JP6848140B2 - 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, the present invention relates to a liquid crystal composition having a negative dielectric anisotropy, and a liquid crystal display device containing the composition and having modes such as IPS, VA, FFS, and FPA. It also relates to a polymer-supported orientation type liquid crystal display element.

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, multiplex and the like, and AM is classified into TFT (thin film transistor), MIM (metal insulator metal) and the like. The classification of TFTs is amorphous silicon and polycrystal silicon. The latter is classified into a high temperature type and a low temperature type according to the manufacturing process. The classification based on the light source is a reflective type that uses natural light, a transmissive type that uses a backlight, and a semi-transmissive type that uses both natural light and a backlight.

The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the characteristics of this composition, an AM element having good characteristics can be obtained. The relationship between the two characteristics is 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 even more preferred.

The optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large optical anisotropy or a small optical anisotropy, 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. This value ranges from about 0.30 μm to about 0.40 μm for VA mode devices and from about 0.20 μm to about 0.30 μm for IPS or FFS mode devices. In these cases, 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, a 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 device. When this stability is high, the life of the device is long. Such characteristics are preferable for AM elements used in liquid crystal projectors, liquid crystal televisions, and the like.

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

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 the polymer support orientation type AM device, a composition having positive or negative dielectric anisotropy is used. Examples of the first component of the present application are disclosed in the following Patent Documents 1 to 3.

Japanese Unexamined Patent Publication No. 2000-38583 Japanese Unexamined Patent Publication No. 2000-53602 Japanese Unexamined Patent Publication No. 2002-193853

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 negatively large dielectric anisotropy, a large specific resistance, and a high stability against ultraviolet rays. A liquid crystal composition that satisfies at least one property in terms of properties such as high stability against heat and a large elastic constant. Another object is a liquid crystal composition having an appropriate balance between at least two properties. Another object is a liquid crystal display device containing such a composition. Another object is an AM device that has characteristics such as short response time, high voltage retention, low threshold voltage, high contrast ratio, and long life.

式（１）において、Ｒ^１およびＲ^２は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルであり；環Ａ、環Ｂ、環Ｃ、および環Ｄ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、テトラヒドロピラン−２，５−ジイル、１，４−フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレン、ナフタレン−２，６−ジイル、少なくとも１つの水素がフッ素または塩素で置き換えられたナフタレン−２，６−ジイル、クロマン−２，６−ジイル、または少なくとも１つの水素がフッ素または塩素で置き換えられたクロマン−２，６−ジイルであり；ただし、環Ａ、環Ｂ、環Ｃ、および環Ｄの少なくとも１つは、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、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^１、Ｚ^２、およびＺ^３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；ただし、Ｚ^１、Ｚ^２、およびＺ^３の少なくとも１つはエチレンである。 The present invention comprises a liquid crystal composition containing at least one compound selected from the group of compounds represented by the formula (1) as a first component, and having a nematic phase and negative permittivity anisotropy, and a liquid crystal composition thereof. A liquid crystal display element containing a composition.

In formula (1), R ¹ and R ² 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, an alkenyloxy having 2 to 12 carbon atoms, or At least one hydrogen is an alkyl having 1 to 12 carbon atoms in which fluorine or chlorine is replaced; ring A, ring B, ring C, and ring D are independently 1,4-cyclohexylene, 1,4-. Cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine, naphthalene-2,6-diyl, at least one hydrogen Naphthalene-2,6-diyl, chroman-2,6-diyl replaced with fluorine or chlorine, or chroman-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine; however, ring A , Ring B, Ring C, and Ring D are 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 3,4,5-trifluoro. be a naphthalene-2,6-diyl or ^{7,8-difluoro-chroman-2,6-diyl,;} Z 1, ^{Z 2,} and ^{Z 3} are each independently a single bond, ethylene, carbonyloxy or methyleneoxy, Yes; however, at least one of ^{Z 1} , Z ² , and Z ^{3 is ethylene.}

One of the advantages of the present invention is the high upper limit temperature of the nematic phase, the lower lower limit temperature of the nematic phase, small viscosity, appropriate optical anisotropy, negatively large dielectric anisotropy, large specific resistance, and high stability against ultraviolet rays. A liquid crystal composition that satisfies at least one property in terms of properties such as high stability against heat and a large elastic constant. Another advantage is a liquid crystal composition that has an appropriate balance between at least two properties. Another advantage is a liquid crystal display device containing such a composition. Another advantage is an AM device that has characteristics such as short response time, high voltage retention, low threshold voltage, high contrast ratio, and 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 a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and a compound having no liquid crystal phase, but is composed for the purpose of adjusting characteristics such as temperature range, viscosity, and dielectric constant anisotropy of the nematic phase. It is a general term for compounds that are mixed with substances. This compound has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod-like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. The proportion (content) of the liquid crystal compound is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition. Additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, and a polymerization inhibitor are added to the liquid crystal composition as needed. The ratio of the additive (addition amount) is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition, similarly to the ratio of the liquid crystal compound. Parts per million (ppm) by weight may also be used. The proportions of polymerization initiators and polymerization inhibitors are 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". "Large 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 device 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 at 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 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 (2) may be abbreviated as "Compound (2)". "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'".

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 (3), when b is 2, there are two rings G. In this compound, the two rings represented by the two rings G may be the same or different. This rule also applies to any two rings G when b is greater than 2. This rule, Z ^4, is applied to symbols such as ring E. This rule also applies to cases such as the ^{two -Sp 2-} P ⁵ in compound (4-27).

Symbols such as A, B, and C enclosed in hexagons correspond to six-membered rings such as ring A, ring B, and ring C, respectively. In compound (4), the hexagon represents a six-membered ring or a fused ring. The diagonal lines across this hexagon indicate that any hydrogen on the ring may be replaced by a group such as ^{-Sp 1-} P ^1. Subscripts such as e indicate the number of replaced groups. When the subscript is 0, there is no such replacement. When e is 2 or more, there are a plurality of −Sp ¹ −P ^{1 on the ring K.} -Sp ^{1 The} plurality of groups represented by -P ¹ may be the same or different.

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 ring-derived asymmetric divalent groups, such as tetrahydropyran-2,5-diyl. This rule also applies to divalent binding groups such as carbonyloxy (-COO- or -OCO-).

The present invention includes the following items.

式（１）において、Ｒ^１およびＲ^２は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルであり；環Ａ、環Ｂ、環Ｃ、および環Ｄ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、テトラヒドロピラン−２，５−ジイル、１，４−フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレン、ナフタレン−２，６−ジイル、少なくとも１つの水素がフッ素または塩素で置き換えられたナフタレン−２，６−ジイル、クロマン−２，６−ジイル、または少なくとも１つの水素がフッ素または塩素で置き換えられたクロマン−２，６−ジイルであり；ただし、環Ａ、環Ｂ、環Ｃ、および環Ｄの少なくとも１つは、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、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^１、Ｚ^２、およびＺ^３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；ただし、Ｚ^１、Ｚ^２、およびＺ^３の少なくとも１つはエチレンである。 Item 1. A liquid crystal composition containing at least one compound selected from the group of compounds represented by the formula (1) as a first component, and having a nematic phase and negative dielectric anisotropy.

In formula (1), R ¹ and R ² 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, an alkenyloxy having 2 to 12 carbon atoms, or At least one hydrogen is an alkyl having 1 to 12 carbon atoms in which fluorine or chlorine is replaced; ring A, ring B, ring C, and ring D are independently 1,4-cyclohexylene, 1,4-. Cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine, naphthalene-2,6-diyl, at least one hydrogen Naphthalene-2,6-diyl, chroman-2,6-diyl replaced with fluorine or chlorine, or chroman-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine; however, ring A , Ring B, Ring C, and Ring D are 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 3,4,5-trifluoro. be a naphthalene-2,6-diyl or ^{7,8-difluoro-chroman-2,6-diyl,;} Z 1, ^{Z 2,} and ^{Z 3} are each independently a single bond, ethylene, carbonyloxy or methyleneoxy, Yes; however, at least one of ^{Z 1} , Z ² , and Z ^{3 is ethylene.}

式（１−１）から式（１−１４）において、Ｒ^１およびＲ^２は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素が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 (1-14) as a first component.

In formulas (1-1) to (1-14), R ¹ and R ² are independently alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and carbon. Alkenyloxy of numbers 2 to 12, or alkyls of carbons 1 to 12 in which at least one hydrogen is replaced with fluorine or chlorine.

Item 3. Item 2. The liquid crystal composition according to Item 1 or 2, wherein the proportion of the first component is in the range of 3% by weight to 50% by weight based on the weight of the liquid crystal composition.

式（２）において、Ｒ^３およびＲ^４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Ｅおよび環Ｆ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；ａは、１、２、または３である。 Item 4. Item 6. The liquid crystal composition according to any one of Items 1 to 3, which contains at least one compound selected from the group of compounds represented by the formula (2) as a second component.

In formula (2), R ³ and R ⁴ are independently replaced by an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, and at least one hydrogen being replaced with fluorine or chlorine. Alkyl with 1 to 12 carbon atoms, or alkenyl with 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; Ring E and Ring F are independently 1,4-cyclohexylene. 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ⁴ is a single bond, ethylene, or carbonyloxy; a is 1 2, or 3.

式（２−１）から式（２−１３）において、Ｒ^３およびＲ^４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のアルケニルである。 Item 5. Item 2. 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 formulas (2-1) to (2-13) as the second component. Stuff.

In formulas (2-1) to (2-13), R ³ and R ⁴ are independently alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or at least. An alkyl having 1 to 12 carbon atoms in which one hydrogen has been replaced with fluorine or chlorine, or an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine.

