JP6821996B2 - Liquid crystal composition and liquid crystal display element - Google Patents

Description

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

In liquid crystal display elements, the classification based on the operation mode of liquid crystal molecules is PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS. (In-plane switching), VA (vertical alignment), FFS (fringe field switching), FPA (field-induced photo-reactive alignment) and other modes. The classifications based on the drive method of the element are 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). The classification of TFT is amorphous silicon (amorphous silicon) and polycrystalline silicon (polycrystal 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 is a reflective type that uses natural light, a transmissive type that uses a backlight, and a transflective type that uses both natural light and a backlight.

The liquid crystal display element 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 properties of the composition will be further described based on commercially available AM devices. The temperature range of the nematic phase is related to the temperature range in which the device can be used. The preferred upper limit temperature of the nematic phase is about 70 ° C. or higher, and the preferred lower limit 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 preferred for displaying moving images on the device. A shorter response time of even 1 millisecond is desirable. Therefore, a small viscosity in the composition is preferred. Small viscosities at low temperatures are 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 more 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, an appropriate optical anisotropy is required. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate product value depends on the type of operating mode. For devices in modes 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. The large permittivity anisotropy in the composition contributes to the low threshold voltage, low power consumption and large contrast ratio in the device. Therefore, large dielectric anisotropy is preferred. A large resistivity in the composition contributes to a large voltage retention and a large contrast ratio in the device. Therefore, a composition having a large resistivity at an initial stage not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable. After long-term use, a composition having a large resistivity not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable. The stability of the composition against UV and heat is related to the life of the liquid crystal display device. When these stability is high, the life of this device is long. Such characteristics are preferable for AM elements used in liquid crystal projectors, liquid crystal televisions, and the like.

In the AM device having the TN mode, a composition having a positive dielectric anisotropy is used. In the AM device having the VA mode, a composition having a negative dielectric anisotropy is used. In an AM device having an IPS mode or an FFS mode, a composition having positive or negative dielectric anisotropy is used. In a polymer sustained alignment (PSA) type AM device, a composition having positive or negative dielectric anisotropy is used. An example of a liquid crystal composition having a positive dielectric anisotropy is disclosed in Patent Document 1 below.

Japanese Unexamined Patent Publication No. 4-18089 Japanese Unexamined Patent Publication No. 2000-87039 Japanese Unexamined Patent Publication No. 2006-8928 Japanese Unexamined Patent Publication No. 2006-70080 JP-A-2007-91796

One object of the present invention is a high upper limit temperature of the nematic phase, a lower lower limit temperature of the nematic phase, a small viscosity, an appropriate optical anisotropy, a large permittivity anisotropy, a large permittivity of a liquid crystal molecule in the minor axis direction, It is an object of the present invention to provide a liquid crystal composition satisfying at least one of properties such as high specific resistance, high stability against ultraviolet rays, high stability against heat, and large elastic constant. Another object is to provide a liquid crystal composition having an appropriate balance between at least two of these properties. Another object is to provide a liquid crystal display device containing such a composition. Another object is to provide an AM device with characteristics such as short response time, high voltage retention, low threshold voltage, high contrast ratio, long life.

式（１）および式（２）において、Ｒ^１は、炭素数１から１２のアルキルまたは炭素数２から１２のアルケニルであり、これらの基において、少なくとも１つの−ＣＨ_２−は、−Ｏ−で置き換えられてもよく；Ｒ^２およびＲ^３は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素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、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は、テトラヒドロピラン−２，５−ジイルまたは１，３−ジオキサン−２，５−ジイルであり；環Ｂは独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，３−ジフルオロ−１，４−フェニレン、２，６−ジフルオロ−１，４−フェニレン、ピリミジン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはテトラヒドロピラン−２，５−ジイルであり；Ｚ^１およびＺ^２は独立して、単結合、エチレン、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、ここでＺ^１またはＺ^２のうち少なくとも１つはジフルオロメチレンオキシであり；Ｘ^１およびＸ^２は独立して、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；ａは０、１、２、または３であり；ｎは０、１、２、または３である。 In the present invention, at least one compound selected from the group of compounds represented by the formula (1) as the first component, and at least one selected from the group of compounds represented by the formula (2) as the second component. The present invention relates to a liquid crystal composition containing one compound and having a nematic phase, and a liquid crystal display element containing this composition.

In formulas (1) and (2), R ¹ is an alkyl having 1 to 12 carbon atoms or an alkenyl having 2 to 12 carbon atoms, and in these groups, at least one −CH ₂ − is −O−. R ² and R ³ may be independently replaced by an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, and at least one hydrogen being fluorine or chlorine. An alkyl having 1 to 12 carbon atoms replaced, or an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine; ring A is tetrahydropyran-2,5-diyl or 1,3. -Dioxane-2,5-diyl; Ring B is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2 , 3-Difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidin-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5 -Diyl; Z ¹ and Z ² are independently single-bonded, ethylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy, where at least one of Z ¹ or Z ² is difluoromethyleneoxy. Yes; X ¹ and X ² are independently hydrogen or fluorine; Y ¹ is fluorine, chlorine, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine, at least one hydrogen. Is an alkoxy having 1 to 12 carbon atoms replaced with fluorine or chlorine, or at least one hydrogen is an alkenyloxy having 2 to 12 carbon atoms replaced with fluorine or chlorine; a is 0, 1, 2, or 3 ; N is 0, 1, 2, or 3.

The advantages of the present invention are high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, appropriate optical anisotropy, large permittivity anisotropy, large permittivity of liquid crystal molecules in the minor axis direction, large ratio. It is an object of the present invention to provide a liquid crystal composition that satisfies at least one of properties such as resistance, high stability against ultraviolet rays, high stability against heat, and a large elastic constant. Another advantage is to provide a liquid crystal composition having an appropriate 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 AM devices with characteristics such as short response time, high voltage retention, low threshold voltage, high contrast ratio, long life.

The usage of terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "composition" and "element", respectively. "Liquid crystal display element" is a general term for a liquid crystal display panel and a liquid crystal display module. The "liquid crystal compound" is composed for the purpose of adjusting characteristics such as a temperature range, viscosity, and dielectric anisotropy of a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and a nematic phase having no liquid crystal phase. It is a general term for compounds mixed in a product. This compound has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod-like. A "polymerizable compound" is a compound added for the purpose of forming a polymer in a composition. Liquid crystal compounds with alkenyl are not polymerizable in that sense.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are added to the liquid crystal composition as needed. To. The proportion of the liquid crystal compound is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive even when the additive is added. The ratio of the additive is expressed as a weight percentage (% by weight) based on the weight 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 weight of the liquid crystal compound. Parts per million (ppm) by weight may also be used. The ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.

The "upper limit temperature of the nematic phase" may be abbreviated as the "upper limit temperature". The "lower limit temperature of the nematic phase" may be abbreviated as the "lower limit temperature". "High resistivity" means that the composition has a large resistivity not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase in the initial stage, and after long-term use, it reaches the upper limit temperature of the nematic phase as well as room temperature. It means that it has a large resistivity even at a close temperature. "Large voltage retention" means that the element has a large voltage retention not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase in the initial stage, and after long-term use, not only the room temperature but also the upper limit temperature of the nematic phase. It means that it has a large voltage retention even at a temperature close to. The characteristics of the composition or device may be examined before and after the aging test (including the accelerated deterioration test). The expression "increase the dielectric anisotropy" means that when the composition has a positive dielectric anisotropy, its value increases positively, and the composition has a negative dielectric anisotropy. When it is a thing, it means that its value increases negatively.

The compound represented by the formula (1) may be abbreviated as "compound (1)". At least one compound selected from the group of compounds represented by the formula (1) may be abbreviated as "Compound (1)". "Compound (1)" means one compound represented by the formula (1), 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'A'" means that the number of'A'is arbitrary. The expression "at least one'A'may be replaced by'B'" is that when the number of'A's is 1, the position of the'A'is arbitrary and the number of'A's is 2. When there is more than one, their positions can be selected without limitation. This rule also applies to the expression "at least one'A'has been replaced by a'B'".

Expressions such as "at least one -CH _2- may be replaced by -O-" are used herein. In this case, −CH ₂ −CH ₂ −CH ₂₋ may be converted to −O−CH ₂₋ O− by replacing the non-adjacent −CH ₂₋ with −O−. However, the adjacent −CH ₂₋ is not replaced by −O−. This is because -O-O-CH _2- (peroxide) is produced by this replacement. That is, this expression includes both "one -CH _2- may be replaced by -O-" and "at least two non-adjacent -CH _2- may be replaced by -O-". means. This rule applies not only to the replacement with -O-, but also with the replacement with divalent groups such as -CH = CH- and -COO-.

In the chemical formulas of the component compounds, with symbols of terminal groups R ¹ to a plurality of compounds. In these compounds, two groups represented by any two of R ¹ may be may be the same or different. For example, there are cases where R ^{1 of} compound (1-1) is ethyl and R ¹ of compound (1-2) is ethyl. In some cases, R ^{1 of} compound (1-1) is ethyl and R ¹ of compound (1-2) is propyl. This rule also applies to symbols such as other end groups. In equation (1), when the subscript'a'is 2, there are two rings B. In this compound, the two rings represented by the two rings B may be the same or different. This rule also applies to any two rings B when the subscript'a'is greater than 2. This rule, Z ^3, applies to such rings C.

2-Fluoro-1,4-phenylene means the following two divalent groups. In the chemical formula, fluorine may be left-facing (L) or right-facing (R). This rule also applies to asymmetric divalent groups generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl. This rule also applies to divalent binding groups such as carbonyloxy (-COO- or -OCO-).

The alkyl of the liquid crystal compound is linear or branched and does not contain cyclic alkyl. Linear alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. The configuration for 1,4-cyclohexylene is preferably trans over cis in order to raise the upper temperature limit.

The present invention includes the following items.

式（１）および式（２）において、Ｒ^１は、炭素数１から１２のアルキルまたは炭素数２から１２のアルケニルであり、これらの基において、少なくとも１つの−ＣＨ_２−は、−Ｏ−で置き換えられてもよく；Ｒ^２およびＲ^３は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素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、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は、テトラヒドロピラン−２，５−ジイルまたは１，３−ジオキサン−２，５−ジイルであり；環Ｂは独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，３−ジフルオロ−１，４−フェニレン、２，６−ジフルオロ−１，４−フェニレン、ピリミジン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはテトラヒドロピラン−２，５−ジイルであり；Ｚ^１およびＺ^２は独立して、単結合、エチレン、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、ここでＺ^１またはＺ^２のうち少なくとも１つはジフルオロメチレンオキシであり；Ｘ^１およびＸ^２は独立して、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；ａは０、１、２、または３であり；ｎは０、１、２、または３である。 Item 1. Contains at least one compound selected from the group of compounds represented by the formula (1) as the first component and at least one compound selected from the group of compounds represented by the formula (2) as the second component. A liquid crystal composition having a nematic phase.

