according to the method described in “(3) Viscosity”, it was 24.7 mPa·s.

3-HBB(F)-F (3) 10.8%
5-HBB(F)-F (3) 9.0%
3-HH2B-OCF3 (3) 4.5%
5-HH2B-OCF3 (3) 4.5%
3-HB(F)BH-3 (2-12) 1.8%
5-HB(F)BH-3 (2-12) 1.8%
5-HB(F)BH-5 (2-12) 1.8%
5-HB-F (-) 9.0%
6-HB-F (-) 7.2%
7-HB-F (-) 5.4%
2-HHB-OCF3 (3) 7.2%
3-HHB-OCF3 (3) 10.8%
4-HHB-OCF3 (3) 6.3%
5-HHB-OCF3 (3) 9.9%
3-dhBB(F)B(F,F)-F(-) 10.0%
NI=102.2° C.; Δn[589 nm; 20° C.]=+0.1097; ε⊥[1 kHz, 20° C.]=3.3; Δε[1 kHz, 20° C.]=+6.9.

[Example 1]
3-dh2BB(F)B(F,F)-F (1-1) 5%
2-HH-3 (2-1) 5%
3-HH-4 (2-1) 5%
3-HH-V (2-1) 20%
1-BB-3 (2-3) 5%
3-HHEH-3 (2-4) 4%
3-HHB-1 (2-5) 13%
V-HHB-1 (2-5) 13%
1-BB(F)B-2V (2-8) 8%
3-BB(F)B-2V (2-8) 7%
3-GB(F)B(F,F)-F (3-12) 3%
3-BB(F)B(F,F)-F (3-15) 4%
3-GB(F)B(F,F)XB(F,F)-F (3-26) 5%
3-HHB(2F,3F)-O2 (4-8) 3%
NI=102.9° C.; Tc<−20° C.; η=18.0 mPa·s; Δn=0.119; Δε=3.0.

[Example 2]
3-dh2BB(F)B(F,F)-F (1-1) 10%
2-HH-3 (2-1) 12%
3-HH-V (2-1) 25%
5-HB-O2 (2-2) 3%
V-HHB-1 (2-5) 15%
V2-HHB-1 (2-5) 11%
5-HBB(F)B-2 (2-13) 10%
3-GB(F,F)XB(F,F)-F (3-14) 3%
3-GB(F)B(F,F)XB(F,F)-F (3-26) 4%
5-BB(F)B(F,F)XB(F,F)-F (3-28) 4%
V-HB(2F,3F)-O4 (4-1) 3%
NI=104.0° C.; Tc<−20° C.; η=19.8 mPa·s; Δn=0.107; Δε=3.9.

[Example 3]
3-dh2BB(F)B(F,F)-F (1-1) 8%
3-dhB2B(F)B(F,F)-F (1-2) 5%
3-HH-V (2-1) 27%
3-HH-V1 (2-1) 5%
1-BB-3 (2-3) 12%
3-HHB-1 (2-5) 9%
V-HHB-1 (2-5) 8%
3-B2BB-2 (2-9) 2%
5-HBB(F)B-2 (2-13) 8%
3-BB(F,F)XB(F,F)-F (3-18) 3%
3-HBB(F,F)XB(F,F)-F (3-24) 5%
5-BB(F)B(F,F)XB(F,F)-F (3-28) 3%
V-HHB(2F,3F)-O2 (4-8) 5%
NI=97.2° C.; Tc<−20° C.; η=19.9 mPa·s; Δn=0.117; Δε=3.2.

[Example 4]
3-dh2BB(F)B(F,F)-F (1-1) 5%
3-dh2B(F)B(F,F)B(F,F)-F(1-1) 5%
3-HH-V (2-1) 30%
3-HH-V1 (2-1) 7%
V-HHB-1 (2-5) 10%
V2-HHB-1 (2-5) 6%
3-HBB-2 (2-6) 4%
1-BB(F)B-2V (2-8) 3%
3-HHEBH-3 (2-11) 3%
5-HXB(F,F)-F (3-1) 7%
3-HBB(F,F)XB(F,F)-F (3-24) 5%
4-BB(F)B(F,F)XB(F,F)-F (3-28) 3%
3-BB(F,F)XB(F)B(F,F)-F (3-29) 4%
3-H1OB(2F,3F)-O2 (4-3) 4%
5-HHB(2F,3F)-O2 (4-8) 4%
NI=92.7° C.; Tc<−20° C.; η=19.7 mPa·s; Δn=0.100; Δε=4.0.