Item 6. Item 4. The liquid crystal composition according to Item 4 or 5, wherein the proportion of the second component is in the range of 10% by weight to 70% by weight based on the weight of the liquid crystal composition.

式（３）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、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルであり；環Ｇおよび環Ｊ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、テトラヒドロピラン−２，５−ジイル、１，４−フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレン、ナフタレン−２，６−ジイル、少なくとも１つの水素がフッ素または塩素で置き換えられたナフタレン−２，６−ジイル、クロマン−２，６−ジイル、または少なくとも１つの水素がフッ素または塩素で置き換えられたクロマン−２，６−ジイルであり；環Ｉ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；ｂは、１または２であり；ｃは、０または１であり；ｂとｃとの和は２以下である。 Item 7. Item 6. The liquid crystal composition according to any one of Items 1 to 6, 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 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, an alkenyloxy having 2 to 12 carbon atoms, or At least one hydrogen is an alkyl having 1 to 12 carbon atoms in which fluorine or chlorine is replaced; ring G and ring J are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-. 2,5-Diyl, 1,4-phenylene, at least one hydrogen replaced with fluorine or chlorine 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen replaced with fluorine or chlorine Naphthalene-2,6-diyl, chroman-2,6-diyl, or chroman-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine; ring I 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-be difluorochroman-2,6-diyl; ^{Z 5} and ^{Z 6} are each independently a single bond, ethylene, carbonyloxy or methyleneoxy,; b is 1 or 2; c is 0 or 1; the sum of b and c is 2 or less.

式（３−１）から式（３−２２）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、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルである。 Item 8. Item 2. The liquid crystal composition according to any one of Items 1 to 7, which contains at least one compound selected from the group of compounds represented by the formulas (3-1) to (3-22) as the third component. Stuff.

In formulas (3-1) to (3-22), R ⁵ and R ⁶ are independently alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and carbon. Alkenyloxy of numbers 2 to 12, or alkyls of carbons 1 to 12 in which at least one hydrogen is replaced with fluorine or chlorine.

Item 9. Item 7. The liquid crystal composition according to Item 7 or 8, wherein the proportion of the third component is in the range of 10% by weight to 80% by weight based on the weight of the liquid crystal composition.

式（４）において、環Ｋおよび環Ｍは独立して、シクロヘキシル、シクロヘキセニル、フェニル、１−ナフチル、２−ナフチル、テトラヒドロピラン−２−イル、１，３−ジオキサン−２−イル、ピリミジン−２−イル、またはピリジン−２−イルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、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１から１２のアルキルで置き換えられてもよく；環Ｌは、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、ナフタレン−１，２−ジイル、ナフタレン−１，３−ジイル、ナフタレン−１，４−ジイル、ナフタレン−１，５−ジイル、ナフタレン−１，６−ジイル、ナフタレン−１，７−ジイル、ナフタレン−１，８−ジイル、ナフタレン−２，３−ジイル、ナフタレン−２，６−ジイル、ナフタレン−２，７−ジイル、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、またはピリジン−２，５−ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、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１から１２のアルキルで置き換えられてもよく；Ｚ^７およびＺ^８は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ_３）−、または−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｐ^１、Ｐ^２、およびＰ^３は独立して、重合性基であり；Ｓｐ^１、Ｓｐ^２、およびＳｐ^３は独立して、単結合、または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ｄは、０、１、または２であり；ｅ、ｆ、およびｇは独立して、０、１、２、３、または４であり；そしてｅ、ｆ、およびｇの和は、１以上である。 Item 10. Item 2. The liquid crystal composition according to any one of Items 1 to 9, which contains at least one polymerizable compound selected from the group of compounds represented by the formula (4) as an additive component.

In formula (4), ring K and ring M are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-. 2-Il or pyridine-2-yl, in these rings at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least one hydrogen. It may be replaced with an alkyl having 1 to 12 carbon atoms replaced with fluorine or chlorine; ring L is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1, 2-Diyl, Naphthalene-1,3-Diyl, Naphthalene-1,4-Diyl, Naphthalene-1,5-Diyl, Naphthalene-1,6-Diyl, Naphthalene-1,7-Diyl, Naphthalene-1,8- Diyl, Naphthalene-2,3-Diyl, Naphthalene-2,6-Diyl, Naphthalene-2,7-Diyl, Tetrahydropyran-2,5-Diyl, 1,3-Dioxane-2,5-Diyl, Pyrimidine-2 , 5-Diyl, or pyridine-2,5-Diyl, in which at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least 1 One hydrogen may be replaced with an alkyl having 1 to 12 carbon atoms replaced with fluorine or chlorine; Z ⁷ and Z ⁸ are independently single-bonded or alkylenes having 1 to 10 carbon atoms, and in this alkylene. , At least one −CH ₂ − may be replaced by −O −, −CO−, −COO−, or −OCO−, and at least one −CH ₂ −CH ₂₋ is −CH = CH−. , -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )-, at least one of these groups. Hydrogen may be replaced with fluorine or chlorine; P ¹ , P ² , and P ³ are independently polymerizable groups; Sp ¹ , Sp ² , and Sp ³ are independently single-bonded, Alternatively, it is an alkylene having 1 to 10 carbon atoms, in which at least one -CH _2- may be replaced with -O-, -COO-, -OCO-, or -OCOO-, and at least one. -CH ₂ -CH _2- is -C It may be replaced by H = CH- or -C≡C-, in these groups at least one hydrogen may be replaced by fluorine or chlorine; d is 0, 1, or 2; e, f, and g are independently 0, 1, 2, 3, or 4; and the sum of e, f, and g is greater than or equal to 1.

式（Ｐ−１）から式（Ｐ−６）において、Ｍ^１、Ｍ^２、およびＭ^３は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルであり；
式（４）において、ｅ個のＰ^１およびｇ個のＰ^３のすべてが、式（Ｐ−４）で表される基であるとき、ｅ個のＳｐ^１およびｇ個のＳｐ^３のうちの少なくとも１つは、少なくとも１つの−ＣＨ_２−が、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられた、炭素数１から１０のアルキレンである。 Item 11. In formula (4), ^{terms in which P 1} , P ² , and P ³ are independently polymerizable groups selected from the group of groups represented by formulas (P-1) to (P-6). 10. The liquid crystal composition according to 10.

In formulas (P-1) to (P-6), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine. Alkyl with 1 to 5 carbon atoms replaced by;
In formula (4), when all of e P ¹ and g P ³ are groups represented by formula (P-4), of e Sp ¹ and g Sp ³ . At least one is _{an alkylene having 1 to 10 carbon atoms in which at least one -CH 2-} has been replaced with -O-, -COO-, -OCO-, or -OCOO-.

式（４−１）から式（４−２７）において、Ｐ^４、Ｐ^５、およびＰ^６は独立して、式（Ｐ−１）から式（Ｐ−３）で表される基の群から選択された重合性基であり；

式（Ｐ−１）から式（Ｐ−３）において、Ｍ^１、Ｍ^２、およびＭ^３は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルであり；
式（４−１）から式（４−２７）において、Ｓｐ^１、Ｓｐ^２、およびＳｐ^３は独立して、単結合、または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。 Item 12. Item 2. The item according to any one of Items 1 to 11, which contains at least one polymerizable compound selected from the group of compounds represented by the formulas (4-1) to (4-27) as an additive component. Liquid crystal composition.

In the formula (4-27) from equation ^(4-1), P 4, ^{P 5,} and ^{P 6} are each independently from the group of radicals represented by the formula (P-1) by the formula (P-3) It is the polymerizable group of choice;

In formulas (P-1) to (P-3), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine. Alkyl with 1 to 5 carbon atoms replaced by;
In formulas (4-1) to (4-27), Sp ¹ , Sp ² , and Sp ³ are independently single bonds or alkylenes having 1 to 10 carbon atoms, and at least one of the alkylenes. −CH ₂ − may be replaced by −O −, −COO−, −OCO−, or −OCOO−, and at least one −CH ₂ −CH ₂₋ is −CH = CH− or −C≡ It may be replaced with C-, and in these groups at least one hydrogen may be replaced with fluorine or chlorine.

Item 13. Item 2. The liquid crystal composition according to any one of Items 10 to 12, wherein the addition ratio of the additive component is in the range of 0.03% by weight to 10% by weight based on the weight of the liquid crystal composition.

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

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

Item 16. A polymer-supported oriented liquid crystal display device containing the liquid crystal composition according to any one of Items 1 to 13 or having a polymerizable compound in the liquid crystal composition polymerized.

Item 17. Use of the liquid crystal composition according to any one of Items 1 to 13 in a liquid crystal display element.

Item 18. Use of the liquid crystal composition according to any one of Items 1 to 13 in a polymer-supported orientation type liquid crystal display device.

The present invention also includes the following sections. (A) The above composition further containing at least one additive such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, and a polymerization inhibitor. (B) AM device containing the above composition. (C) A polymer-supported orientation (PSA) type AM device containing the above composition further containing a polymerizable compound. (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 constituent compounds in 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. Thirdly, the combination of components in the composition, the preferable ratio of the components, and the rationale thereof will be described. Fourth, preferable forms of the component 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 constituent compounds in the composition will be described. The compositions of the present invention are classified into composition A and composition B. The composition A may further contain other liquid crystal compounds, additives and the like in addition to the liquid crystal compound selected from the compound (1), the compound (2) and the compound (3). The "other liquid crystal compound" is a liquid crystal compound different from the compound (1), the compound (2), and the compound (3). 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 and the like.