In formulas (1) and (2), R ¹ is an alkyl having 1 to 12 carbon atoms or an alkenyl having 2 to 12 carbon atoms, and in these groups, at least one −CH ₂ − is −O−. R ² and R ³ may be independently replaced by an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, and at least one hydrogen being fluorine or chlorine. An alkyl having 1 to 12 carbon atoms replaced, or an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine; ring A is tetrahydropyran-2,5-diyl or 1,3. -Dioxane-2,5-diyl; Ring B is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2 , 3-Difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidin-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5 -Diyl; Z ¹ and Z ² are independently single-bonded, ethylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy, where at least one of Z ¹ or Z ² is difluoromethyleneoxy. Yes; X ¹ and X ² are independently hydrogen or fluorine; Y ¹ is fluorine, chlorine, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine, at least one hydrogen. Is an alkoxy having 1 to 12 carbon atoms replaced with fluorine or chlorine, or at least one hydrogen is an alkenyloxy having 2 to 12 carbon atoms replaced with fluorine or chlorine; a is 0, 1, 2, or 3 ; N is 0, 1, 2, or 3.

式（１−１）から式（１−９）において、Ｒ^１は、炭素数１から１２のアルキルまたは炭素数２から１２のアルケニルであり、これらの基において、少なくとも１つの−ＣＨ_２−は、−Ｏ−で置き換えられてもよく；環Ｂは独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，３−ジフルオロ−１，４−フェニレン、２，６−ジフルオロ−１，４−フェニレン、ピリミジン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはテトラヒドロピラン−２，５−ジイルであり；Ｘ^１およびＸ^２は独立して、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；ｎは０、１、２、または３である。 Item 2. Item 2. The liquid crystal composition according to Item 1, which contains at least one compound selected from the group of compounds represented by formulas (1-1) to (1-9) as a first component.

In formulas (1-1) to (1-9), R ¹ is an alkyl having 1 to 12 carbon atoms or an alkenyl having 2 to 12 carbon atoms, and in these groups, at least one −CH ₂ − is , -O- may be replaced; ring B is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2 , 3-Difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidin-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5 -Diyl; X ¹ and X ² are independently hydrogen or fluorine; Y ¹ is fluorine, chlorine, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine, at least. One hydrogen is an alkoxy having 1 to 12 carbon atoms replaced with fluorine or chlorine, or at least one hydrogen is an alkenyloxy having 2 to 12 carbon atoms replaced with fluorine or chlorine; n is 0, 1, 2 , Or 3.

式（１−１−１）から式（１−１−４）、式（１−２−１）から式（１−２−５）、式（１−３−１）から式（１−３−５）、式（１−５−１）、式（１−６−１）、式（１−７−１）から式（１−７−５）、式（１−８−１）から式（１−８−５）および式（１−９−１）において、Ｒ^１は、炭素数１から１２のアルキルまたは炭素数２から１２のアルケニルであり、これらの基において、少なくとも１つの−ＣＨ_２−は、−Ｏ−で置き換えられてもよく；Ｘ^１およびＸ^２は独立して、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；ｎは０、１、２、または３である。 Item 3. As the first component, formulas (1-1-1) to formulas (1-1-4), formulas (1-2-1) to formulas (1-2-5), and formulas (1-3-1) to formulas (1-3-5), formula (1-5-1), formula (1-6-1), formula (1-7-1) to formula (1-7-5), formula (1-8-) Item 2. The liquid crystal composition according to Item 1 or 2, which contains at least one compound selected from the group of compounds represented by the formulas (1-8-5) and (1-9-1) from 1).

Formulas (1-1-1) to formulas (1-1-4), formulas (1-2-1) to formulas (1-2-5), formulas (1-3-1) to formulas (1-3) -5), formula (1-5-1), formula (1-6-1), formula (1-7-1) to formula (1-7-5), formula (1-8-1) to formula In (1-8-5) and formula (1-9-1), R ¹ is an alkyl having 1 to 12 carbon atoms or an alkenyl having 2 to 12 carbon atoms, and at least one -CH in these groups. ₂ − may be replaced with −O −; X ¹ and X ² are independently hydrogen or fluorine; Y ¹ is fluorine, chlorine, at least one hydrogen replaced with fluorine or chlorine. Alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine, or alkenyloxy with 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine. Yes; n is 0, 1, 2, or 3.

Item 4. Item 2. The liquid crystal composition according to any one of Items 1 to 3, wherein the ratio of the first component is in the range of 1% by weight to 30% by weight, and the ratio of the second component is in the range of 5% by weight to 70% by weight. Stuff.

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、２−フルオロ−１，４−フェニレン、２，３−ジフルオロ−１，４−フェニレン、２，６−ジフルオロ−１，４−フェニレン、ピリミジン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはテトラヒドロピラン−２，５−ジイルであり；Ｚ^３は、単結合、エチレン、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^３およびＸ^４は独立して、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 5. Item 6. The liquid crystal composition according to any one of Items 1 to 4, which contains at least one compound selected from the group of compounds represented by the formula (3) as a third component.

In formula (3), ^{R 4} is alkyl of from 1 to 12 carbons, alkenyl alkoxy of 1 to 12 carbons, or 2 to 12 carbons; ring C is 1,4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3- Dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z ³ is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy; X ³ and X ⁴ are independently hydrogen. Or fluorine; Y ² is fluorine, chlorine, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, and 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine. Aalkoxy, or an alkenyloxy having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; b is 1, 2, 3, or 4.

式（３−１）から式（３−３５）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。 Item 6. Item 2. The liquid crystal composition according to any one of Items 1 to 5, which contains at least one compound selected from the group of compounds represented by the formulas (3-1) to (3-35) as the third component. Stuff.

In the formula (3-35) from equation (3-1), ^{R 4} is an alkenyl alkyl of 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 2 to 12 carbons.

Item 7. Item 5. The liquid crystal composition according to Item 5 or 6, wherein the proportion of the third component is in the range of 10% by weight to 80% by weight.

式（４）において、Ｒ^５およびＲ^６は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、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Ｄおよび環Ｅは独立して、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、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、またはカルボニルオキシであり；ｃは、１、２、または３であり；ｃが１であるときの環Ｅは、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−フェニレンである。 Item 8. Item 6. The liquid crystal composition according to any one of Items 1 to 7, further containing at least one compound selected from the group of compounds represented by the formula (4) as the fourth component.

In formula (4), R ⁵ and R ⁶ are independently an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, or at least one hydrogen being fluorine or chlorine. It is an alkenyl having 2 to 12 carbon atoms replaced; rings D and ring E are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5. -Difluoro-1,4-phenylene; Z ⁴ is single bond, ethylene, or carbonyloxy; c is 1, 2, or 3; ring E when c is 1 is 1. , 4-Phenylene, 2-Fluoro-1,4-Phenylene, or 2,5-Difluoro-1,4-Phenylene.

式（４−１）から式（４−１２）において、Ｒ^５およびＲ^６は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、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 9. Item 2. The liquid crystal composition according to any one of Items 1 to 8, which contains at least one compound selected from the group of compounds represented by the formulas (4-1) to (4-12) as the fourth component. Stuff.

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

Item 10. Item 8. The liquid crystal composition according to Item 8 or 9, wherein the proportion of the fourth component is in the range of 5% by weight to 60% by weight.

式（５）において、Ｒ^７およびＲ^８は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、または炭素数２から１２のアルケニルオキシであり；環Ｆおよび環Ｉは独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレン、またはテトラヒドロピラン−２，５−ジイルであり；環Ｇは、２，３−ジフルオロ−１，４−フェニレン、２−クロロ−３−フルオロ−１，４−フェニレン、２，３−ジフルオロ−５−メチル−１，４−フェニレン、３，４，５−トリフルオロナフタレン−２，６−ジイル、または７，８−ジフルオロクロマン−２，６−ジイルであり；Ｚ^５およびＺ^６は独立して、単結合、エチレン、カルボニルオキシ、またはメチレンオキシであり；ｄは、１、２、または３であり、ｅは、０または１であり、ｄとｅとの和は３以下である。 Item 11. Item 6. The liquid crystal composition according to any one of Items 1 to 10, which contains at least one compound selected from the group of compounds represented by the formula (5) as a fifth component.

In formula (5), R ⁷ and R ⁸ are independently composed of an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, or an alkenyloxy having 2 to 12 carbon atoms. Yes; Rings F and I are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine. , Or tetrahydropyran-2,5-diyl; ring G 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-trifluoro-2,6-diyl or 7,8-be difluorochroman-2,6-diyl; ^{Z 5} and ^{Z 6} are each independently , Single bond, ethylene, carbonyloxy, or methyleneoxy; d is 1, 2, or 3, e is 0 or 1, and the sum of d and e is 3 or less.

式（５−１）から式（５−２２）において、Ｒ^７およびＲ^８は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、または炭素数２から１２のアルケニルオキシである。 Item 12. Item 2. The liquid crystal composition according to any one of Items 1 to 11, which contains at least one compound selected from the group of compounds represented by the formulas (5-1) to (5-22) as the fifth component. Stuff.

In formulas (5-1) to (5-22), R ⁷ and R ⁸ are independently alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or It is an alkenyloxy having 2 to 12 carbon atoms.

Item 13. Item 2. The liquid crystal composition according to Item 11 or 12, wherein the proportion of the fifth component is in the range of 3% by weight to 30% by weight.

Item 14. The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy (measured at 25 ° C.) at a wavelength of 589 nm is 0.07 or higher, and the dielectric anisotropy (measured at 25 ° C.) at a frequency of 1 kHz is 2. Item 2. The liquid crystal composition according to any one of Items 1 to 13.

Item 15. A liquid crystal display device containing the liquid crystal composition according to any one of Items 1 to 14.

Item 16. Item 15. The liquid crystal display element according to Item 15, wherein the operation mode of the liquid crystal display element is TN mode, ECB mode, OCB mode, IPS mode, FFS mode, or FPA mode, and the drive method of the liquid crystal display element is the active matrix method. ..

Item 17. Use of the liquid crystal composition according to any one of Items 1 to 14 in a liquid crystal display device.