[Example 5]
3-dh2BB(F)B(F,F)-F (1-1) 5%
3-HH-V (2-1) 30%
3-HH-V1 (2-1) 4%
V-HH-V1 (2-1) 7%
V-HHB-1 (2-5) 13%
V2-HHB-1 (2-5) 10%
1-BB(F)B-2V (2-8) 6%
3-BB(F)B-2V (2-8) 7%
3-HBBBX(F,F)-F (3-23) 3%
3-HBB(F,F)XB(F,F)-F (3-24) 5%
4-BB(F)B(F,F)XB(F,F)-F (3-28) 7%
3-HBB(2F,3F)-O2 (4-14) 3%
NI=106.6° C.; Tc<−20° C.; η=14.7 mPa·s; Δn=0.122; Δε=3.1.

[Example 6]
3-dh2BB(F)B(F,F)-F (1-1) 5%
3-dhBB(F)2B(F,F)-F (1-3) 5%
3-HH-V (2-1) 35%
3-HH-V1 (2-1) 5%
V-HHB-1 (2-5) 10%
3-B(F)BB-2 (2-7) 3%
2-BB(F)B-5 (2-8) 5%
1-HHB(F,F)-F (3-2) 5%
3-HHB(F,F)-F (3-2) 3%
3-HHXB(F,F)-F (3-4) 5%
3-BBXB(F,F)-F (3-17) 6%
3-HBB(F,F)XB(F,F)-F (3-24) 5%
V-HB(2F,3F)-O4 (4-1) 5%
5-HBB(2F,3F)-O2 (4-14) 3%
NI=80.2° C.; Tc<−20° C.; η=15.5 mPa·s; Δn=0.098; Δε=3.1.

[Example 7]
3-dh2BB(F)B(F,F)-F (1-1) 10%
2-HH-3 (2-1) 10%
3-HH-V (2-1) 25%
3-HH-V1 (2-1) 6%
V2-HHB-1 (2-5) 10%
1-BB(F)B-2V (2-8) 4%
3-BB(F)B-2V (2-8) 8%
3-HB(F)HH-5 (2-10) 3%
5-HB(F)BH-3 (2-12) 5%
5-HHB(F,F)-F (3-2) 3%
3-HHXB(F,F)-CF3 (3-5) 3%
3-BB(F,F)XB(F,F)-F (3-18) 3%
4-BB(F)B(F,F)XB(F,F)-F (3-28) 4%
3-HB(2F,3F)BXB(F,F)-F (3-33) 3%
V-HHB(2F,3F)-O4 (4-8) 3%
NI=103.1° C.; Tc<−20° C.; η=19.6 mPa·s; Δn=0.114; Δε=3.3.

[Example 8]
3-dh2BB(F)B(F,F)-F (1-1) 5%
3-dh2B(F)B(2F)B(F,F)-F (1-1) 5%
2-HH-3 (2-1) 7%
3-HH-V (2-1) 27%
1-BB-5 (2-3) 3%
V-HHB-1 (2-5) 10%
V2-HHB-1 (2-5) 13%
3-BB(F)B-2V (2-8) 10%
2-HHEB(F,F)-F (3-3) 3%
3-HGB(F,F)-F (3-6) 3%
3-BB(F,F)XB(F,F)-F (3-18) 5%
4-BB(F)B(F,F)XB(F,F)-F (3-28) 4%
3-H1OB(2F,3F)-O2 (4-3) 3%
2-HBB(2F,3F)-O2 (4-14) 2%
NI=88.9° C.; Tc<−20° C.; η=18.3 mPa·s; Δn=0.110; Δε=3.0.

[Example 9]
3-dh2BB(F)B(F,F)-F (1-1) 5%
2-HH-3 (2-1) 10%
3-HH-V (2-1) 20%
3-HH-V1 (2-1) 7%
V2-BB-1 (2-3) 5%
3-HHB-O1 (2-5) 7%
V-HHB-1 (2-5) 10%
3-BB(F)B-5 (2-8) 3%
1-BB(F)B-2V (2-8) 5%
3-BB(F)B-2V (2-8) 7%
3-BB(F,F)XB(F,F)-F (3-18) 5%
3-HBBBX(F,F)-F (3-23) 5%
4-BB(F)B(F,F)XB(F,F)-F (3-28) 5%
3-HB(2F,3F)-O2 (4-1) 3%
1O1-HBBH-5 (-) 3%
NI=96.7° C.; Tc<−20° C.; η=14.9 mPa·s; Δn=0.120; Δε=3.0.