The composition B is substantially composed of only a liquid crystal compound selected from the compound (1), the compound (2), and the compound (3). "Substantially" means that the composition may contain additives but does not contain other liquid crystal compounds. Composition B has a smaller number of components than 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 properties of 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, with 0 (zero) meaning that the value is zero or 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) raises the upper temperature limit and raises the dielectric anisotropy. Compound (2) raises the upper temperature limit or lowers the viscosity. Compound (3) increases the dielectric anisotropy and lowers the lower limit temperature. Compound (4) gives a polymer by polymerization, which reduces the response time of the device and improves image burn-in.

Thirdly, the combination of 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 + additive component, 1st component + 2nd component + 1st component. Three components + additive components. More preferable combinations are 1st component + 2nd component + 3rd component, 1st component + 2nd component + 3rd component + additive component.

The preferable ratio of the first component is about 3% by weight or more in order to increase the dielectric anisotropy, and about 50% by weight or less in order to decrease the viscosity. A more preferred ratio is in the range of about 5% by weight to about 40% by weight. A particularly preferred proportion is in the range of about 5% by weight to about 30% by weight.

The preferred proportion of the second component is about 10% by weight or more to raise the upper limit temperature or lower the viscosity, and about 70% by weight or less to increase the dielectric anisotropy. A more preferred proportion is in the range of about 15% to about 60% by weight. A particularly preferred proportion is in the range of about 20% by weight to about 50% 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 20% by weight to about 75% by weight. A particularly preferred proportion is in the range of about 30% by weight to about 70% by weight.

Compound (4) is added to the composition for the purpose of adapting to a polymer support oriented device. The preferable ratio of the additive component is about 0.03% by weight or more for aligning the liquid crystal molecules, and about 10% by weight or less for preventing display defects of the device. A more preferred ratio is in the range of about 0.1% by weight to about 2% by weight. A particularly preferred ratio is in the range of about 0.2% by weight to about 1.0% by weight.

Fourth, preferable forms of the component compounds will be described. Equation (1), equation (2), Equation (3), and in formula ^(4), R ^1, R 2, ^{R 5,} and ^{R 6} are each independently alkyl of 1 to 12 carbons, carbons 1 To 12 alkoxy, 2 to 12 carbon alkenyl, 2 to 12 carbon alkenyloxy, or 1 to 12 carbon alkyl in which at least one hydrogen is replaced with fluorine or chlorine. Preferred R ^1, R 2, ^R 5 or R ^6, is an alkyl having 1 to 12 carbons for increasing the stability, alkenyl having 1 to 12 carbons for decreasing the viscosity, dielectric anisotropy It is an alkoxy having 1 to 12 carbon atoms in order to improve its properties. R ³ and R ⁴ 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 ³ or R ⁴ 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. Alkyl 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.

Preferred alkyls are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. More preferred alkyls are ethyl, propyl, butyl, pentyl, or heptyl 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. In alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl, trans is preferable for lowering the viscosity. Sis is preferred for alkenyl such as 2-butenyl, 2-pentenyl, 2-hexenyl.

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, Ring B, Ring C, and Ring D are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one. 1,4-Phenylene, naphthalene-2,6-diyl in which hydrogen is replaced with fluorine or chlorine, naphthalene-2,6-diyl, chroman-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine , Or at least one hydrogen replaced with fluorine or chlorine is chroman-2,6-diyl. However, at least one of ring A, ring B, ring C, and ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 3,4. 5-Trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl. Preferred ring A, ring B, ring C, or ring D is 1,4-cyclohexylene for lowering the viscosity or raising the upper temperature limit and 1,4-phenylene for lowering the lower limit temperature. , 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine to increase the dielectric anisotropy. The configuration for 1,4-cyclohexylene is preferably trans over cis in order to raise the upper temperature limit. Tetrahydropyran-2,5-diyl is

Or

And preferably

Is.

Rings E and F are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. Preferred ring E or ring F is 1,4-cyclohexylene for lowering the viscosity or raising the upper temperature limit and 1,4-phenylene for lowering the lower limit temperature.

Ring G and Ring J independently replace 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen with fluorine or chlorine. 1,4-Phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl, chromane-2,6-diyl, or at least one hydrogen in which at least one hydrogen has been replaced with fluorine or chlorine. Chroman-2,6-diyl replaced with fluorine or chlorine. The preferred ring G is 1,4-cyclohexylene to reduce the viscosity or raise the upper temperature limit. Preferred ring J is 1,4-cyclohexylene for lowering the viscosity or raising the upper temperature limit and 1,4-phenylene for lowering the lower limit temperature. Ring I is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4. 5-Trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl. Preferred ring I is 2,3-difluoro-1,4-phenylene to reduce viscosity, 2-chloro-3-fluoro-1,4-phenylene to reduce optical anisotropy, and dielectric constant. 7,8-Difluorochroman-2,6-diyl to increase anisotropy.

Z ¹ , Z ² , and Z ³ are independently single-bonded, ethylene, carbonyloxy, or methyleneoxy. However, at least one of ^{Z 1} , Z ² , and Z ^{3 is ethylene.} Z ⁵ and Z ⁶ are independently single bonds, ethylene, carbonyloxy, or methyleneoxy. Preferred Z ¹ , Z ² , Z ³ , Z ⁵ and Z ⁶ are single bonds to reduce the viscosity and ethylene to increase the elastic constant or lower the lower limit temperature, making the modulus anisotropy. Methyleneoxy to raise. Z ⁴ is a single bond, ethylene or carbonyloxy. Preferred Z ⁴ is a single bond for increased stability.

a is 1, 2, or 3. Preferred a is 1 for lowering the viscosity and 2 or 3 for raising the upper temperature limit. b is 1 or 2, c is 0 or 1, and the sum of b and c is less than or equal to 2. The preferred b is 1 for lowering the viscosity and 2 for raising the upper limit temperature. The preferred c is 0 to lower the viscosity and 1 to lower the lower limit temperature.

In formula (4), P ¹ , P ² and P ³ are independently polymerizable groups. Preferred P ¹ , P ² , or P ³ are polymerizable groups selected from the group of groups represented by formulas (P-1) to (P-6). More preferred P ¹ , P ² , or P ³ is a group represented by formula (P-1), formula (P-2), or formula (P-3). Particularly preferred P ¹ , P ² or P ³ is a group represented by the formula (P-1) or the formula (P-2). The most preferable P ¹ , P ² , or P ³ is a group represented by the formula (P-1). The preferred group represented by the formula (P-1) is -OCO-CH = CH ₂ or -OCO-C (CH ₃ ) = CH ₂ . The wavy lines of the formulas (P-1) to (P-6) indicate the sites to be combined.

In formulas (P-1) to (P-6), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine. It is an alkyl having 1 to 5 carbon atoms replaced with. Preferred M ¹ , M ² , or M ³ is hydrogen or methyl to increase reactivity. The more preferred M ¹ is hydrogen or methyl, and the more preferred M ² or M ³ is hydrogen.

Sp ¹ , Sp ² , and Sp ³ are independently single-bonded or alkylenes with 1 to 10 carbon atoms, in which at least one -CH ₂ − is -O-, -COO-, -OCO. -Or -OCOO- may be replaced, and at least one -CH ₂ -CH _2- may be replaced by -CH = CH- or -C≡C-, and at least 1 in these groups. One hydrogen may be replaced with fluorine or chlorine. Preferred Sp ¹ , Sp ² , or Sp ³ are single bonds, -CH _2- CH _{2- , -CH 2} O-, -OCH _2- , -COO-, -OCO-, -CO-CH = CH-, Or -CH = CH-CO-. More preferred Sp ¹ , Sp ² , or Sp ³ are single bonds.

In formula (4), when all of e P ¹ and g P ³ are groups represented by formula (P-4), of e Sp ¹ and g Sp ³ . At least one is _{an alkylene having 1 to 10 carbon atoms in which at least one -CH 2-} has been replaced with -O-, -COO-, -OCO-, or -OCOO-.

Ring K and Ring M are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl, or pyridine. -2-yl, in these rings at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least one hydrogen is replaced with fluorine or chlorine. It may be replaced with an alkyl having 1 to 12 carbon atoms. The preferred ring K or ring M is phenyl. Ring L is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene. -1,5-Diyl, Naphthalene-1,6-Diyl, Naphthalene-1,7-Diyl, Naphthalene-1,8-Diyl, Naphthalene-2,3-Diyl, Naphthalene-2,6-Diyl, Naphthalene-2 , 7-Diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings. At least one hydrogen is replaced with fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, or alkyl with 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. May be good. The preferred ring L is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁷ and Z ⁸ are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, or-. may be replaced by OCO-, at least one _-CH 2 -CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, or -C It may be replaced by (CH ₃ ) = C (CH ₃ ) −, and in these groups at least one hydrogen may be replaced by fluorine or chlorine. Preferred Z ⁷ or Z ⁸ are single bonds, -CH _2- CH _{2- , -CH 2} O-, -OCH _2- , -COO-, or -OCO-. A more preferred Z ⁷ or Z ⁸ is a single bond.

d is 0, 1, or 2. Preferred d is 0 or 1. e, f, and g are independently 0, 1, 2, 3, or 4, and the sum of e, f, and g is greater than or equal to 1. Preferred e, f, or g is 1 or 2.

Fifth, preferred component compounds are shown. Preferred compounds (1) are compounds (1-1) to compounds (1-14) according to Item 2. In these compounds, at least one of the first components is compound (1-1), compound (1-2), compound (1-3), compound (1-5), compound (1-6), compound ( It is preferably 1-7) or compound (1-12). It is preferred that at least two of the first components are a combination of compound (1-3) and compound (1-6).