The present invention also includes the following sections. (A) The above composition further containing at least one of additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound. Stuff. (B) AM device containing the above composition. (C) The above composition further containing a polymerizable compound, and a polymer-supported orientation (PSA) type AM device containing this composition. (D) A polymer-supported orientation (PSA) type AM device containing the above composition 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 device containing the above composition. (G) Use of the above composition as a composition having a nematic phase. (H) Use as an optically active composition by adding an optically active compound to the above composition.

The composition of the present invention will be described in the following order. First, the composition of the composition will be described. Secondly, the main properties of the constituent compounds and the main effects of this compound on the composition will be described. Third, the combination of ingredients in the composition, the preferred proportions of the ingredients and the rationale thereof will be described. Fourth, preferred forms of the constituent compounds will be described. Fifth, preferred component compounds are shown. Sixth, additives that may be added to the composition will be described. Seventh, a method for synthesizing a component compound will be described. Finally, the use of the composition will be described.

First, the composition of the composition will be described. The compositions of the present invention are classified into composition A and composition B. The composition A includes a liquid crystal compound selected from the compound (1), the compound (2), the compound (3), the compound (4), and the compound (5), as well as other liquid crystal compounds, additives, and the like. May be further contained. The "other liquid crystal compound" is a liquid crystal compound different from the compound (1), the compound (2), the compound (3), the compound (4), and the compound (5). Such compounds are mixed into the composition for the purpose of further adjusting the properties. Additives include optically active compounds, antioxidants, UV absorbers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like.

The composition B is substantially composed of only a liquid crystal compound selected from the compound (1), the compound (2), the compound (3), the compound (4), and the compound (5). "Substantially" means that the composition may contain additives but does not contain other liquid crystal compounds. The composition B has a smaller number of components than the composition A. The composition B is preferable to the composition A from the viewpoint of reducing the cost. Composition A is preferable to composition B from the viewpoint that the properties can be further adjusted by mixing other liquid crystal compounds.

Secondly, the main properties of the constituent compounds and the main effects of this compound on the composition will be described. The main properties of the component compounds are summarized in Table 2 based on the effects of the present invention. In the symbols in Table 2, L means large or high, M means medium, and S means small or low. The symbols L, M, and S are classifications based on qualitative comparisons between the constituent compounds, and 0 (zero) means that the value is close to zero.

When the component compound is mixed with the composition, the main effects of the component compound on the properties of the composition are as follows. Compound (1) increases the dielectric anisotropy of liquid crystal molecules. Compound (2) lowers the viscosity or lowers the lower limit temperature. Compound (3) increases the dielectric anisotropy. Compound (4) raises the upper limit temperature or lowers the lower limit temperature. Compound (5) increases the dielectric constant in the minor axis direction.

Thirdly, the combination of the components in the composition, the preferable ratio of the component compounds, and the rationale thereof will be described. Preferred combinations of components in the composition are 1st component + 2nd component, 1st component + 2nd component + 3rd component, 1st component + 2nd component + 4th component, 1st component + 2nd component + 1st component. Five components, first component + second component + third component + fourth component, first component + second component + third component + fifth component, first component + second component + fourth component + fifth component , Or the first component + the second component + the third component + the fourth component + the fifth component. A more preferable combination is the first component + the second component + the third component + the fourth component.

The preferable ratio of the first component is about 1% by weight or more in order to increase the dielectric constant of the liquid crystal molecule in the long axis direction, and about 30% by weight or less in order to lower the lower limit temperature. A more preferred ratio is in the range of about 1% by weight to about 20% by weight. A particularly preferred proportion is in the range of about 1% by weight to about 15% by weight.

The preferred proportion of the second component is about 5% by weight or more for lowering the viscosity and about 70% by weight or less for increasing the dielectric anisotropy. A more preferred ratio is in the range of about 10% by weight to about 65% by weight. A particularly preferred proportion is in the range of about 20% by weight to about 60% by weight.

The preferable ratio of the third component is about 10% by weight or more in order to increase the dielectric anisotropy, and about 80% by weight or less in order to lower the lower limit temperature. A more preferred proportion is in the range of about 15% by weight to about 70% by weight. A particularly preferred proportion is in the range of about 20% by weight to about 60% by weight.

The preferred proportion of the fourth component is about 5% by weight or more in order to raise the upper limit temperature or lower the viscosity, and about 60% by weight or less in order to raise the dielectric anisotropy. A more preferred ratio is in the range of about 5% by weight to about 50% by weight. A particularly preferable ratio is in the range of about 10% by weight to about 40% by weight.

The preferable ratio of the fifth component is about 3% by weight or more in order to increase the dielectric constant of the liquid crystal molecule in the minor axis direction, and about 30% by weight or less in order to lower the lower limit temperature. A more preferred proportion is in the range of about 3% by weight to about 20% by weight. A particularly preferred proportion is in the range of about 3% by weight to about 10% by weight.

Fourth, preferred forms of the constituent compounds will be described. In formulas (1), (2), formula (3), formula (4), and formula (5), R ¹ is an alkyl having 1 to 12 carbon atoms or an alkenyl having 2 to 12 carbon atoms. Under the basis of, at least one −CH ₂₋ may be replaced by −O−. Preferred R ¹ is 2 to 6 to reduce the viscosity. R ² and R ³ are independently from alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, and 1 carbon with at least one hydrogen replaced by fluorine or chlorine. Twelve alkyl, or alkenyl with 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. Preferred R ² or R ³ is an alkenyl having 2 to 12 carbon atoms to reduce the viscosity and an alkyl having 1 to 12 carbon atoms to increase stability against ultraviolet rays and heat. R ⁴ is alkenyl alkyl of 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 2 to 12 carbons. Preferred R ⁴ is, in order to increase the stability to ultraviolet light or heat, is alkyl of 1 to 12 carbons. R ⁵ and R ⁶ are independently alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, or 2 carbons in which at least one hydrogen is replaced with fluorine or chlorine. To 12 alkenyl. Preferred R ⁵ or R ⁶ is an alkenyl having 2 to 12 carbon atoms to reduce the viscosity and an alkyl having 1 to 12 carbon atoms to increase stability against ultraviolet rays and heat. R ⁷ and R ⁸ are independently alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or alkenyloxy with 2 to 12 carbon atoms. Preferred R ⁷ or R ⁸ is an alkyl having 1 to 12 carbon atoms to increase stability against ultraviolet rays and heat, and an alkoxy having 1 to 12 carbon atoms to increase the dielectric constant in the minor axis direction.

Preferred alkyls are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. More preferred alkyls are methyl, ethyl, propyl, butyl, or pentyl to reduce viscosity.

Preferred alkoxys are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. More preferred alkoxys for reducing viscosity are methoxy or ethoxy.

Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More preferred alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl to reduce the viscosity. The preferred configuration of -CH = CH- in these alkenyl 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, 3-hexenyl for the purpose of lowering the viscosity. Sith is preferred for alkenyl such as 2-butenyl, 2-pentenyl, 2-hexenyl. Of these alkenyl, straight chain alkenyl is preferred over branched.

Preferred alkenyloxys are vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. More preferred alkenyloxy to reduce viscosity are allyloxy or 3-butenyloxy.

Preferred examples of alkyl in which at least one hydrogen is replaced with fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl. , Or 8-fluorooctyl. More preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl to increase the dielectric anisotropy.

Preferred examples of alkenyl in which at least one hydrogen is replaced with 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 to reduce the viscosity.

または

であり、好ましくは

である。 Ring A is tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl. The preferred ring A is 1,3-dioxane-2,5-diyl. Ring B is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, It is 2,6-difluoro-1,4-phenylene, pyrimidin-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl. The preferred ring B is 1,4-cyclohexylene to raise the upper temperature limit and 1,4-phenylene to raise the optical anisotropy. Tetrahydropyran-2,5-diyl is

Or

And preferably

Is.

Ring C is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene. , Pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl. Preferred ring C is 1,4-cyclohexylene to increase the upper temperature limit, 1,4-phenylene to increase the optical anisotropy, and 2,6-difluoro to increase the dielectric anisotropy. -1,4-Phenylene. Rings D and E are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. Preferred ring D or ring E is 1,4-cyclohexylene to lower the viscosity or to raise the upper temperature limit and 1,4-phenylene to lower the lower limit temperature. Rings F and I are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine, or Tetrahydropyran-2,5-diyl. Preferred ring F or ring I is 1,4-cyclohexylene to reduce viscosity, tetrahydropyran-2,5-diyl to increase dielectric anisotropy, and to increase optical anisotropy. It is 1,4-phenylene. Ring G is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4. 5-Trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl. The preferred ring G is 2,3-difluoro-1,4-phenylene to reduce the viscosity, 2-chloro-3-fluoro-1,4-phenylene to reduce the optical anisotropy, and the dielectric constant. 7,8-Difluorochroman-2,6-diyl to increase anisotropy.

Z ¹ and Z ² are independently single bonds, ethylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy, where at least one of Z ¹ or Z ² is difluoromethyleneoxy. Preferred Z ¹ or Z ² is a single bond to reduce viscosity and difluoromethyleneoxy to increase dielectric anisotropy. Z ³ is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy. Preferred Z ³ is a single bond to reduce viscosity and difluoromethyleneoxy to increase dielectric anisotropy. Z ⁴ is a single bond, ethylene or carbonyloxy. Preferred Z ⁴ is a single bond to reduce viscosity. Z ⁵ and Z ⁶ are independently single bonds, ethylene, carbonyloxy, or methyleneoxy. Preferred Z ⁶ or Z ⁷ is a single bond to reduce the viscosity, ethylene to lower the lower limit temperature, and methyleneoxy to increase the dielectric anisotropy.

X ¹ , X ² , X ³ , and X ⁴ are independently hydrogen or fluorine. Preferred X ¹ , X ² , X ³ or X ⁴ are fluorine to increase the dielectric anisotropy.

Y ¹ and Y ² are fluorine, chlorine, alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, and alkoxy having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine. , Or an alkenyloxy having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. Preferred Y ¹ or Y ² is fluorine to lower the lower limit temperature.

a is 0, 1, 2, or 3. Preferred a is 0 or 1 to lower the lower limit temperature and 2 or 3 to raise the upper limit temperature. b is 1, 2, 3, or 4. The preferred b is 2 to lower the lower limit temperature and 3 to raise the upper limit temperature. c is 1, 2, or 3, and when c is 1, the ring E is 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-. Phenylene. The preferred c is 1 to reduce the viscosity and 2 or 3 to raise the upper temperature limit. d is 1, 2, or 3, e is 0 or 1, and the sum of d and e is 3 or less. The preferred d is 1 to reduce the viscosity and 2 or 3 to raise the upper temperature limit. Preferred e is 0 to lower the viscosity and 1 to lower the lower limit temperature. n is 0, 1, 2, or 3. Preferred n is 2 or 3 to increase the dielectric anisotropy.