[Example 10]
3-dh2BB(F)B(F,F)-F (1-1) 10%
2-HH-3 (2-1) 9%
3-HH-V (2-1) 30%
V-HHB-1 (2-5) 6%
V2-HHB-1 (2-5) 6%
1-BB(F)B-2V (2-8) 10%
3-BB(F)B-2V (2-8) 7%
3-GHB(F,F)-F (3-7) 2%
3-HB(F)B(F,F)-F (3-9) 5%
3-BB(F)B(F,F)-CF3 (3-16) 5%
3-BB(F)B(F,F)XB(F)B(F,F)-F (3-30) 3%
3-BB(2F,3F)BXB(F,F)-F(3-34) 2%
3-H1OB(2F,3F)-O2 (4-3) 3%
3-HBB(2F,3F)-O2 (4-14) 2%
NI=90.1° C.; Tc<−20° C.; η=19.1 mPa·s; Δn=0.126; Δε=4.5.

[Example 11]
3-dh2BB(F)B(F,F)-F (1-1) 5%
2-HH-3 (2-1) 5%
3-HH-V (2-1) 25%
V-HH-V1 (2-1) 7%
V2-HHB-1 (2-5) 10%
1V2-HHB-1 (2-5) 8%
1-BB(F)B-2V (2-8) 10%
3-HBB(F,F)-F (3-8) 3%
3-HBEB(F,F)-F (3-10) 2%
3-HHBB(F,F)-F (3-19) 3%
4-GBB(F,F)XB(F,F)-F (3-25) 3%
3-BB(2F,3F)XB(F,F)-F (3-31) 7%
3-B(2F,3F)BXB(F,F)-F(3-32) 5%
3-BB(2F,3F)-O2 (4-6) 3%
3-HH1OB(2F,3F)-O2 (4-10) 4%
NI=90.7° C.; Tc<−20° C.; η=17.4 mPa·s; Δn=0.113; Δε=3.1.

[Example 12]
3-dh2BB(F)B(F,F)-F (1-1) 10%
2-HH-3 (2-1) 5%
2-HH-5 (2-1) 5%
3-HH-V (2-1) 30%
V-HH-V1 (2-1) 5%
5-HBB(F)B-2 (2-13) 3%
5-HXB(F,F)-F (3-1) 8%
3-GB(F)B(F)-F (3-11) 3%
3-BBXB(F,F)-F (3-17) 11%
3-HHB(F)B(F,F)-F (3-20) 3%
3-GB(F)B(F)B(F)-F (3-21) 2%
3-GBB(F)B(F,F)-F (3-22) 2%
3-BB(F)B(F,F)XB(F)-F (3-27) 4%
3-H1OB(2F,3F)-O2 (4-3) 4%
3-HBB(2F,3F)-O2 (4-14) 3%
2O-DBTF2-O4 (4-34) 2%
NI=70.8° C.; Tc<−20° C.; η=18.1 mPa·s; Δn=0.100; Δε=4.4.

[Example 13]
3-dh2BB(F)B(F,F)-F (1-1) 12%
2-HH-3 (2-1) 5%
2-HH-5 (2-1) 5%
3-HH-V (2-1) 22%
1V2-HH-3 (2-1) 4%
3-HHB-O1 (2-5) 5%
V-HHB-1 (2-5) 10%
V2-HHB-1 (2-5) 10%
1-BB(F)B-2V (2-8) 6%
3-BB(F)B-2V (2-8) 7%
3-GB(F,F)XB(F)-F (3-13) 3%
3-BB(F,F)XB(F,F)-F (3-18) 4%
3-BB(F)B(F,F)XB(F,F)-F (3-28) 3%
V-HB(2F,3F)-O2 (4-1) 2%
3-HB(2F,3F)-O2 (4-1) 2%
NI=98.4° C.; Tc<−20° C.; η=18.6 mPa·s; Δn=0.117; Δε=3.3.

[Example 14]
3-dh2BB(F)B(F,F)-F (1-1) 5%
3-HH-V (2-1) 30%
3-HH-V1 (2-1) 5%
V-HH-V1 (2-1) 6%
V-HHB-1 (2-5) 4%
V2-HHB-1 (2-5) 4%
1-BB(F)B-2V (2-8) 6%
3-BB(F)B-2V (2-8) 5%
3-HHXB(F,F)-F (3-4) 5%
3-HBBBX(F,F)-F (3-23) 10%
3-HBB(F,F)XB(F,F)-F (3-24) 8%
4-BB(F)B(F,F)XB(F,F)-F (3-28) 7%
3-HHB(2F,3F)-O2 (4-8) 5%
NI=102.1° C.; Tc<−20° C.; η=19.5 mPa·s; Δn=0.119; Δε=5.4.

The viscosity of the composition of Comparative Example 1 was 24.7 mPa·s. On the other hand, the viscosity of the composition of Example 1 was 18.0 mPa·s. Thus, the composition of the example had a lower viscosity than the composition of the comparative example. Therefore, it is concluded that the liquid crystal composition of the present invention has excellent properties.

The liquid crystal composition of the present invention can be used for liquid crystal monitors, liquid crystal televisions, and the like.