Preferred compounds (2) are compounds (2-1) to compounds (2-13) according to Item 5. In these compounds, at least one of the second components is compound (2-1), compound (2-3), compound (2-5), compound (2-6), or compound (2-7). Is preferable. It is preferable that at least two of the second components are a combination of compound (2-1) and compound (2-3), compound (2-1) and compound (2-5).

Preferred compounds (3) are compounds (3-1) to compounds (3-22) according to Item 8. In these compounds, at least one of the third components is compound (3-1), compound (3-2), compound (3-3), compound (3-4), compound (3-6), compound ( 3-7), compound (3-8), or compound (3-10) is preferred. At least two of the third components are compound (3-1) and compound (3-6), compound (3-1) and compound (3-10), compound (3-3) and compound (3-6), It is preferably a combination of compound (3-3) and compound (3-10), compound (3-4) and compound (3-6), or compound (3-4) and compound (3-10).

Preferred compounds (4) are compounds (4-1) to compounds (4-27) according to Item 12. In these compounds, at least one of the additive components is compound (4-1), compound (4-2), compound (4-24), compound (4-25), compound (4-26), or compound. (4-27) is preferable. At least two of the additive components are compound (4-1) and compound (4-2), compound (4-1) and compound (4-18), compound (4-2) and compound (4-24), Compound (4-2) and compound (4-25), compound (4-2) and compound (4-26), compound (4-25) and compound (4-26), or compound (4-18) and It is preferably a combination of compounds (4-24).

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 and the like. An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules to give a twist angle. Examples of such compounds are compound (5-1) to compound (5-5). The preferred proportion of the optically active compound is about 5% by weight or less. A more preferred proportion is in the range of about 0.01% by weight to about 2% by weight.

Antioxidants are 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 (6) in which n is an integer of 1 to 9.

In compound (6), preferred n is 1, 3, 5, 7, or 9. A more preferable n is 7. Since the compound (6) having n 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 and the like 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 used to adapt to polymer-supported orientation (PSA) type devices. Compound (4) is suitable for this purpose. A polymerizable compound different from the compound (4) may be added to the composition together with the compound (4). Instead of compound (4), a polymerizable compound different from compound (4) may be added to the composition. Preferred examples of such polymerizable compounds are compounds such as acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxylane, oxetane), vinyl ketones and the like. A more preferred example is a derivative of acrylate or methacrylate. The preferred proportion of compound (4) is about 10% by weight or more based on the weight of the polymerizable compound. A more preferable ratio is about 50% by weight or more. A particularly preferable ratio is about 80% by weight or more. The most preferable ratio is 100% by weight.

A polymerizable compound such as compound (4) is polymerized by irradiation with ultraviolet rays. Polymerization may be carried out in the presence of a suitable initiator such as a photopolymerization initiator. Appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those of skill in the art and are described in the literature. For example, the photoinitiators Irgacure651®, Irgacure184® (registered trademark; BASF), or Darocur1173® 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 a polymerizable compound such as compound (4), 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 (2-1) is synthesized by the method described in JP-A-59-176221. Compound (3-6) is synthesized by the method described in JP-A-2000-53602. Compound (4-18) is synthesized by the method described in JP-A-7-101900. Antioxidants are commercially available. The compound of formula (6) where n is 1 can be obtained from Sigma-Aldrich Corporation. Compound (6) and the like having n of 7 are synthesized by the method described in US Pat. No. 3,660,505.

Compounds for which synthetic methods were not described are Organic Syntheses, John Wiley & Sons, Inc., Organic Reactions, John Wiley & Sons, Inc., and Comprehensive Organic Synthesis ( Comprehensive Organic Synthesis, Pergamon Press), New Experimental Chemistry Course (Maruzen), etc. can be synthesized by the methods described in the books. 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. Most compositions have a lower limit temperature of about −10 ° C. or lower, an upper limit temperature of about 70 ° C. or higher, and an optical anisotropy in the range of about 0.07 to about 0.20. Compositions having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the proportions of the constituent compounds or by mixing other liquid crystal compounds. Furthermore, a composition having an optical anisotropy in the range of about 0.10 to about 0.30 may be prepared by this method. 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. 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 elements or polycrystalline silicon-TFT elements. It can also be used for an NCAP (nematic curvilinear aligned phase) type device produced by microencapsulating this composition and a PD (polymer dispersed) type device 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 compound, composition and device 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 obtained 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 and the device, 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 this ratio at 25 ° C., 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 that 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. The upper limit temperature of the nematic phase may be abbreviated as "upper limit temperature".

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

(3) Viscosity (bulk viscosity; η; measured at 20 ° C.; mPa · s): An E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used for 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 VA element having a distance (cell gap) between two glass substrates of 20 μm. A stepwise application was applied to this device in the range of 39 to 50 volts in 1 volt increments. After no application for 0.2 seconds, application was repeated under the conditions of only one square wave (square pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. These measurements and M.I. The value of rotational viscosity was obtained from the paper by Imai et al., Calculation formula (8) on page 40. The dielectric anisotropy required for this calculation was measured in item (6).

(5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25 ° C.): The measurement was performed 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 of Δn = n ‖ −n ⊥.

(6) Permittivity anisotropy (Δε; measured at 25 ° C.): The value of permittivity anisotropy was calculated from the equation Δε = ε‖−ε⊥. The permittivity (ε‖ and ε⊥) was measured as follows.
1) Measurement of permittivity (ε‖): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a well-washed glass substrate. After rotating the glass substrate with a spinner, it was heated at 150 ° C. for 1 hour. The sample was placed in a VA element in which the distance (cell gap) between the two glass substrates was 4 μm, and this element was sealed with an adhesive that cures with ultraviolet rays. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the permittivity (ε ‖) of the liquid crystal molecule in the long axis direction was measured.
2) Measurement of permittivity (ε⊥): A polyimide solution was applied to a well-cleaned glass substrate. After firing this glass substrate, the obtained alignment film was subjected to a rubbing treatment. The sample was placed in a TN element in which the distance (cell gap) between the two glass substrates was 9 μm and the twist angle was 80 degrees. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the permittivity (ε⊥) of the liquid crystal molecule in the minor axis direction was measured.

(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. A sample is placed in a VA element in normally black mode in which the distance (cell gap) between two glass substrates is 4 μm and the rubbing direction is anti-parallel, and an adhesive that cures this element with ultraviolet rays is applied. Sealed using. The voltage (60 Hz, square wave) applied to this device was gradually increased by 0.02 V from 0 V to 20 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 10%.

(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 device 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 device used for the measurement had a polyimide alignment film, and the cell gap was 5 μm. A sample was injected into this device and 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 in a constant temperature bath at 80 ° C. for 500 hours, the voltage retention rate was measured and stability against heat was measured. Was evaluated. In the VHR-4 measurement, 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 black mode VA element in which the distance between the two glass substrates (cell gap) was 4 μm and the rubbing direction was antiparallel. This element was sealed with an UV curable adhesive. A square wave (60 Hz, 10 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 response time was expressed as the time required for the transmittance to change from 90% to 10% (fall time; fall time; millisecond).

(13) 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 (electrical capacity of container)} / {(DC current) x (vacuum permittivity)}.

(14) Elastic constant (K11: splay elastic constant, K33: bend elastic constant; measured at 25 ° C; pN): For measurement, use an EC-1 type elastic constant measuring device manufactured by Toyo Technica Co., Ltd. Using. The sample was placed in a vertically oriented element in which the distance (cell gap) between the two glass substrates was 20 μm. A charge of 20 to 0 volts was applied to this device, and the capacitance and applied voltage were measured. Fitting the measured capacitance (C) and applied voltage (V) values using the equations (2.98) and (2.11) on page 75 of the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun). Then, the value of the elastic constant was obtained from the equation (2.10).

Compound (1-5) is synthesized by the method described below.

First step:
A solution of (methoxymethyl) triphenylphosphonium chloride (482.08 g, 1.41 mol) in THF (2 L) was cooled to −60 ° C., potassium t-butoxide (215.66 g, 1.92 mol) was added dropwise, and 1 hour. Stirred. A solution of compound (T-3) (300.67 g, 1.26 mol) synthesized by a known method in THF (900 mL) was added dropwise thereto, and the mixture was returned to room temperature with stirring. The reaction mixture was poured into water, subjected to normal post-treatment, and purified by silica gel chromatography to obtain compound (T-4) (293.17 g, 1.10 mol; 87%).

Second step:
6N hydrochloric acid (180 mL, 1.08 mol) in an acetone solution of compound (T-4) (293.17 g, 1.10 mol) and 2,2-dimethyl-1,3-propanediol (125.71 g, 1.21 mol). ) Was added dropwise, and the mixture was stirred at room temperature for several days. The usual post-treatment was carried out and purified by silica gel chromatography and recrystallization to obtain compound (T-5) (140.51 g, 0.48 mol; 43%).

Third step:
A solution of (methoxymethyl) triphenylphosphonium chloride (197.39 g, 0.58 mol) in THF (700 mL) was cooled to −60 ° C., potassium t-butoxide (59.29 g, 0.53 mol) was added dropwise, and 1 hour. Stirred. A solution of compound (T-5) (140 g, 0.48 mol) synthesized by a known method in THF (700 mL) was added dropwise thereto, and the mixture was returned to room temperature with stirring. The reaction mixture was poured into water, subjected to normal post-treatment, and purified by silica gel chromatography to obtain compound (T-6) (153.51 g, 0.48 mol; quantitative).