Fifth, preferred component compounds are shown. Preferred compounds (1) are compounds (1-1) to compounds (1-9) according to Item 2. In these compounds, it is preferred that at least one of the first components is compound (1-2), (1-3), or (1-5). At least two of the first components are compound (1-2) and compound (1-3), compound (1-2) and compound (1-5), or compound (1-3) and compound (1-5). The combination of is preferable.

Preferred compounds (3) are compounds (3-1) to compounds (3-35) according to Item 6. 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 (3-27), compound (3-29), or compound (3-30) is preferred. At least two of the third components are compound (3-12) and compound (3-15), compound (3-14) and compound (3-27), compound (3-18) and compound (3-24), It is preferably a combination of compound (3-18) and compound (3-29), compound (3-24) and compound (3-29), or compound (3-29) and compound (3-30).

Preferred compounds (4) are compounds (4-1) to compounds (4-12) according to Item 9. In these compounds, at least one of the fourth components is compound (4-2), compound (4-4), compound (4-5), compound (4-6), compound (4-8), or compound. (4-12) is preferable. At least two of the fourth components are compound (4-2) and compound (4-4), compound (4-2) and compound (4-6), or compound (4-4) and compound (4-6). The combination of is preferable.

Preferred compounds (5) are compounds (5-1) to compounds (5-22) according to Item 12. In these compounds, at least one of the fifth components is compound (5-1), compound (5-3), compound (5-4), compound (5-6), compound (5-8), or compound. It is preferably (5-10). At least two of the fifth components are compound (5-1) and compound (5-6), compound (5-3) and compound (5-6), compound (5-3) and compound (5-10), It is preferably a combination of compound (5-4) and compound (5-6), compound (5-4) and compound (5-8), or compound (5-6) and compound (5-10).

Sixth, additives that may be added to the composition will be described. Such additives include optically active compounds, antioxidants, UV absorbers, 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 the helical structure of the liquid crystal to give a twist angle. Examples of such compounds are compound (6-1) to compound (6-5). The preferred proportion of the optically active compound is about 5% by weight or less. A more preferred ratio is in the range of about 0.01% by weight to about 2% by weight.

An antioxidant is composed to prevent a decrease in resistivity due to heating in the atmosphere, or to maintain a large voltage retention not only at room temperature but also at temperatures close to the upper limit temperature after long-term use of the device. It is added to the thing. Preferred examples of the antioxidant are compound (7) in which t is an integer of 1 to 9.

In compound (7), the preferred t is 1, 3, 5, 7, or 9. A more preferable t is 7. Since the compound (7) having t of 7 has low volatility, it is effective in maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after the device has been used for a long time. The preferable ratio of the antioxidant is about 50 ppm or more in order to obtain the effect, and is about 600 ppm or less so as not to lower the upper limit temperature or raise the lower limit temperature. A more preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferred examples of the UV absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as sterically hindered amines are also preferred. The preferable ratio of these absorbents and stabilizers is about 50 ppm or more in order to obtain the effect, and about 10,000 ppm or less so as not to lower the upper limit temperature or raise the lower limit temperature. A more preferred ratio is in the range of about 100 ppm to about 10000 ppm.

Dichroic dyes such as azo dyes, anthraquinone dyes, etc. are added to the composition to accommodate devices in GH (guest host) mode. The preferred proportion of dye is in the range of about 0.01% by weight to about 10% by weight. To prevent foaming, a defoaming agent such as dimethyl silicone oil or methyl phenyl silicone oil is added to the composition. The preferable ratio of the defoaming agent is about 1 ppm or more in order to obtain the effect, and about 1000 ppm or less in order to prevent display defects. A more preferred ratio is in the range of about 1 ppm to about 500 ppm.

Polymerizable compounds are added to the composition to accommodate polymer-supported orientation (PSA) type devices. Preferred examples of the polymerizable compound are compounds having a polymerizable group such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxylane, oxetane), vinyl ketone and the like. A more preferred example is a derivative of acrylate or methacrylate. The preferable ratio of the polymerizable compound is about 0.05% by weight or more in order to obtain the effect, and about 10% by weight or less in order to prevent display defects. A more preferred ratio is in the range of about 0.1% by weight to about 2% by weight. The polymerizable compound is polymerized by irradiation with ultraviolet rays. Polymerization may be carried out in the presence of an initiator such as a photopolymerization initiator. Appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those of skill in the art and are described in the literature. For example, the photoinitiators Irgacure 651®, Irgacure 184® (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF) are suitable for radical polymerization. The preferred proportion of photopolymerization initiator is in the range of about 0.1% by weight to about 5% by weight based on the weight of the polymerizable compound. A more preferred ratio is in the range of about 1% by weight to about 3% by weight.

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 polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine and the like.

Seventh, a method for synthesizing a component compound will be described. These compounds can be synthesized by known methods. An example of the synthesis method. The method for synthesizing compound (1) is described in the section of Examples. Compound (2) is synthesized by the method described in JP-A-59-176221. Compound (3-2) and compound (3-8) are synthesized by the method described in JP-A-2-233626. Compound (4-6) is synthesized by the method described in Special Table 2006-503130. Compound (5-1) and compound (5-6) are synthesized by the method published in JP-A-2-503441. Antioxidants are commercially available. The compound of formula (7) where t is 1 can be obtained from Sigma-Aldrich Corporation. Compound (7) and the like having t of 7 are synthesized by the method described in US Pat. No. 3,660,505.

Compounds for which synthetic methods are not described are Organic Syntheses, John Wiley & Sons, Inc, Organic Reactions, John Wiley & Sons, Inc, Comprehensive Organic. It can be synthesized by the methods described in books such as Synthesis, Pergamon Press) and New Experimental Chemistry Course (Maruzen). The composition is prepared from the compound thus obtained by a known method. For example, the constituent compounds are mixed and dissolved by heating.

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

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

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

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

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

Chloroform, hexane or the like may be used as the solvent for diluting the sample. The following capillary columns may be used to separate the constituent compounds. 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 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 proportion of the liquid crystal compound contained in the composition may be calculated by the following method. A mixture of liquid crystal compounds is detected by gas chromatography (FID). The area ratio of the peak in the gas chromatogram corresponds to the ratio (weight ratio) of the liquid crystal compound. When the capillary column described above is used, the correction coefficient of each liquid crystal compound may be regarded as 1. Therefore, the proportion (% by weight) of the liquid crystal compound can be calculated from the area ratio of the peak.

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

The following mother liquid crystal was used. The ratio of the component compounds is shown in% by weight.

Measurement method: The characteristics were measured by the following method. Many of these are methods described in the JEITA standard (JEITA ED-2521B) deliberated and enacted by the Japan Electronics and Information Technology Industries Association (hereinafter referred to as JEITA), or modified. It was a method. A thin film transistor (TFT) was not attached to the TN element used for the measurement.

(1) Upper limit temperature of nematic phase (NI; ° C.): A sample was placed on a hot plate of a melting point measuring device equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature when a part of the sample changed from the nematic phase to the isotropic liquid was measured.

(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, _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.

(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 the measurement.

(4) Viscosity (rotational viscosity; γ1; measured at 25 ° C.; mPa · s): The measurement was carried out according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). I obeyed. The sample was placed in a TN device having a twist angle of 0 ° and a distance (cell gap) between the two glass substrates of 5 μm. A stepwise application was applied to this device in 0.5 V increments in the range of 16 V to 19.5 V. After no application for 0.2 seconds, application was repeated under the conditions of only one square 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 calculation formula (8) described on page 40 in the paper by M. Imai et al. The value of the dielectric anisotropy required for this calculation was obtained 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 light having a wavelength of 589 nm and using an Abbe refractometer with a polarizing plate attached to the eyepiece. After rubbing the surface of the main prism in one direction, the sample was dropped onto the main prism. The refractive index n‖ was measured when the direction of polarization was parallel to the direction of rubbing. The refractive index n⊥ was measured when the direction of polarization was perpendicular to the direction of rubbing. The value of optical anisotropy was calculated from the equation Δn = n ‖ −n ⊥.

(6) Dielectric constant anisotropy (Δε; measured at 25 ° C.): The sample was placed in a TN element having a distance (cell gap) between two glass substrates of 9 μm and a twist angle of 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 long axis direction was measured. A sine wave (0.5V, 1kHz) was applied to this device, and the dielectric constant (ε⊥) of the liquid crystal molecule in the minor axis direction was measured 2 seconds later. The value of permittivity anisotropy was calculated from the equation Δε ＝ ε‖−ε⊥.

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

(8) Voltage retention rate (VHR-1; measured at 25 ° C.;%): The TN element used for the measurement had a polyimide alignment film, and the distance (cell gap) between the two glass substrates was 5 μm. .. This element was sealed with an adhesive that cures with ultraviolet light after the sample was placed. A pulse voltage (60 microseconds at 5 V) was applied to the TN element to charge it. The decaying voltage was measured with a high-speed voltmeter for 16.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit period was determined. Area B was the area when there was no attenuation. The voltage holding ratio is expressed as a percentage of the area A with respect to the area B.

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

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

(11) Voltage retention rate (VHR-4; measured at 25 ° C.;%): After heating the TN element into which the sample was injected for 500 hours in a constant temperature bath at 80 ° C., the voltage retention rate was measured and stability against heat was measured. Was evaluated. In the measurement of VHR-4, the voltage decayed for 16.7 milliseconds was measured. Compositions with large VHR-4 have great stability to heat.

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

(13) Elastic constant (K; measured at 25 ° C.; pN): An HP4284A type LCR meter manufactured by Yokogawa Hewlett-Packard Co., Ltd. was used for the measurement. The sample was placed in a horizontally oriented element in which the distance (cell gap) between the two glass substrates was 20 μm. A charge of 0 to 20 volts was applied to this device, and the capacitance and applied voltage were measured. Fit the measured capacitance (C) and applied voltage (V) values using the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), formulas (2.98) and formula (2.11) on page 75. Then, the values of K11 and K33 were obtained from the formula (2.99). Next, K22 was calculated using the values of K11 and K33 obtained earlier in the formula (3.18) on page 171 of the same. The elastic constant was represented by the average value of K11, K22, and K33 obtained in this way.