Claims (16)

A liquid crystal composition containing as a first component at least one compound selected from the compounds represented by formula (1).

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 2 carbons in which at least one hydrogen is replaced by fluorine or chlorine. To 12 alkenyl; X ¹ , X ² , X ³ , X ⁴ , X ⁵ , and X ⁶ are hydrogen or fluorine; Y ¹ is fluorine, chlorine, at least one hydrogen is fluorine or chlorine. A substituted alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or an alkyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine Alkenyloxy; Z ¹ , Z ² , and Z ³ are single bonds, ethylene, vinylene, methyleneoxy, or carbonyloxy, and at least one of Z ¹ , Z ² , and Z ³ is ethylene. The liquid crystal composition according to claim 1, containing at least one compound selected from compounds represented by formulas (1-1) to (1-3) as a first component.

In formulas (1-1) to (1-3), R ¹ represents alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen being fluorine. Or alkenyl having 2 to 12 carbon atoms substituted with chlorine; X ¹ , X ² , X ³ , X ⁴ , X ⁵ , and X ⁶ are hydrogen or fluorine; Y ¹ is fluorine, chlorine, Alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen being fluorine or chlorine. It is a substituted alkenyloxy having 2 to 12 carbons. The liquid crystal composition according to claim 1, wherein the ratio of the first component is in the range of 5% by mass to 50% by mass. The liquid crystal composition according to claim 1, containing at least one compound selected from the compounds represented by formula (2) as the second component.

In formula (2), R ² and R ³ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen is replaced with fluorine or chlorine. C2-C12 alkenyl; Ring A and Ring B are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4. - be a phenylene; ^{Z 4} is a single bond, ethylene, vinylene, methyleneoxy or carbonyloxy,; a is 1, 2 or 3. The liquid crystal composition according to any one of claims 1 to 4, containing at least one compound selected from compounds represented by formulas (2-1) to (2-13) as a second component. ..

In formulas (2-1) to (2-13), R ² and R ³ are each alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one. It is alkenyl having 2 to 12 carbons in which hydrogen is replaced by fluorine or chlorine. The liquid crystal composition according to claim 4, wherein the ratio of the second component is in the range of 10% by mass to 80% by mass. 7. The liquid crystal composition according to claim 1, containing at least one compound selected from the compounds represented by formula (3) as the third component.

In formula (3), R ⁴ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons; ring C is 1,4-cyclohexylene, 1, 4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, pyrimidine-2,5-diyl, or 1,3-dioxane-2,5-diyl; Z ⁵ is a single A bond, ethylene, vinylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy; X ⁷ and X ⁸ are hydrogen or fluorine; Y ² is fluorine, chlorine, at least one hydrogen is replaced by fluorine or chlorine. An alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or an alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Is oxy; b is 1, 2, 3, or 4. 8. The liquid crystal composition according to claim 1, containing at least one compound selected from compounds represented by formulas (3-1) to (3-34) as a third component. ..

In formulas (3-1) to (3-34), R ⁴ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons. The liquid crystal composition according to claim 7, wherein the ratio of the third component is in the range of 10% by mass to 70% by mass. 10. The liquid crystal composition according to claim 1, containing at least one compound selected from the compounds represented by formula (4) as the fourth component.

In formula (4), R ⁵ and R ⁶ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons. Ring D and ring F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen being replaced by fluorine or chlorine. 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen is fluorine or Chroman-2,6-diyl substituted with chlorine; 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, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluoro Fluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2, 5-diyl; Z ⁶ and Z ⁷ are single bonds, ethylene, vinylene, methyleneoxy, or carbonyloxy; c is 0, 1, 2, or 3, and d is 0 or 1. And the sum of c and d is 3 or less. 11. The liquid crystal composition according to claim 1, containing at least one compound selected from compounds represented by formulas (4-1) to (4-35) as a fourth component. ..

In formulas (4-1) to (4-35), R ⁵ and R ⁶ represent hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon. It is an alkenyloxy of the numbers 2 to 12. The liquid crystal composition according to claim 10, wherein the ratio of the fourth component is in the range of 3% by mass to 50% by mass. The maximum temperature of the nematic phase is 70° C. or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25° C.) is 0.07 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25° C.) is 2 The liquid crystal composition according to any one of claims 1 to 12, which is the above. A liquid crystal display device containing the liquid crystal composition according to claim 1. The liquid crystal display according to claim 14, wherein the operation mode of the liquid crystal display element is a TN mode, an ECB mode, an OCB mode, an IPS mode, an FFS mode, or an FPA mode, and the driving method of the liquid crystal display element is an active matrix method. element. Use of the liquid crystal composition according to any one of claims 1 to 13 in a liquid crystal display device.