Fourth step:
6N hydrochloric acid (380 mL, 1.14 mol) was added dropwise to a solution of compound (T-6) (153 g, 0.47 mol) and tetrabutylammonium bromide (TBAB; 9.28 g, 0.029 mol) in methylene chloride (600 mL). , Stirred for 22 hours. After performing the usual post-treatment, NaOH (1.13 g, 0.028 mol) and Solmix A-11 (1.1 L) were added to the post-treated solution, and the mixture was stirred at room temperature for 18 hours. The usual post-treatment was carried out to obtain compound (T-7) (150.28 g, 0.49 mol, cis / trans = 9/91; quantitative). Solmix® A-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropyl alcohol (1.1%), and was obtained from Japan Alcohol Trading Co., Ltd.

Fifth step:
An ethanol (500 mL) solution of sodium borohydride (11.21 g, 0.30 mol) was ice-cooled, and an ethanol (600 mL) solution of compound (T-7) (146.21 g, 0.47 mol) was added dropwise to room temperature. Was stirred for 18 hours. The usual post-treatment was carried out and purified by silica gel chromatography and recrystallization to obtain compound (T-8) (81.97 g, 0.26 mol; 56%).

6th step:
A solution of compound (T-8) (30.54 g, 0.098 mol), imidazole (8.82 g, 0.13 mol) and triphenylphosphine (34.06 g, 0.13 mol) in toluene (200 mL) was ice-cooled. A solution of iodine (32.9 g, 0.13 mol) in toluene (300 mL) was added dropwise, and the mixture was stirred at room temperature for several days. The usual post-treatment was carried out and purified by silica gel chromatography and recrystallization to obtain compound (T-9) (31.59 g, 0.075 mol; 77%).

7th step:
Compound (T-9) (31.59 g, 0.075 mol) with triethylamine (0.8 g, 7.91 mmol), triphenylphosphine (20.89 g, 0.080 mol) and 1,3-dimethyl-3,4. 5,6-Tetrahydro-2 (1H) -pyrimidinone (11 mL) was added, and the mixture was heated and stirred for 7 days. The usual treatment was carried out to obtain compound (T-10) (47.56 g, 0.07 mol; 93%).

Eighth step:
A solution of compound (T-10) (15.61 g, 0.023 mol) in THF (100 mL) was cooled to −60 ° C., potassium t-butoxide (2.80 g, 0.025 mol) was added dropwise, and the mixture was stirred for 1 hour. .. A solution of compound (T-11) (5.37 g, 0.02 mol) synthesized by a known method in THF (40 mL) was added dropwise thereto, and the mixture was returned to room temperature with stirring. The reaction mixture was poured into water, subjected to normal post-treatment, and purified by silica gel chromatography to obtain compound (T-12) (10.10 g, 0.019 mol; 93%).

9th step:
Compound (T-12) (10.10 g, 0.019 mol) is dissolved in toluene (100 mL) and isopropyl alcohol (IPA; 100 mL), and Pd / C (0.24 g) is further added to absorb hydrogen under a hydrogen atmosphere. Stir at room temperature until no more. After removing Pd / C, purification was performed by silica gel chromatography and recrystallization to obtain compound (T-13) (6.21 g, 0.011 mol; 61%).

10th step:
87% formic acid (40 mL) was added to a solution of compound (T-13) (6.21 g, 0.011 mol) and tetrabutylammonium bromide (TBAB; 0.84 g, 2.61 mmol) in toluene (300 mL) for 11 hours. It was heated and stirred. The usual post-treatment was carried out to obtain compound (T-14) (6.47 g, 0.014 mol, cis / trans = 24/76; quantitative).

11th step:
Toluene (75 mL), methanol (150 mL) and p-toluenesulfonic acid (PTSA; 0.71 g, 3.73 mmol) were added to compound (T-14) (5.23 g, 0.011 mol), and the mixture was heated and stirred for 3 hours. .. The usual post-treatment was carried out to obtain compound (T-15) (5.40 g, 0.011 mol; quantitative).

12th step:
87% formic acid (20 mL) was added to a solution of compound (T-15) (5.40 g, 0.011 mol) and tetrabutylammonium bromide (TBAB; 0.76 g, 2.36 mmol) in toluene (100 mL) at room temperature. Stirred for several hours. The usual post-treatment was carried out to obtain compound (T-16) (3.72 g, 8.08 mmol; 77%).

13th step:
A solution of methyltriphenylphosphonium bromide (3.47 g, 10.47 mol) in THF (50 mL) was cooled to −70 ° C., potassium t-butoxide (1.21 g, 10.78 mmol) was added dropwise, and the mixture was stirred for 1 hour. A solution of compound (T-16) (3.72 g, 8.08 mmol) in THF (50 mL) was added dropwise thereto, and the mixture was returned to room temperature with stirring. The reaction mixture was poured into water, subjected to normal post-treatment and purified by silica gel chromatography and recrystallization to give compound (1-5) (2.86 g, 6.24 mmol; 77%).

^{1 1} H-NMR (CDCl ₃ ; δppm): 6.86-6.80 (1H, m), 6.66 (1H, dt, 7.5Hz, 1.5Hz), 5.81-5.73 (1H) , M), 4.95 (1H, d, 16Hz), 4.87 (1H, d, 10.5Hz), 4.08 (2H, q, 7.5Hz), 2.74 (1H, m), 1.85-1.69 (12H, m), 1.44-1.41 (6H, m), 1.21-1.19 (5H, m), 1.09-1.07 (10H, m) ), 1.04-1.02 (3H, m).

The compounds in the examples are represented by symbols based on the definitions in Table 3 below. In Table 3, the molecular configuration for 1,4-cyclohexylene is trance. The number in parentheses after the symbol corresponds to the compound number. 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-2002-193853. The rationale is that this composition contains compound (2-2), compound (3-1), and compound (3-6) and has the smallest γ1. The components and properties of this composition were as follows.
5-HB-3 (2-2) 13%
5-HB (2F, 3F) -O2 (3-1) 13%
3-HHB (2F, 3F) -O2 (3-6) 14%
5-HHB (2F, 3F) -O2 (3-6) 14%
2-HHB (2F, 3F) -1 (3-6) 12%
3-HHB (2F, 3F) -1 (3-6) 12%
5-HHHB (2F, 3F) -1 (-) 5%
3-HB (2F, 3F) HH-3 (-) 5%
2-HB (2F, 3F) HH-3 (-) 3%
5-HB (2F, 3F) -O4 (3-1) 9%
NI = 112.6 ° C.; γ1 = 241.0 mPa · s; Δn = 0.093; Δε = -4.1.

[Example 1]
V-HH2BB (2F, 3F) -O2 (1-6) 7%
3-HH-V (2-1) 30%
V-HHB-1 (2-5) 4%
3-HB (2F, 3F) -O2 (3-1) 3%
V-HB (2F, 3F) -O2 (3-1) 6%
3-BB (2F, 3F) -O2 (3-4) 6%
3-HHB (2F, 3F) -O2 (3-6) 7%
V-HHB (2F, 3F) -O1 (3-6) 3%
V-HHB (2F, 3F) -O2 (3-6) 8%
V-HHB (2F, 3F) -O4 (3-6) 8%
3-HBB (2F, 3F) -O2 (3-10) 7%
V-HBB (2F, 3F) -O2 (3-10) 7%
V-HBB (2F, 3F) -O4 (3-10) 4%
NI = 99.8 ° C; Tc <-30 ° C; γ1 = 127.0 mPa · s; Δn = 0.108; Δε = -3.8; Vth = 2.26V; K33 = 17.3pN.

[Example 2]
3-HH2HB (2F, 3F) -O2 (1-5) 3%
V-HH2HB (2F, 3F) -O2 (1-5) 4%
V-HH2BB (2F, 3F) -O4 (1-6) 5%
V-HH-V (2-1) 18%
V-HH-2V (2-1) 6%
V-HHB-1 (2-5) 8%
V2-HHB-1 (2-5) 8%
2-H1OB (2F, 3F) -O2 (3-3) 6%
3-BB (2F, 3F) -O2 (3-4) 8%
V2-BB (2F, 3F) -O2 (3-4) 8%
3-HH2B (2F, 3F) -O2 (3-7) 8%
3-HDhB (2F, 3F) -O2 (3-16) 8%
3-dhBB (2F, 3F) -O2 (3-17) 7%
5-HBBH-1O1 (-) 3%
NI = 101.1 ° C; Tc <-20 ° C; γ1 = 131.7 mPa · s; Δn = 0.110; Δε = -3.4.

[Example 3]
3-H2HHB (2F, 3F) -O2 (1-1) 3%
2-HH2BB (2F, 3F) -O2 (1-6) 3%
2-BB (F) B2B (2F, 3F) -3 (1-14) 3%
V-HH-V (2-1) 21%
2-HH-3 (2-1) 6%
3-HHB-1 (2-5) 6%
3-HHB-O1 (2-5) 5%
5-HBB (F) B-3 (2-13) 3%
3-H2B (2F, 3F) -O2 (3-2) 5%
2-BB (2F, 3F) -O2 (3-4) 4%
3-BB (2F, 3F) -O2 (3-4) 4%
2O-BB (2F, 3F) -O2 (3-4) 5%
V-HHB (2F, 3F) -O2 (3-6) 8%
V2-HHB (2F, 3F) -O2 (3-6) 8%
2-HH1OB (2F, 3F) -O2 (3-8) 3%
3-HH1OB (2F, 3F) -O2 (3-8) 5%
V-HH1OB (2F, 3F) -O2 (3-8) 5%
3-HHB (2F, 3CL) -O2 (3-12) 3%
NI = 103.7 ° C; Tc <-20 ° C; γ1 = 135.1 mPa · s; Δn = 0.108; Δε = -3.7.