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

(15) Spiral pitch (P; measured at room temperature; μm): The spiral pitch was measured by the wedge method. See "LCD Handbook", page 196 (published in 2000, Maruzen). The sample was injected into a wedge-shaped cell, allowed to stand at room temperature for 2 hours, and then the spacing of the dispersion lines (d2-d1) 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 expressed as θ. P = 2 × (d2-d1) × tan θ.

(16) Permittivity in the minor axis direction (ε⊥; measured at 25 ° C.): The sample was placed in a TN element having a distance (cell gap) between two glass substrates of 9 μm and a twist angle of 80 degrees. .. A sine wave (0.5V, 1kHz) was applied to this device, and the dielectric constant (ε⊥) of the liquid crystal molecule in the minor axis direction was measured 2 seconds later.

Compound (1-2-4) was synthesized by the method described below.

Step 1 Under a nitrogen atmosphere, compound (S101) (0.90 g, 8.5 mmol), p-toluenesulfonic acid monohydrate (0.05 g, 0.25 mmol) and acetone (27 ml) were placed in a reaction vessel. , Stirred for 12 hours at room temperature. Triethylamine was added to the reaction mixture, and the solvent was distilled off with an evaporator. The residue was purified by silica gel chromatophy to obtain compound (S102).

Second step Under a nitrogen atmosphere, the compound (S102) (1.1 g, 7.8 mmol), sodium hydride (60%; 0.47 g, 11.7 mmol) and THF (11 ml) obtained in the first step were reacted. It was placed in a container and stirred at room temperature for 30 minutes. 1-Iodoethane (3.6 g, 23.4 mmol) was added thereto, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was poured into pure water, and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with pure water and saturated brine, dried over magnesium sulfate, and the solvent was distilled off with an evaporator. The residue was purified by silica gel chromatophy to obtain compound (S103).

Third step The compound (S103) (0.95 g, 5.4 mmol), p-toluenesulfonic acid monohydrate (0.1 g, 0.54 mmol), and methanol (4) obtained in the second step under a nitrogen atmosphere. .7 ml) was placed in a reaction vessel and stirred at room temperature for 12 hours. Triethylamine was added to the reaction mixture, and the solvent was distilled off with an evaporator. The residue was purified by silica gel chromatophy to obtain compound (S104).

Step 4 Under a nitrogen atmosphere, the compound (S104) (0.62 g, 4.6 mmol), 4- (difluoro ((2,3', 4', 5'-tetrafluoro- [1]) obtained in the third step , 1'-biphenyl] -4-yl) oxy) methyl) -3,5-difluorobenzaldehyde (2.0 g, 4.6 mmol), p-toluenesulfonic acid monohydrate (0.06 g, 0.32 mmol) , Calcium sulfate (0.6 g, 4.5 mmol), toluene (6 ml) and cyclopropane (6 ml) were placed in a reaction vessel and heated under reflux for 3 hours. After returning the reaction mixture to room temperature, it was poured into pure water and the aqueous layer was extracted with toluene. The combined organic layer was washed with pure water and saturated brine, dried over magnesium sulfate, and the solvent was distilled off with an evaporator. The residue was purified by silica gel chromatophy and recrystallization to obtain compound (1-2-4).

^{1 1} H-NMR (δppm; CDCl ₃ ): 7.34 (dd, 1H, J = 8.4Hz, 8.4Hz), 7.19-7.10 (m, 6H), 5.39 (s, 1H) ) 4.28 (dd, 2H, J = 4.6Hz, 11.8Hz) 3.74 (dd, 2H, J = 11.8Hz, 11.8Hz) 3.45 (q, 2H, J = 7) .0Hz), 3.28 (d, 2H, J = 5.8Hz) 2.43 (m, 1H), 1.19 (t, 3H, J = 7.0Hz).
¹⁹ F-NMR (δppm; CFCl ₃ ): -61.43 (t, 2F, J = 28.5Hz), -111.47 (dt, 2F, J = 11.3Hz, 28.5Hz), -114. 86 (dd, 1F, J = 8.5Hz, 10.6Hz), -134.71 (dd, 2F, J = 9.4Hz, 21.4Hz), 161.72 (tt, 1F, J = 6. 7Hz, 21.4Hz).

Examples of the composition are shown below. The component compounds are represented by symbols based on the definitions in Table 3 below. In Table 3, the molecular configuration for 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 compounds. The proportion (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition. Finally, the characteristic values of the composition are summarized.

[Comparative Example 1]
Example 3 was selected from the compositions disclosed in JP-A-2006-70080. The rationale is that this composition contains a compound similar to compound (1) and compound (2) and has the lowest viscosity. The components and properties of this composition are as follows.
1O3-GHB (F) -F (-) 10%
V-HH-5 (2) 15%
3-HB-O2 (4-1) 5%
V-HHB-1 (4-4) 10%
3-HHB (F, F) -F (3-2) 10%
3-HH2B (F, F) -F (3) 5%
3-H2HB (F, F) -F (3) 5%
3-HBB (F, F) -F (3-8) 10%
2-HHB (F) -F (3) 10%
5-HHB (F) -F (3) 10%
V-HHB (F) -F (3) 10%
NI = 87.8 ° C; Tc <-30 ° C; η = 20.0 mPa · s; Δn = 0.083; Δε = 6.1.

[Comparative Example 2]
Example 3 was selected from the compositions disclosed in JP-A-2011-153202. The rationale is that this composition contains a compound similar to compound (1) and compound (2) and has the lowest viscosity. The components and properties of this composition are as follows.
4-GB (F) B (F, F) XB (F, F) -F (3-27) 4%
5-GB (F) B (F, F) XB (F, F) -F (3-27) 5%
5-HH-V (2) 8%
3-HH-V1 (2) 8%
V-HHB-1 (4-4) 4%
3-BB (F) B (F, F) XB (F, F) -F (3-29) 2%
4-BB (F) B (F, F) XB (F, F) -F (3-29) 8%
5-BB (F) B (F, F) XB (F, F) -F (3-29) 3%
3-HGB (F, F) XB (F, F) -F (3) 3%
4-HGB (F, F) XB (F, F) -F (3) 6%
3-BB (F, F) XB (F, F) -F (3-18) 10%
1-HHXB (F, F) -F (3-4) 6%
3-HHXB (F, F) -F (3-4) 13%
3-GHB (F, F) -F (3-7) 3%
4-GHB (F, F) -F (3-7) 7%
5-GHB (F, F) -F (3-7) 10%
NI = 75.0 ° C.; Tc <-30 ° C.; Δn = 0.100; Δε = 19.9; γ1 = 181.0 mPa · s.

[Example 1]
2O1-GB (F, F) XB (F, F) -F (1-1-3) 2%
1O1-GB (F, F) XB (F) B (F, F) -F (1-2-4) 2%
2O1-GB (F, F) XB (F) B (F, F) -F (1-2-4) 2%
2O1-GB (F) B (F, F) XB (F, F) -F (1-3-4) 2%
3-HH-V (2) 30%
3-HH-V1 (2) 4%
3-HHXB (F, F) -F (3-4) 3%
3-BB (F, F) XB (F, F) -F (3-18) 3%
3-HHB (F) B (F, F) -F (3-20) 3%
3-dhBB (F, F) XB (F, F) -F (3-25) 3%
3-BB (F) B (F, F) XB (F, F) -F (3-29) 3%
4-BB (F) B (F, F) XB (F, F) -F (3-29) 3%
3-HHB-OCF3 (3) 4%
3-HB-O2 (4-1) 4%
V-HHB-1 (4-4) 16%
V2-HHB-1 (4-4) 16%
NI = 98.5 ° C; Tc <-20 ° C; Δn = 0.095; Δε = 5.9; Vth = 1.78V; γ1 = 74.0mPa · s.

[Example 2]
2O1-GB (F) XB (F) B (F) -F (1-2) 3%
3O1-GB (F, F) XB (F) B (F, F) -F (1-2-4) 3%
3-HH-V (2) 25%
5-HH-V (2) 5%
5-HHB (F, F) -F (3-2) 5%
3-HHEB (F, F) -F (3-3) 6%
2-HBB (F, F) -F (3-8) 3%
3-HB (F) B (F, F) -F (3-9) 5%
3-HBEB (F, F) -F (3-10) 3%
3-BBXB (F, F) -F (3-17) 4%
3-BB (F, F) XB (F, F) -F (3-18) 3%
3-BB (F) B (F, F) XB (F, F) -F (3-29) 4%
4-BB (F) B (F, F) XB (F, F) -F (3-29) 3%
5-BB (F) B (F, F) XB (F, F) -F (3-29) 4%
V2-B (2F, 3F) BXB (F, F) -F (3-33) 3%
V-HHB-1 (4-4) 4%
V2-HHB-1 (4-4) 6%
V-HBB-2 (4-5) 5%
5-B (F) BB-3 (4-7) 3%
3-HHEBH-4 (4-10) 3%
NI = 84.8 ° C; Tc <-20 ° C; η = 16.0 mPa · s; Δn = 0.112; Δε = 9.7; Vth = 1.40 V; γ1 = 68.3 mPa · s.

[Example 3]
3O-GB (F, F) XB (F) B (F, F) -F (1-2-4) 2%
4O1-GB (F, F) XB (F) B (F, F) -F (1-2-4) 2%
2O1-GB (F, F) XB (F) B (F) -F (1-2-4) 2%
2-HH-3 (2) 14%
3-HH-V (2) 20%
3-HHB (F, F) -F (3-2) 3%
4-HHEB (F, F) -F (3-3) 3%
5-HB (F) B (F, F) -F (3-9) 4%
2-GB (F, F) XB (F, F) -F (3-14) 3%
3-BB (F) B (F, F) -CF3 (3-16) 3%
3-HHBB (F, F) -F (3-19) 4%
3-BB (F) B (F, F) XB (F) -F (3-28) 3%
4-BB (F) B (F, F) XB (F) -F (3-28) 5%
3-BB (F) B (F, F) XB (F, F) -F (3-29) 5%
3-HB (2F, 3F) BXB (F, F) -F (3-34) 3%
3-BB (2F, 3F) BXB (F, F) -F (3-35) 3%
1-BB-3 (4-2) 3%
V2-HHB-1 (4-4) 6%
1V-HBB-2 (4-5) 4%
5-B (F) BB-3 (4-7) 4%
3-HHEBH-4 (4-10) 4%
NI = 87.6 ° C; Tc <-20 ° C; η = 15.6 mPa · s; Δn = 0.115; Δε = 9.2; Vth = 1.45 V; γ1 = 66.7 mPa · s.