[Example 4]
2-H2HBB (2F, 3F) -O2 (1-2) 3%
4-H2HBB (2F, 3F) -O2 (1-2) 3%
V-H2HBB (2F, 3F) -O2 (1-2) 3%
V-HBB2B (2F, 3F) -O2 (1-12) 3%
V-HH-2V1 (2-1) 10%
3-HH-V (2-1) 20%
3-HH-VFF (2-1) 3%
3-HB (2F, 3F) -O2 (3-1) 4%
5-HB (2F, 3F) -O2 (3-1) 3%
3-BB (2F, 3F) -O2 (3-4) 6%
3-HHB (2F, 3F) -O2 (3-6) 7%
V-HHB (2F, 3F) -O2 (3-6) 8%
V-HHB (2F, 3F) -O4 (3-6) 8%
3-HBB (2F, 3F) -O2 (3-10) 5%
V-HBB (2F, 3F) -O2 (3-10) 6%
V-HBB (2F, 3F) -O4 (3-10) 5%
3-B (2F) B (2F, 3F) -O2 (3-22) 3%
NI = 104.1 ° C; Tc <-20 ° C; γ1 = 140.1 mPa · s; Δn = 0.115; Δε = -3.6.

[Example 5]
V-H2BBB (2F, 3F) -O2 (1-3) 5%
3-B2BBB (2F, 3F) -O2 (1-4) 3%
V-HH2BB (2F, 3F) -O2 (1-6) 4%
V-HH2BB (2F, 3F) -O4 (1-6) 4%
V-HHB2B (2F, 3F) -O2 (1-11) 4%
2-HH-3 (2-1) 16%
2-HH-5 (2-1) 6%
3-HH-4 (2-1) 6%
5-HB (F) BH-3 (2-12) 3%
3-HB (2F, 3F) -O2 (3-1) 5%
V2-HB (2F, 3F) -O2 (3-1) 5%
V-H1OB (2F, 3F) -O2 (3-3) 5%
2-BB (2F, 3F) -O2 (3-4) 5%
3-BB (2F, 3F) -O2 (3-4) 6%
3-HHB (2F, 3F) -O2 (3-6) 5%
V-HHB (2F, 3F) -O2 (3-6) 5%
V2-HHB (2F, 3F) -O2 (3-6) 5%
V2-BB (2F, 3F) B-1 (3-9) 5%
5-BB (2F) B (2F, 3F) -O2 (3-20) 3%
NI = 99.5 ° C; Tc <-20 ° C; γ1 = 144.5 mPa · s; Δn = 0.126; Δε = -3.7.

[Example 6]
2-H2BBB (2F, 3F) -O2 (1-3) 3%
3-H2BBB (2F, 3F) -O2 (1-3) 3%
5-H2BBB (2F, 3F) -O2 (1-3) 3%
3-HB2BB (2F, 3F) -O2 (1-7) 3%
V-HB2BB (2F, 3F) -O2 (1-7) 3%
V-HH-2V1 (2-1) 6%
3-HH-V (2-1) 25%
1-BB-3 (2-3) 5%
1-BB (F) B-2V (2-7) 3%
3-HB (2F, 3F) -O2 (3-1) 3%
2-BB (2F, 3F) -O2 (3-4) 6%
1V2-BB (2F, 3F) -O2 (3-4) 3%
V2-HHB (2F, 3F) -O2 (3-6) 4%
1V-HHB (2F, 3F) -O2 (3-6) 5%
5-HH2B (2F, 3F) -O2 (3-7) 4%
3-HBB (2F, 3F) -O2 (3-10) 5%
5-HBB (2F, 3F) -O2 (3-10) 4%
V-HBB (2F, 3F) -O2 (3-10) 5%
V-HBB (2F, 3F) -O4 (3-10) 4%
3-BB (F) B (2F, 3F) -O2 (3-21) 3%
NI = 111.4 ° C; Tc <-20 ° C; γ1 = 130.2 mPa · s; Δn = 0.146; Δε = -3.4.

[Example 7]
3-H2HHB (2F, 3F) -O2 (1-1) 4%
V2-H2HHB (2F, 3F) -O2 (1-1) 3%
2-BB2B (2F) B (2F, 3F) -3 (1-9) 3%
V-HH-V (2-1) 24%
1-BB-5 (2-3) 5%
V-HHB-1 (2-5) 6%
3-HHEBH-3 (2-11) 3%
3-HB (2F, 3F) -O2 (3-1) 5%
3-HB (2F, 3F) -O4 (3-1) 3%
3-BB (2F, 3F) -O2 (3-4) 3%
5-BB (2F, 3F) -O2 (3-4) 4%
3-HHB (2F, 3F) -O2 (3-6) 5%
5-HHB (2F, 3F) -O2 (3-6) 5%
V-HHB (2F, 3F) -O1 (3-6) 3%
V-HHB (2F, 3F) -O2 (3-6) 5%
V-HHB (2F, 3F) -O4 (3-6) 3%
1V2-HHB (2F, 3F) -O2 (3-6) 5%
3-HBB (2F, 3F) -O2 (3-10) 3%
V2-HBB (2F, 3F) -O2 (3-10) 5%
2-HchB (2F, 3F) -O2 (3-19) 3%
NI = 104.7 ° C; Tc <-20 ° C; γ1 = 135.0 mPa · s; Δn = 0.111; Δε = -3.5.

[Example 8]
4-B2BBB (2F, 3F) -O2 (1-4) 3%
5-B2BBB (2F, 3F) -O2 (1-4) 3%
3-HH2BB (2F, 3F) -O2 (1-6) 3%
4-HH2BB (2F, 3F) -O2 (1-6) 3%
2-HH-3 (2-1) 20%
2-HH-5 (2-1) 8%
1-HH-2V1 (2-1) 3%
V2-BB-1 (2-3) 5%
3-HBB-2 (2-6) 5%
5-HB (2F, 3F) -O2 (3-1) 3%
2-HHB (2F, 3F) -1 (3-6) 3%
3-HHB (2F, 3F) -1 (3-6) 4%
V-HH2B (2F, 3F) -O2 (3-7) 6%
3-HBB (2F, 3F) -O2 (3-10) 7%
V-HBB (2F, 3F) -O2 (3-10) 7%
V-HBB (2F, 3F) -O4 (3-10) 4%
3-HDhB (2F, 3F) -O2 (3-16) 5%
5-HDhB (2F, 3F) -O2 (3-16) 5%
3-chB (2F, 3F) -O2 (3-18) 3%
NI = 104.2 ° C; Tc <-20 ° C; γ1 = 137.8 mPa · s; Δn = 0.118; Δε = -3.3.

[Example 9]
V2-H2BBB (2F, 3F) -O2 (1-3) 4%
V2-HH2HB (2F, 3F) -O2 (1-5) 3%
3-BB2BB (2F, 3F) -O2 (1-8) 3%
5-BB2BB (2F, 3F) -O2 (1-8) 3%
3-HH-V (2-1) 23%
4-HH-V (2-1) 6%
3-HHEH-3 (2-4) 5%
1-BB (F) B-2V (2-7) 4%
3-HB (F) HH-2 (2-10) 3%
V-HB (2F, 3F) -O2 (3-1) 5%
V-HB (2F, 3F) -O4 (3-1) 3%
3-H1OB (2F, 3F) -O2 (3-3) 5%
3-BB (2F, 3F) -O2 (3-4) 5%
3-B (2F, 3F) B (2F, 3F) -O2 (3-5) 2%
V-HHB (2F, 3F) -O2 (3-6) 8%
V-HHB (2F, 3F) -O4 (3-6) 7%
2-BB (2F, 3F) B-3 (3-9) 5%
2-BB (2F, 3F) B-4 (3-9) 3%
V-dhBB (2F, 3F) -O2 (3-17) 3%
NI = 96.5 ° C; Tc <-20 ° C; γ1 = 138.4 mPa · s; Δn = 0.124; Δε = -3.2.

[Example 10]
3-H2HHB (2F, 3F) -O2 (1-1) 3%
V-H2HHB (2F, 3F) -O2 (1-1) 3%
V-H2BBB (2F, 3F) -O2 (1-3) 4%
5-HH2HB (2F, 3F) -O2 (1-5) 3%
V-HH-V (2-1) 10%
V-HH-2V (2-1) 12%
3-HH-2V1 (2-1) 3%
3-HHB-3 (2-5) 5%
V-HHB-1 (2-5) 6%
V-HBB-2 (2-6) 4%
V-HB (2F, 3F) -O2 (3-1) 6%
5-H2B (2F, 3F) -O2 (3-2) 4%
3-BB (2F, 3F) -O2 (3-4) 6%
V-HHB (2F, 3F) -O1 (3-6) 4%
V-HHB (2F, 3F) -O2 (3-6) 5%
1V-HHB (2F, 3F) -O2 (3-6) 5%
V2-HBB (2F, 3F) -O2 (3-10) 3%
V-HBB (2F, 3F) -O2 (3-10) 5%
V-HBB (2F, 3F) -O4 (3-10) 3%
5-HDhB (2F, 3F) -O2 (3-16) 3%
V-HDhB (2F, 3F) -O2 (3-16) 3%
NI = 109.8 ° C; Tc <-20 ° C; γ1 = 137.8 mPa · s; Δn = 0.116; Δε = -3.3.

[Example 11]
3-H2HBB (2F, 3F) -O2 (1-2) 3%
V-H2HBB (2F, 3F) -O1 (1-2) 3%
3-HH2HB (2F, 3F) -O2 (1-5) 3%
5-HH2BB (2F, 3F) -O2 (1-6) 3%
V-HH2BB (2F, 3F) -O2 (1-6) 5%
V-HH2BB (2F, 3F) -O4 (1-6) 3%
V-HH-V (2-1) 15%
3-HH-V (2-1) 16%
V2-BB2B-1 (2-9) 4%
1-BB2B-2V (2-9) 4%
3-HB (2F, 3F) -O2 (3-1) 5%
V2-HB (2F, 3F) -O2 (3-1) 4%
1V2-BB (2F, 3F) -O2 (3-4) 5%
2-HHB (2F, 3F) -1 (3-6) 6%
3-HHB (2F, 3F) -1 (3-6) 3%
V-HHB (2F, 3F) -O2 (3-6) 8%
3-HBB (2F, 3F) -O2 (3-10) 7%
3-HH1OCro (7F, 8F) -5 (3-15) 3%
NI = 109.6 ° C; Tc <-20 ° C; γ1 = 114.8 mPa · s; Δn = 0.115; Δε = -3.4.

[Example 12]
5-H2HBB (2F, 3F) -O2 (1-2) 3%
5-HH2BB (2F, 3F) -O2 (1-6) 3%
V-HH2BB (2F, 3F) -O2 (1-6) 4%
V-HH2BB (2F, 3F) -O4 (1-6) 3%
V-HH-2V1 (2-1) 10%
4-HH-V (2-1) 15%
7-HB-1 (2-2) 4%
V-HHB-1 (2-5) 4%
5-B (F) BB-3 (2-8) 3%
V-HB (2F, 3F) -O2 (3-1) 9%
3-H1OB (2F, 3F) -O2 (3-3) 6%
1V2-BB (2F, 3F) -O2 (3-4) 5%
3-HHB (2F, 3F) -O2 (3-6) 4%
V-HHB (2F, 3F) -O1 (3-6) 3%
V-HHB (2F, 3F) -O2 (3-6) 5%
1V-HH1OB (2F, 3F) -O2 (3-8) 3%
2-HBB (2F, 3F) -O2 (3-10) 5%
3-HBB (2F, 3F) -O2 (3-10) 4%
5-HBB (2F, 3F) -O2 (3-10) 4%
3-H1OCro (7F, 8F) -5 (3-14) 3%
NI = 98.6 ° C; Tc <-20 ° C; γ1 = 140.3 mPa · s; Δn = 0.111; Δε = -3.7.

[Example 13]
2-H2HHB (2F, 3F) -O2 (1-1) 3%
3-H2HHB (2F, 3F) -O2 (1-1) 3%
2-HH2BB (2F, 3F) -O2 (1-6) 3%
2-BB2BB (2F, 3F) -O2 (1-8) 3%
V-HH-V (2-1) 13%
V-HH-V1 (2-1) 6%
2-HH-3 (2-1) 10%
3-HB-O2 (2-2) 3%
3-HB (2F, 3F) -O2 (3-1) 6%
5-HB (2F, 3F) -O2 (3-1) 5%
V-H1OB (2F, 3F) -O4 (3-3) 3%
V2-H1OB (2F, 3F) -O4 (3-3) 3%
V-HHB (2F, 3F) -O2 (3-6) 6%
V-HHB (2F, 3F) -O4 (3-6) 5%
1V2-HHB (2F, 3F) -O2 (3-6) 4%
3-HBB (2F, 3F) -O2 (3-10) 6%
4-HBB (2F, 3F) -O2 (3-10) 3%
V-HBB (2F, 3F) -O2 (3-10) 6%
V-HBB (2F, 3F) -O4 (3-10) 6%
3-HBB (2F, 3CL) -O2 (3-13) 3%
NI = 97.8 ° C; Tc <-20 ° C; γ1 = 142.1 mPa · s; Δn = 0.112; Δε = -3.9.

[Example 14]
V-HH2HB (2F, 3F) -O2 (1-5) 4%
V-HH2BB (2F, 3F) -O2 (1-6) 5%
5-HB2BB (2F, 3F) -O2 (1-7) 3%
2-BB (F) B2B (2F, 3F) -3 (1-14) 3%
3-HH-V (2-1) 25%
5-HH-V (2-1) 5%
1V2-BB-1 (2-3) 4%
V-HHB-1 (2-5) 4%
V2-HHB-1 (2-5) 4%
5-HB (2F, 3F) -O2 (3-1) 5%
V2-HB (2F, 3F) -O2 (3-1) 6%
V2-H2B (2F, 3F) -O2 (3-2) 3%
V2-BB (2F, 3F) -O2 (3-4) 5%
3-HHB (2F, 3F) -O2 (3-6) 7%
V-HHB (2F, 3F) -O2 (3-6) 5%
3-HBB (2F, 3F) -O2 (3-10) 6%
V-HHB (2F, 3CL) -O2 (3-12) 3%
V2-HHB (2F, 3CL) -O2 (3-12) 3%
NI = 102.7 ° C; Tc <-20 ° C; γ1 = 119.7 mPa · s; Δn = 0.109; Δε = -3.3.

[Example 15]
5-H2HHB (2F, 3F) -O2 (1-1) 3%
V-HH2HB (2F, 3F) -O2 (1-5) 3%
3-HB2BB (2F, 3F) -O2 (1-7) 3%
V-HBB2B (2F, 3F) -O2 (1-12) 3%
3-HH-V (2-1) 25%
3-HH-V1 (2-1) 5%
V-HHB-1 (2-5) 5%
V-HB (2F, 3F) -O2 (3-1) 7%
3-BB (2F, 3F) -O2 (3-4) 6%
V-HHB (2F, 3F) -O1 (3-6) 3%
V-HHB (2F, 3F) -O2 (3-6) 8%
V-HHB (2F, 3F) -O4 (3-6) 8%
V-HH2B (2F, 3F) -O4 (3-7) 3%
3-HBB (2F, 3F) -O2 (3-10) 6%
V-HBB (2F, 3F) -O2 (3-10) 6%
V-HBB (2F, 3F) -O4 (3-10) 3%
3-HEB (2F, 3F) B (2F, 3F) -O2 (3-11) 3%
NI = 108.4 ° C; Tc <-20 ° C; γ1 = 137.5 mPa · s; Δn = 0.115; Δε = -3.7.

[Example 16]
3-H2HHB (2F, 3F) -O2 (1-1) 5%
V-H2HBB (2F, 3F) -O2 (1-2) 3%
2-HH2HB (2F, 3F) -O2 (1-5) 3%
V-HH2BB (2F, 3F) -O3 (1-6) 3%
V-HH-V (2-1) 24%
V-HHB-1 (2-5) 5%
V2-HHB-1 (2-5) 3%
3-HB (2F, 3F) -O2 (3-1) 3%
V-HB (2F, 3F) -O2 (3-1) 5%
V2-BB (2F, 3F) -O2 (3-4) 6%
5-HHB (2F, 3F) -O2 (3-6) 5%
V-HHB (2F, 3F) -O2 (3-6) 6%
V-HHB (2F, 3F) -O4 (3-6) 4%
V2-HHB (2F, 3F) -O2 (3-6) 7%
3-HBB (2F, 3F) -O2 (3-10) 7%
V-HBB (2F, 3F) -O2 (3-10) 7%
V-HBB (2F, 3F) -O4 (3-10) 4%
NI = 112.5 ° C; Tc <-20 ° C; γ1 = 143.0 mPa · s; Δn = 0.114; Δε = -3.8.

[Example 17]
V-HH2BB (2F, 3F) -O2 (1-6) 5%
V-HH2BB (2F, 3F) -O4 (1-6) 5%
3-HH-V (2-1) 28%
2-BB (F) B-3 (2-7) 4%
V-HB (2F, 3F) -O2 (3-1) 6%
V2-HB (2F, 3F) -O2 (3-1) 3%
3-BB (2F, 3F) -O2 (3-4) 6%
2-HHB (2F, 3F) -O2 (3-6) 3%
3-HHB (2F, 3F) -O2 (3-6) 4%
V-HHB (2F, 3F) -O1 (3-6) 3%
V-HHB (2F, 3F) -O2 (3-6) 8%
1V-HHB (2F, 3F) -O2 (3-6) 4%
1V2-HHB (2F, 3F) -O2 (3-6) 4%
3-HBB (2F, 3F) -O2 (3-10) 7%
V-HBB (2F, 3F) -O2 (3-10) 6%
V-HBB (2F, 3F) -O4 (3-10) 4%
NI = 105.9 ° C; Tc <-20 ° C; γ1 = 138.9 mPa · s; Δn = 0.119; Δε = -3.9.

[Example 18]
V-HH2HB (2F, 3F) -O2 (1-5) 7%
3-HH-V (2-1) 30%
V-HHB-1 (2-5) 2%
V-HB (2F, 3F) -O2 (3-1) 7%
V2-BB (2F, 3F) -O2 (3-4) 3%
3-BB (2F, 3F) -O2 (3-4) 6%
3-HHB (2F, 3F) -O1 (3-6) 7%
V-HHB (2F, 3F) -O1 (3-6) 3%
V-HHB (2F, 3F) -O2 (3-6) 9%
V-HHB (2F, 3F) -O4 (3-6) 8%
3-HBB (2F, 3F) -O2 (3-10) 7%
V-HBB (2F, 3F) -O2 (3-10) 7%
V-HBB (2F, 3F) -O4 (3-10) 4%
NI = 98.1 ° C.; Tc <-30 ° C.; γ1 = 122.0 mPa · s; Δn = 0.106; Δε = -3.8; K33 = 17.2 pN.