[Example 4]
1O2-GB (F, F) XB (F) B (F, F) -F (1-2-4) 2%
2O1-GB (F, F) XB (F, F) B (F) -F (1-2-5) 2%
4O1-GB (F) B (F, F) XB (F, F) -F (1-3-4) 2%
3-HH-V (2) 33%
5-HHEB (F, F) -F (3-3) 9%
5-GHB (F, F) -F (3-7) 3%
2-BB (F) B (F, F) -F (3-15) 3%
3-BB (F) B (F, F) -F (3-15) 3%
5-HHBB (F, F) -F (3-19) 4%
3-BB (F) B (F, F) XB (F) -F (3-28) 5%
4-BB (F) B (F, F) XB (F) -F (3-28) 4%
3-BB (F) B (F, F) XB (F, F) -F (3-29) 3%
5-BB (F) B (F, F) XB (F, F) -F (3-29) 6%
3-BB (2F, 3F) XB (F, F) -F (3-32) 3%
1-BB-5 (4-2) 4%
V-HHB-1 (4-4) 5%
3-BB (F) B-2V (4-6) 5%
5-HBB (F) B-2 (4-12) 4%
NI = 83.2 ° C; Tc <-20 ° C; η = 18.6 mPa · s; Δn = 0.124; Δε = 10.1; Vth = 1.39 V; γ1 = 79.6 mPa · s.

[Example 5]
1O2O1-GB (F, F) XB (F) B (F, F) -F (1-2-4) 2%
1O1-GB (F) B (F, F) XB (F, F) -F (1-3-4) 2%
2O1-GB (F) B (F, F) XB (F, F) -CF3 (1-3-4) 2%
2-HH-3 (2) 22%
3-HH-V (2) 15%
3-HHB (F, F) -F (3-2) 3%
2-HBB (F, F) -F (3-8) 3%
3-HB (F) B (F, F) -F (3-9) 5%
3-GB (F, F) XB (F) -F (3-13) 3%
3-GB (F, F) XB (F, F) -F (3-14) 3%
2-BB (F, F) XB (F, F) -F (3-18) 3%
3-BB (F) B (F, F) XB (F, F) -F (3-29) 3%
4-BB (F) B (F, F) XB (F, F) -F (3-29) 5%
5-BB (F) B (F, F) XB (F, F) -F (3-29) 7%
5-BB (F) B (F, F) XB (F) B (F, F) -F (3-31) 3%
V-HHB-1 (4-4) 5%
V2-HHB-1 (4-4) 6%
3-BB (F) B-2V (4-6) 5%
5-HBB (F) B-2 (4-12) 3%
NI = 73.8 ° C; Tc <-20 ° C; η = 13.5 mPa · s; Δn = 0.110; Δε = 11.6; Vth = 1.29 V; γ1 = 57.8 mPa · s.

[Example 6]
2O1-GB (F, F) XB (F) B (F) -OCF3 (1-2-4) 2%
3O1-GB (F, F) XB (F, F) B (F) -F (1-2-5) 2%
3O1-GB (F) B (F, F) XB (F, F) -F (1-3-4) 2%
3-HH-V (2) 22%
3-HH-V1 (2) 16%
1-HHB (F, F) -F (3-2) 3%
3-HBB (F, F) -F (3-8) 3%
3-BB (F, F) XB (F, F) -F (3-18) 3%
4-HHB (F) B (F, F) -F (3-20) 3%
5-GB (F) B (F) B (F) -F (3-21) 4%
3-GB (F) B (F, F) XB (F, F) -F (3-27) 3%
3-BB (F) B (F, F) XB (F, F) -F (3-29) 5%
5-BB (F) B (F, F) XB (F, F) -F (3-29) 6%
3-BB (F, F) XB (F) B (F, F) -F (3-30) 3%
3-HB-O2 (4-1) 4%
1-BB-5 (4-2) 3%
V2-HHB-1 (4-4) 3%
3-HBB-2 (4-5) 3%
V-HBB-2 (4-5) 3%
5-B (F) BB-3 (4-7) 4%
3-HBB (2F, 3F) -O2 (5-10) 3%
NI = 82.0 ° C; Tc <-20 ° C; η = 14.5 mPa · s; Δn = 0.118; Δε = 9.5; Vth = 1.47V; γ1 = 62.0 mPa · s.

[Example 7]
4O1-GB (F, F) XB (F) B (F) -F (1-2-4) 2%
2O1-GBB (F, F) XB (F, F) -F (1-3-3) 2%
4O1-GB (F) B (F, F) XB (F) -F (1-3-4) 4%
2O1-GB (F) B (F, F) XB (F) B (F, F) -F
(1-5-1) 2%
3-HH-V (2) 25%
4-HH-V (2) 5%
5-HH-V (2) 7%
1-HHXB (F, F) -F (3-4) 6%
3-HB (F) B (F, F) -F (3-9) 3%
V-HB (F) B (F, F) -F (3-9) 3%
3-HBEB (F, F) -F (3-10) 3%
2-HHBB (F, F) -F (3-19) 3%
5-GB (F) B (F, F) XB (F) -F (3-26) 3%
4-BB (F) B (F, F) XB (F, F) -F (3-29) 5%
5-BB (F) B (F, F) XB (F, F) -F (3-29) 4%
V2-BB-1 (4-2) 9%
3-HHB-3 (4-4) 5%
V2-HHB-1 (4-4) 6%
3-BB (F) B-5 (4-6) 3%
NI = 73.7 ° C; Tc <-20 ° C; η = 10.6 mPa · s; Δn = 0.105; Δε = 9.0; Vth = 1.50 V; γ1 = 45.3 mPa · s.

[Example 8]
2O1-GB (F, F) XB (F, F) -F (1-1-3) 2%
1O1-GB (F, F) XB (F) B (F, F) -F (1-2-4) 2%
2O1-dhB (F, F) XB (F) B (F, F) -F (1-7-4) 2%
3-HH-V (2) 26%
3-HH-V1 (2) 4%
3-HH-VFF (2) 7%
5-HHB (F, F) -F (3-2) 5%
2-HBEB (F, F) -F (3-10) 3%
3-GB (F, F) XB (F, F) -F (3-14) 3%
3-BB (F) B (F, F) -F (3-15) 3%
3-BB (F) B (F, F) -CF3 (3-16) 3%
2-HHB (F) B (F, F) -F (3-20) 3%
3-HHB (F) B (F, F) -F (3-20) 2%
3-HBBXB (F, F) -F (3-23) 6%
3-dhBB (F, F) XB (F, F) -F (3-25) 3%
4-GB (F) B (F, F) XB (F) -F (3-26) 3%
3-BB (F) B (F, F) XB (F) -F (3-28) 4%
3-HB-O2 (4-1) 3%
V2-HHB-1 (4-4) 5%
1-BB (F) B-2V (4-6) 3%
5-B (F) BB-2 (4-7) 5%
3-HB (F) HH-5 (4-9) 3%
NI = 83.7 ° C; Tc <-20 ° C; η = 13.7 mPa · s; Δn = 0.113; Δε = 9.7; Vth = 1.39 V; γ1 = 58.7 mPa · s.

[Example 9]
2O1-GB (F, F) XB (F) B (F, F) -F (1-2-4) 2%
3O1-GB (F, F) XB (F) B (F, F) -F (1-2-4) 2%
2O1-GB (F, F) XB (F, F) B (F) -F (1-2-5) 2%
3O1-GB (F, F) XB (F, F) B (F) -F (1-2-5) 2%
3-HH-V (2) 10%
3-HH-V1 (2) 5%
4-HH-V (2) 15%
3-HHXB (F, F) -CF3 (3-5) 3%
3-HB (F) B (F, F) -F (3-9) 3%
3-HBEB (F, F) -F (3-10) 3%
3-GB (F, F) XB (F) -F (3-13) 3%
3-BB (F) B (F, F) -F (3-15) 3%
3-HBB (F, F) XB (F, F) -F (3-24) 3%
3-BB (F) B (F, F) XB (F) -F (3-28) 5%
4-BB (F) B (F, F) XB (F) -F (3-28) 4%
5-BB (F) B (F, F) XB (F, F) -F (3-29) 3%
3-HB-O2 (4-1) 6%
7-HB-1 (4-1) 4%
V2-BB-1 (4-2) 7%
V-HHB-1 (4-4) 3%
V2-HHB-1 (4-4) 6%
2-BB (F) B-2V (4-6) 3%
5-HB (F) BH-3 (4-11) 3%
NI = 71.2 ° C; Tc <-20 ° C; η = 10.1 mPa · s; Δn = 0.111; Δε = 9.4; Vth = 1.47V; γ1 = 43.3 mPa · s.

[Example 10]
1O2-GB (F, F) XB (F) B (F, F) -F (1-2-4) 2%
1O1-GB (F) B (F, F) XB (F, F) -F (1-3-4) 2%
4O1-GB (F) B (F, F) XB (F, F) -F (1-3-4) 3%
2-HH-5 (2) 3%
3-HH-V (2) 24%
3-HH-V1 (2) 7%
5-GHB (F, F) -F (3-7) 5%
2-BB (F) B (F, F) -F (3-15) 3%
3-BB (F) B (F, F) -F (3-15) 3%
3-BB (F) B (F, F) -CF3 (3-16) 3%
4-GB (F) B (F, F) XB (F, F) -F (3-27) 3%
3-BB (F) B (F, F) XB (F) -F (3-28) 3%
4-BB (F) B (F, F) XB (F, F) -F (3-29) 3%
5-BB (F) B (F, F) XB (F, F) -F (3-29) 3%
3-BB (F, F) XB (F) B (F, F) -F (3-30) 3%
1V2-BB-1 (4-2) 6%
V-HHB-1 (4-4) 7%
V2-HHB-1 (4-4) 5%
V-HBB-2 (4-5) 4%
5-B (F) BB-2 (4-7) 3%
V2-BB2B-1 (4-8) 3%
1-BB2B-2V (4-8) 2%
NI = 80.4 ° C; Tc <-20 ° C; η = 12.9 mPa · s; Δn = 0.126; Δε = 10.7; Vth = 1.32 V; γ1 = 55.0 mPa · s.