[Example 19]
V-H2BBB (2F, 3F) -O2 (1-3) 5%
3-HH-V (2-1) 23%
3-HHB-1 (2-5) 3%
V-HHB-1 (2-5) 10%
V2-HHB-1 (2-5) 8%
3-DhB (2F, 3F) -O2 (3) 9%
2-BB (2F, 3F) -O2 (3-4) 7%
3-BB (2F, 3F) -O2 (3-4) 8%
3-HH2B (2F, 3F) -O2 (3-7) 6%
3-HDhB (2F, 3F) -O2 (3-16) 11%
3-dhBB (2F, 3F) -O2 (3-17) 10%
NI = 86.5 ° C; Tc <-30 ° C; γ1 = 127.0 mPa · s; Δn = 0.111; Δε = -3.6; Vth = 2.15 V.

The viscosity (γ1) of the composition of Comparative Example 1 was 241.0 mPa · s. On the other hand, the compositions of Examples 1 to 19 had a smaller viscosity than that of Comparative Example 1. 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, a large elastic constant, an appropriate optical anisotropy, a negatively large dielectric anisotropy, a large resistivity, a high stability against ultraviolet rays, and heat. Satisfies at least one property, or has an appropriate balance with respect to at least two properties, such as high stability against. A liquid crystal display element containing this composition has characteristics such as a short response time, a large voltage retention rate, a low threshold voltage, a large contrast ratio, and a long life, and therefore can be used in liquid crystal projectors, liquid crystal televisions, and the like. ..

Claims (17)

A liquid crystal composition containing at least one compound selected from the group of compounds represented by the formula (1) as a first component, and having a nematic phase and negative dielectric anisotropy. However, the first component contains at least one compound selected from the group of compounds represented by the formulas (1-1) to (1-14).

In formula (1), R ¹ and R ² 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, an alkenyloxy having 2 to 12 carbon atoms, or At least one hydrogen is an alkyl having 1 to 12 carbon atoms in which fluorine or chlorine is replaced; ring A, ring B, ring C, and ring D are independently 1,4-cyclohexylene, 1,4-. Cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine, naphthalene-2,6-diyl, at least one hydrogen Naphthalene-2,6-diyl, chroman-2,6-diyl replaced with fluorine or chlorine, or chroman-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine; however, ring A , Ring B, Ring C, and Ring D are 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 3,4,5-trifluoro. be a naphthalene-2,6-diyl or ^{7,8-difluoro-chroman-2,6-diyl,;} Z 1, ^{Z 2,} and ^{Z 3} are each independently a single bond, ethylene, carbonyloxy or methyleneoxy, There ^proviso, Ri least one ethylene der of Z 1, ^{Z 2,} and ^{Z 3;}
In formulas (1-1) to (1-14), R ¹ and R ² are independently alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and carbon. Alkenyloxy of numbers 2 to 12, or alkyls of carbons 1 to 12 in which at least one hydrogen is replaced with fluorine or chlorine. Based on the weight of the liquid crystal composition, the ratio of the first component is from 3 wt% to 50 wt%, the liquid crystal composition according to claim 1. 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 formula (2) as a second component.

In formula (2), R ³ and R ⁴ are independently replaced by an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, and at least one hydrogen being replaced with fluorine or chlorine. Alkyl with 1 to 12 carbon atoms, or alkenyl with 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; Ring E and Ring F are independently 1,4-cyclohexylene. 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ⁴ is a single bond, ethylene, or carbonyloxy; a is 1 2, or 3. The liquid crystal according to any one of claims 1 to 3 , which contains at least one compound selected from the group of compounds represented by the formulas (2-1) to (2-13) as the second component. Composition.

In formulas (2-1) to (2-13), R ³ and R ⁴ are independently alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or at least. An alkyl having 1 to 12 carbon atoms in which one hydrogen has been replaced with fluorine or chlorine, or an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine. The liquid crystal composition according to claim 3 or 4 , wherein the proportion of the second component is in the range of 10% by weight to 70% by weight based on the weight of the liquid crystal composition. The liquid crystal composition according to any one of claims 1 to 5 , 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 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, an alkenyloxy having 2 to 12 carbon atoms, or At least one hydrogen is an alkyl having 1 to 12 carbon atoms in which fluorine or chlorine is replaced; ring G and ring J are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-. 2,5-Diyl, 1,4-phenylene, at least one hydrogen replaced with fluorine or chlorine 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen replaced with fluorine or chlorine Naphthalene-2,6-diyl, chroman-2,6-diyl, or chroman-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine; ring I 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-be difluorochroman-2,6-diyl; ^{Z 5} and ^{Z 6} are each independently a single bond, ethylene, carbonyloxy or methyleneoxy,; b is 1 or 2; c is 0 or 1; the sum of b and c is 2 or less. The liquid crystal according to any one of claims 1 to 6 , which contains at least one compound selected from the group of compounds represented by formulas (3-1) to (3-22) as a third component. Composition.

In formulas (3-1) to (3-22), R ⁵ and R ⁶ are independently alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and carbon. Alkenyloxy of numbers 2 to 12, or alkyls of carbons 1 to 12 in which at least one hydrogen is replaced with fluorine or chlorine. The liquid crystal composition according to claim 6 or 7 , wherein the proportion of the third component is in the range of 10% by weight to 80% by weight based on the weight of the liquid crystal composition. The liquid crystal composition according to any one of claims 1 to 8 , which contains at least one polymerizable compound selected from the group of compounds represented by the formula (4) as an additive component.

In formula (4), ring K and ring M are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-. 2-Il or pyridine-2-yl, in these rings at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least one hydrogen. It may be replaced with an alkyl having 1 to 12 carbon atoms replaced with fluorine or chlorine; ring L is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1, 2-Diyl, Naphthalene-1,3-Diyl, Naphthalene-1,4-Diyl, Naphthalene-1,5-Diyl, Naphthalene-1,6-Diyl, Naphthalene-1,7-Diyl, Naphthalene-1,8- Diyl, Naphthalene-2,3-Diyl, Naphthalene-2,6-Diyl, Naphthalene-2,7-Diyl, Tetrahydropyran-2,5-Diyl, 1,3-Dioxane-2,5-Diyl, Pyrimidine-2 , 5-Diyl, or pyridine-2,5-Diyl, in which at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least 1 One hydrogen may be replaced with an alkyl having 1 to 12 carbon atoms replaced with fluorine or chlorine; Z ⁷ and Z ⁸ are independently single-bonded or alkylenes having 1 to 10 carbon atoms, and in this alkylene. , At least one −CH ₂ − may be replaced by −O −, −CO−, −COO−, or −OCO−, and at least one −CH ₂ −CH ₂₋ is −CH = CH−. , -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )-, at least one of these groups. Hydrogen may be replaced with fluorine or chlorine; P ¹ , P ² , and P ³ are independently polymerizable groups; Sp ¹ , Sp ² , and Sp ³ are independently single-bonded, Alternatively, it is an alkylene having 1 to 10 carbon atoms, in which at least one -CH _2- may be replaced with -O-, -COO-, -OCO-, or -OCOO-, and at least one. -CH ₂ -CH _2- is -C It may be replaced by H = CH- or -C≡C-, in these groups at least one hydrogen may be replaced by fluorine or chlorine; d is 0, 1, or 2; e, f, and g are independently 0, 1, 2, 3, or 4; and the sum of e, f, and g is greater than or equal to 1. Claim that in formula (4), P ¹ , P ² , and P ³ are independently polymerizable groups selected from the group of groups represented by formula (P-1) to formula (P-6). Item 9. The liquid crystal composition according to Item 9.

In formulas (P-1) to (P-6), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine. Alkyl with 1 to 5 carbon atoms replaced by;
In formula (4), when all of e P ¹ and g P ³ are groups represented by formula (P-4), of e Sp ¹ and g Sp ³ . At least one is _{an alkylene having 1 to 10 carbon atoms in which at least one -CH 2-} has been replaced with -O-, -COO-, -OCO-, or -OCOO-. The invention according to any one of claims 1 to 10 , which contains at least one polymerizable compound selected from the group of compounds represented by the formulas (4-1) to (4-27) as an additive component. Liquid crystal composition.

In the formula (4-27) from equation ^(4-1), P 4, ^{P 5,} and ^{P 6} are each independently from the group of radicals represented by the formula (P-1) by the formula (P-3) It is the polymerizable group of choice;

In formulas (P-1) to (P-3), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine. Alkyl with 1 to 5 carbon atoms replaced by;
In formulas (4-1) to (4-27), Sp ¹ , Sp ² , and Sp ³ are independently single bonds or alkylenes having 1 to 10 carbon atoms, and at least one of the alkylenes. −CH ₂ − may be replaced by −O −, −COO−, −OCO−, or −OCOO−, and at least one −CH ₂ −CH ₂₋ is −CH = CH− or −C≡ It may be replaced with C-, and in these groups at least one hydrogen may be replaced with fluorine or chlorine. The liquid crystal composition according to any one of claims 9 to 11 , wherein the addition ratio of the additive component is in the range of 0.03% by weight to 10% by weight based on the weight of the liquid crystal composition. A liquid crystal display device containing the liquid crystal composition according to any one of claims 1 to 12. The liquid crystal display element according to claim 13 , wherein the operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and the drive method of the liquid crystal display element is an active matrix method. A polymer-supported oriented liquid crystal display device containing the liquid crystal composition according to any one of claims 1 to 12, or having a polymerizable compound in the liquid crystal composition polymerized. Use of the liquid crystal composition according to any one of claims 1 to 12 in a liquid crystal display element. Use of the liquid crystal composition according to any one of claims 1 to 12 in a polymer-supported oriented liquid crystal display device.