[Example 11]
3O-GB (F, F) XB (F) B (F, F) -F (1-2-4) 2%
2O1-GB (F, F) XB (F) B (F) -F (1-2-4) 3%
2O1-GB (F) B (F, F) XB (F) B (F, F) -F
(1-5-1) 3%
3-HH-V (2) 30%
3-HH-V1 (2) 5%
3-HHB (F, F) -F (3-2) 10%
2-HGB (F, F) -F (3-6) 3%
3-HGB (F, F) -F (3-6) 2%
3-GHB (F, F) -F (3-7) 3%
5-GHB (F, F) -F (3-7) 3%
5-HBEB (F, F) -F (3-10) 3%
3-BB (F) B (F, F) -F (3-15) 5%
3-HHBB (F, F) -F (3-19) 3%
5-HBBXB (F, F) -F (3-23) 3%
4-BB (F) B (F, F) XB (F) -F (3-28) 3%
5-BB (F) B (F, F) XB (F, F) -F (3-29) 5%
7-HB-1 (4-1) 5%
3-HHB-3 (4-4) 3%
1-BB (F) B-2V (4-6) 3%
3-BB (F) B-2V (4-6) 3%
NI = 75.0 ° C.; Tc <-20 ° C.; η = 15.2 mPa · s; Δn = 0.104; Δε = 9.5; Vth = 1.46V; γ1 = 65.0 mPa · s.

[Example 12]
2O1-GB (F) XB (F) B (F) -F (1-2) 3%
2O1-GB (F) B (F, F) XB (F, F) -F (1-3-4) 3%
2O1-GB (F) B (F, F) XB (F, F) -CF3 (1-3-4) 1%
2-HH-3 (2) 19%
2-HH-5 (2) 8%
1V2-HH-1 (2) 3%
2-HGB (F, F) -F (3-6) 3%
3-HGB (F, F) -F (3-6) 3%
5-HGB (F, F) -F (3-6) 3%
3-HB (F) B (F, F) -F (3-9) 3%
5-HB (F) B (F, F) -F (3-9) 3%
2-BB (F) B (F, F) -F (3-15) 3%
3-BB (F) B (F, F) -F (3-15) 3%
2-BB (F, F) XB (F, F) -F (3-18) 3%
3-BB (F, F) XB (F, F) -F (3-18) 3%
3-HHB (F) B (F, F) -F (3-20) 3%
3-BB (F) B (F, F) XB (F, F) -F (3-29) 4%
4-BB (F) B (F, F) XB (F, F) -F (3-29) 4%
5-BB (F) B (F, F) XB (F, F) -F (3-29) 4%
2-HHB-1 (4-4) 3%
V-HHB-1 (4-4) 3%
V2-HHB-1 (4-4) 4%
3-HBB-2 (4-5) 5%
5-B (F) BB-2 (4-7) 3%
1O1-HBBH-5 (-) 3%
NI = 77.9 ° C; Tc <-20 ° C; η = 18.5 mPa · s; Δn = 0.111; Δε = 11.5; Vth = 1.31 V; γ1 = 79.1 mPa · s.

[Example 13]
4O1-GB (F, F) XB (F) B (F, F) -F (1-2-4) 3%
2O1-GB (F, F) XB (F) B (F) -OCF3 (1-2-4) 2%
3-HH-V (2) 27%
3-HH-V1 (2) 7%
2-HGB (F, F) -F (3-6) 3%
3-HGB (F, F) -F (3-6) 3%
3-HB (F) B (F, F) -F (3-9) 4%
5-HBEB (F, F) -F (3-10) 3%
3-BB (F) B (F, F) -F (3-15) 5%
4-HHBB (F, F) -F (3-19) 3%
5-BB (F) B (F, F) XB (F, F) -F (3-29) 5%
3-B (2F, 3F) BXB (F, F) -F (3-33) 3%
1V2-BB-1 (4-2) 5%
V-HHB-1 (4-4) 7%
V2-HHB-1 (4-4) 6%
V-HBB-2 (4-5) 6%
3-BB (F) B-5 (4-6) 5%
5-HBB (F) B-3 (4-12) 3%
NI = 85.4 ° C; Tc <-20 ° C; η = 9.4 mPa · s; Δn = 0.117; Δε = 6.5; Vth = 1.72 V; γ1 = 40.1 mPa · s.

[Example 14]
2O1-GBB (F, F) XB (F, F) -F (1-3-3) 2%
4O1-GB (F) B (F, F) XB (F) -F (1-3-4) 2%
3-HH-V (2) 22%
3-HH-V1 (2) 17%
3-HHXB (F, F) -CF3 (3-5) 5%
4-GHB (F, F) -F (3-7) 3%
3-GB (F) B (F) -F (3-11) 8%
2-HHBB (F, F) -F (3-19) 4%
3-HHBB (F, F) -F (3-19) 4%
5-HHBB (F, F) -F (3-19) 3%
5-GB (F) B (F, F) XB (F, F) -F (3-27) 3%
3-BB (F) B (F, F) XB (F) -F (3-28) 7%
3-HB-O2 (4-1) 10%
V2-HHB-1 (4-4) 4%
2-BB (F) B-5 (4-6) 3%
3-BB (F) B-5 (4-6) 3%
NI = 86.4 ° C; Tc <-20 ° C; η = 13.3 mPa · s; Δn = 0.106; Δε = 7.1; Vth = 1.67V; γ1 = 56.9 mPa · s.

[Example 15]
2O1-GB (F) XB (F) B (F) -F (1-2) 5%
4O1-GB (F, F) XB (F) B (F) -F (1-2-4) 3%
3-HH-V (2) 32%
3-HHXB (F, F) -F (3-4) 5%
5-HB (F) B (F, F) -F (3-9) 4%
3-GB (F, F) XB (F, F) -F (3-14) 4%
3-HHB (F) B (F, F) -F (3-20) 3%
3-BB (F) B (F, F) XB (F, F) -F (3-29) 4%
4-BB (F) B (F, F) XB (F, F) -F (3-29) 6%
5-BB (F) B (F, F) XB (F, F) -F (3-29) 5%
5-HB-O2 (4-1) 5%
V-HHB-1 (4-4) 8%
V2-HHB-1 (4-4) 5%
1V-HBB-2 (4-5) 5%
5-B (F) BB-2 (4-7) 3%
5-B (F) BB-3 (4-7) 3%
NI = 86.4 ° C; Tc <-20 ° C; η = 13.2 mPa · s; Δn = 0.116; Δε = 9.5; Vth = 1.46V; γ1 = 56.4 mPa · s.

[Example 16]
4O1-GB (F, F) XB (F) B (F, F) -F (1-2-4) 3%
4O1-GB (F) B (F, F) XB (F, F) -F (1-3-4) 3%
3-HH-4 (2) 7%
3-HH-V (2) 29%
3-HH-V1 (2) 6%
4-HHEB (F, F) -F (3-3) 3%
1-HHXB (F, F) -F (3-4) 3%
3-GB (F, F) XB (F, F) -F (3-14) 3%
3-BBXB (F, F) -F (3-17) 3%
3-BB (F, F) XB (F, F) -F (3-18) 3%
2-HHBB (F, F) -F (3-19) 2%
4-HHB (F) B (F, F) -F (3-20) 3%
3-BB (F) B (F, F) XB (F, F) -F (3-29) 4%
5-BB (F) B (F, F) XB (F, F) -F (3-29) 3%
3-HHEH-3 (4-3) 6%
V-HHB-1 (4-4) 5%
V2-HHB-1 (4-4) 7%
2-BB (F) B-3 (4-6) 3%
5-B (F) BB-2 (4-7) 4%
NI = 85.2 ° C; Tc <-20 ° C; η = 9.4 mPa · s; Δn = 0.098; Δε = 7.0; Vth = 1.68 V; γ1 = 40.3 mPa · s.

[Example 17]
3O1-GB (F, F) XB (F) B (F, F) -F (1-2-4) 3%
2O1-GB (F) B (F, F) XB (F) B (F, F) -F
(1-5-1) 4%
3-HH-V (2) 29%
3-HH-V1 (2) 6%
1V2-HH-3 (2) 6%
3-HHEB (F, F) -F (3-3) 3%
5-HHEB (F, F) -F (3-3) 4%
3-HHXB (F, F) -F (3-4) 6%
3-GB (F) B (F, F) -F (3-12) 3%
5-GB (F) B (F, F) -F (3-12) 3%
3-GB (F) B (F) B (F) -F (3-21) 3%
3-BB (F) B (F, F) XB (F) -F (3-28) 4%
4-BB (F) B (F, F) XB (F) -F (3-28) 8%
1-BB-3 (4-2) 3%
V-HHB-1 (4-4) 4%
3-HBB-2 (4-5) 7%
V2-BB2B-1 (4-8) 4%
NI = 86.0 ° C; Tc <-20 ° C; η = 11.6 mPa · s; Δn = 0.111; Δε = 9.1; Vth = 1.45 V; γ1 = 49.6 mPa · s.

[Example 18]
3O1-GB (F) B (F, F) XB (F, F) -F (1-3-4) 5%
4O1-GB (F) B (F, F) XB (F) -F (1-3-4) 3%
3-HH-V (2) 17%
3-HH-V1 (2) 8%
5-HH-V (2) 5%
4-HHB (F, F) -F (3-2) 3%
5-HHB (F, F) -F (3-2) 3%
2-HBEB (F, F) -F (3-10) 5%
2-BB (F) B (F, F) -F (3-15) 3%
3-BB (F) B (F, F) -F (3-15) 5%
3-BB (F) B (F, F) -CF3 (3-16) 5%
2-dhBB (F, F) XB (F, F) -F (3-25) 3%
3-BB (F) B (F, F) XB (F, F) -F (3-29) 3%
4-BB (F) B (F, F) XB (F, F) -F (3-29) 4%
5-BB (F) B (F, F) XB (F, F) -F (3-29) 5%
3-HB-O2 (4-1) 6%
3-HHB-1 (4-4) 3%
VFF-HHB-1 (4-4) 3%
V-HBB-2 (4-5) 4%
3-BB (F) B-5 (4-6) 4%
3-HHEBH-3 (4-10) 3%
NI = 80.9 ° C; Tc <-20 ° C; η = 18.0 mPa · s; Δn = 0.116; Δε = 10.8; Vth = 1.33 V; γ1 = 76.9 mPa · s.

[Example 19]
2O1-GB (F, F) XB (F, F) -F (1-1-3) 2%
2O1-GB (F) B (F, F) XB (F, F) -F (1-3-4) 3%
3-HH-V (2) 23%
3-HH-V1 (2) 7%
1V2-HH-3 (2) 3%
1-HHB (F, F) -F (3-2) 3%
2-HHB (F, F) -F (3-2) 3%
3-HHB (F, F) -F (3-2) 3%
3-HBB (F, F) -F (3-8) 3%
5-HBB (F, F) -F (3-8) 3%
V-HB (F) B (F, F) -F (3-9) 3%
3-GB (F, F) XB (F) -F (3-13) 3%
3-GBB (F) B (F, F) -F (3-22) 3%
4-BB (F) B (F, F) XB (F) -F (3-28) 5%
4-BB (F) B (F, F) XB (F, F) -F (3-29) 8%
5-BB (F) B (F, F) XB (F) B (F, F) -F (3-31) 3%
3-HHB-O1 (4-4) 3%
V-HHB-1 (4-4) 6%
V2-HHB-1 (4-4) 6%
2-BB (F) B-2V (4-6) 3%
3-HHEBH-5 (4-10) 4%
NI = 94.1 ° C; Tc <-20 ° C; η = 18.1 mPa · s; Δn = 0.112; Δε = 9.3; Vth = 1.48 V; γ1 = 77.5 mPa · s.

[Example 20]
3O1-GB (F) B (F, F) XB (F, F) -F (1-3-4) 2%
4O1-GB (F) B (F, F) XB (F, F) -F (1-3-4) 4%
2-HH-3 (2) 10%
3-HH-4 (2) 7%
3-HH-5 (2) 7%
3-HH-V1 (2) 8%
5-HXB (F, F) -F (3-1) 3%
3-HB (F) B (F, F) -F (3-9) 3%
3-GB (F, F) XB (F, F) -F (3-14) 4%
3-BB (F) B (F, F) -F (3-15) 3%
3-BB (F, F) XB (F, F) -F (3-18) 8%
3-HHBB (F, F) -F (3-19) 5%
2-HHB (F) B (F, F) -F (3-20) 4%
3-HHB (F) B (F, F) -F (3-20) 5%
5-GB (F) B (F, F) XB (F, F) -F (3-27) 3%
3-HB-O2 (4-1) 3%
V-HHB-1 (4-4) 3%
V2-HHB-1 (4-4) 3%
3-HBB-2 (4-5) 6%
2-BB (F) B-5 (4-6) 5%
1-BB2B-2V (4-8) 4%
NI = 82.6 ° C; Tc <-20 ° C; η = 15.5 mPa · s; Δn = 0.109; Δε = 9.5; Vth = 1.45 V; γ1 = 66.3 mPa · s.

The compositions of Examples 1 to 20 had smaller viscosities than those of Comparative Examples 1 and 2. Therefore, it is concluded that the liquid crystal composition of the present invention has excellent properties.

The liquid crystal composition of the present invention has a high upper limit temperature, a lower lower limit temperature, a small viscosity, an appropriate optical anisotropy, a large dielectric anisotropy, a large dielectric constant in the minor axis direction of a liquid crystal molecule, a large specific resistance, and a large elastic modulus. It satisfies at least one property or has an appropriate balance with respect to at least two properties in properties such as constant, high stability to ultraviolet rays, high stability to heat, and large elastic constant. A liquid crystal display element containing this composition has a short response time, a large voltage retention rate, a large contrast ratio, a long life, and the like, and therefore can be used in liquid crystal projectors, liquid crystal televisions, and the like.

Claims (17)

Contains at least one compound selected from the group of compounds represented by the formula (1) as the first component and at least one compound selected from the group of compounds represented by the formula (2) as the second component. A liquid crystal composition having a nematic phase.

In formulas (1) and (2), R ¹ is an alkyl having 1 to 12 carbon atoms or an alkenyl having 2 to 12 carbon atoms, and in these groups, at least one −CH ₂ − is −O−. R ² and R ³ may be independently replaced by an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, and at least one hydrogen being fluorine or chlorine. An alkyl having 1 to 12 carbon atoms replaced, or an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine; ring A is tetrahydropyran-2,5-diyl or 1,3. -Dioxane-2,5-diyl; Ring B is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2 , 3-Difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidin-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5 -Diyl; Z ¹ and Z ² are independently single-bonded, ethylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy, where at least one of Z ¹ or Z ² is difluoromethyleneoxy. Yes , if a is 0, then Z ² is difluoromethyleneoxy ; X ¹ and X ² are independently hydrogen or fluorine; Y ¹ is fluorine, chlorine, at least one hydrogen is fluorine or chlorine. Alkyl with 1 to 12 carbons replaced, alkoxy with 1 to 12 carbons with at least one hydrogen replaced with fluorine or chlorine, or 2 to 12 carbons with at least one hydrogen replaced with fluorine or chlorine It is alkenyloxy; a is 0, 1, 2, or 3; n is 0, 1, 2, or 3.
The liquid crystal composition according to claim 1, which contains at least one compound selected from the group of compounds represented by formulas (1-1) to (1-9) as a first component.

In formulas (1-1) to (1-9), R ¹ is an alkyl having 1 to 12 carbon atoms or an alkenyl having 2 to 12 carbon atoms, and in these groups, at least one −CH ₂ − is , -O- may be replaced; ring B is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2 , 3-Difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidin-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5 -Diyl; X ¹ and X ² are independently hydrogen or fluorine; Y ¹ is fluorine, chlorine, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine, at least. One hydrogen is an alkoxy having 1 to 12 carbon atoms replaced with fluorine or chlorine, or at least one hydrogen is an alkenyloxy having 2 to 12 carbon atoms replaced with fluorine or chlorine; n is 0, 1, 2 , Or 3. As the first component, formulas (1-1-1) to formulas (1-1-4), formulas (1-2-1) to formulas (1-2-5), and formulas (1-3-1) to formulas (1-3-5), formula (1-5-1), formula (1-6-1), formula (1-7-1) to formula (1-7-5), formula (1-8-) The liquid crystal composition according to claim 1 or 2, which contains at least one compound selected from the group of compounds represented by the formulas (1-8-5) and (1-9-1) from 1). ..

Formulas (1-1-1) to formulas (1-1-4), formulas (1-2-1) to formulas (1-2-5), formulas (1-3-1) to formulas (1-3) -5), formula (1-5-1), formula (1-6-1), formula (1-7-1) to formula (1-7-5), formula (1-8-1) to formula In (1-8-5) and formula (1-9-1), R ¹ is an alkyl having 1 to 12 carbon atoms or an alkenyl having 2 to 12 carbon atoms, and at least one -CH in these groups. ₂ − may be replaced with −O −; X ¹ and X ² are independently hydrogen or fluorine; Y ¹ is fluorine, chlorine, at least one hydrogen replaced with fluorine or chlorine. Alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine, or alkenyloxy with 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine. Yes; n is 0, 1, 2, or 3. The liquid crystal according to any one of claims 1 to 3, wherein the ratio of the first component is in the range of 1% by weight to 30% by weight, and the ratio of the second component is in the range of 5% by weight to 70% by weight. Composition. The liquid crystal composition according to any one of claims 1 to 4, which contains at least one compound selected from the group of compounds represented by the formula (3) as a third component.

In formula (3), ^{R 4} is alkyl of from 1 to 12 carbons, alkenyl alkoxy of 1 to 12 carbons, or 2 to 12 carbons; ring C is 1,4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3- Dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z ³ is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy; X ³ and X ⁴ are independently hydrogen. Or fluorine; Y ² is fluorine, chlorine, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, and 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine. Aalkoxy, or an alkenyloxy having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; b is 1, 2, 3, or 4. The liquid crystal according to any one of claims 1 to 5, which contains at least one compound selected from the group of compounds represented by formulas (3-1) to (3-35) as a third component. Composition.

In the formula (3-35) from equation (3-1), ^{R 4} is an alkenyl alkyl of 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 2 to 12 carbons. The liquid crystal composition according to claim 5 or 6, wherein the proportion of the third component is in the range of 10% by weight to 80% by weight. The liquid crystal composition according to any one of claims 1 to 7, further containing at least one compound selected from the group of compounds represented by the formula (4) as the fourth component.

In formula (4), R ⁵ and R ⁶ are independently an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, or at least one hydrogen being fluorine or chlorine. It is an alkenyl having 2 to 12 carbon atoms replaced; rings D and ring E are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5. -Difluoro-1,4-phenylene; Z ⁴ is single bond, ethylene, or carbonyloxy; c is 1, 2, or 3; ring E when c is 1 is 1. , 4-Phenylene, 2-Fluoro-1,4-Phenylene, or 2,5-Difluoro-1,4-Phenylene. The liquid crystal according to any one of claims 1 to 8, which contains at least one compound selected from the group of compounds represented by formulas (4-1) to (4-12) as a fourth component. Composition.

In formulas (4-1) to (4-12), R ⁵ and R ⁶ are independently alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or An alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. The liquid crystal composition according to claim 8 or 9, wherein the proportion of the fourth component is in the range of 5% by weight to 60% by weight. The liquid crystal composition according to any one of claims 1 to 10, which contains at least one compound selected from the group of compounds represented by the formula (5) as a fifth component.

In formula (5), R ⁷ and R ⁸ are independently composed of an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, or an alkenyloxy having 2 to 12 carbon atoms. Yes; Rings F and I are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine. , Or tetrahydropyran-2,5-diyl; ring G 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-trifluoro-2,6-diyl or 7,8-be difluorochroman-2,6-diyl; ^{Z 5} and ^{Z 6} are each independently , Single bond, ethylene, carbonyloxy, or methyleneoxy; d is 1, 2, or 3, e is 0 or 1, and the sum of d and e is 3 or less. The liquid crystal according to any one of claims 1 to 11, which contains at least one compound selected from the group of compounds represented by the formulas (5-1) to (5-22) as the fifth component. Composition.

In formulas (5-1) to (5-22), R ⁷ and R ⁸ are independently alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or It is an alkenyloxy having 2 to 12 carbon atoms. The liquid crystal composition according to claim 11 or 12, wherein the proportion of the fifth component is in the range of 3% by weight to 30% by weight. The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy (measured at 25 ° C.) at a wavelength of 589 nm is 0.07 or higher, and the dielectric anisotropy (measured at 25 ° C.) at a frequency of 1 kHz is 2. The liquid crystal composition according to any one of claims 1 to 13 as described above. A liquid crystal display device containing the liquid crystal composition according to any one of claims 1 to 14. The liquid crystal display according to claim 15, wherein the operation mode of the liquid crystal display element is TN mode, ECB mode, OCB mode, IPS mode, FFS mode, or FPA mode, and the drive method of the liquid crystal display element is the active matrix method. element. Use of the liquid crystal composition according to any one of claims 1 to 14 in a liquid crystal display device.