JP2024026047A - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

[Challenges] High maximum temperature, low minimum temperature, small viscosity, large optical anisotropy, large negative dielectric anisotropy, large elastic constant, large specific resistance, high stability against light, high stability against heat, etc. The present invention provides a liquid crystal composition that satisfies at least one characteristic or has an appropriate balance in at least two characteristics, and an AM element containing this composition. [Solution] Component A contains a specific compound having large optical anisotropy and negatively large dielectric anisotropy, component B contains a specific compound having a high upper limit temperature or small viscosity, and component C contains a specific compound having a large negative dielectric anisotropy. The liquid crystal composition may contain a specific compound having large dielectric constant anisotropy or a specific compound having a polymerizable group as additive X. [Selection diagram] None

Description

The present invention relates to a liquid crystal composition, a liquid crystal display element containing this composition, and the like. In particular, the present invention relates to a liquid crystal composition having negative dielectric anisotropy, and a liquid crystal display element containing this composition and having modes such as IPS, VA, FFS, and FPA. The present invention also relates to a polymer-supported alignment type liquid crystal display element.

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

A liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the properties of this composition, an AM element with good properties can be obtained. The relationships among these properties are summarized in Table 1 below. The properties of the composition will be further explained based on commercially available AM devices. The temperature range of the nematic phase is related to the usable temperature range of the device. The preferable upper limit temperature of the nematic phase is about 70°C or higher, and the preferable 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 preferable for displaying moving images on the device. A shorter response time, even 1 millisecond, is desirable. Therefore, a low viscosity in the composition is preferred. Small viscosities at low temperatures are more preferred.

The optical anisotropy of a composition is related to the contrast ratio of the device. Depending on the mode of the device, large optical anisotropy or small optical anisotropy, ie, 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 value of the product depends on the type of operating mode. This value ranges from about 0.30 μm to about 0.40 μm for devices in VA mode and from about 0.20 μm to about 0.35 μm for devices in IPS or FFS mode. In these cases, compositions with large optical anisotropy are preferred for devices with small cell gaps. The large dielectric anisotropy in the composition contributes to low threshold voltage, low power consumption and high contrast ratio in the device. Therefore, a large dielectric constant anisotropy is preferred. A large resistivity in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, compositions that have a large specific resistance in the initial stage are preferred. Compositions that have a high resistivity after long-term use are preferred. The stability of the composition against light and heat is related to the lifetime of the device. When this stability is high, the lifetime of the device is long. Such characteristics are preferable for AM elements used in liquid crystal monitors, liquid crystal televisions, and the like.

In general-purpose liquid crystal display elements, vertical alignment of liquid crystal molecules is achieved by a specific polyimide alignment film. In a polymer sustained alignment (PSA) type liquid crystal display element, a polymer is combined with an alignment film. First, a composition to which a small amount of a polymerizable compound is added is injected into the device. Next, the composition is irradiated with ultraviolet light while applying a voltage between the substrates of this device. The polymerizable compound polymerizes to form a polymer network in the composition. In this composition, the orientation of liquid crystal molecules can be controlled by the polymer, so the response time of the device is shortened and image sticking is improved. Such effects of the polymer can be expected in devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

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

In order to satisfy the required characteristics of a liquid crystal display element as described above, various compounds have been studied, and in recent years, compounds having a sulfur-containing heterocycle have been developed (Patent Documents 1 and 2, etc.).

Compounds having a thiadiazole ring as such a sulfur-containing heterocycle have been studied for a long time, but most of them are related to ferroelectric liquid crystals (Patent Document 3, etc.). For applications other than ferroelectric liquid crystals, Patent Document 4 discloses a composition containing a compound having a thiadiazole ring as an example of a composition that can be used in a specific device called a vertically aligned splayed nematic liquid crystal display device. .

Thus, compounds having a thiadiazole ring have so far only been studied for specific uses, and no studies have been made for their use in general-purpose liquid crystal display devices.

JP2020-79385A Japanese Patent Application Publication No. 2021-165367 Japanese Patent Application Publication No. 10-213820 International Publication No. 1997/012275

The problems of the present invention are a high upper limit temperature of the nematic phase, a lower lower limit temperature of the nematic phase, a small viscosity, a large optical anisotropy, a large negative dielectric anisotropy, a large elastic constant, a large specific resistance, and a high stability against light. It is an object of the present invention to provide a liquid crystal composition that satisfies at least one of the characteristics such as high stability and high stability against heat. Another challenge is to provide liquid crystal compositions that have an appropriate balance between at least two of these properties. Another object is to provide a liquid crystal display element containing such a composition. Another objective is to provide an AM device with characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long lifetime.

式（１）において、Ｒ^１およびＲ^２は、水素、炭素数１から５のアルキル、炭素数３から５の環状アルキル、炭素数１から５のアルコキシ、炭素数２から５のアルケニル、炭素数２から５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５のアルキルであり；環Ａおよび環Ｂは、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、テトラヒドロピラン－２，５－ジイル、１, ４-ジオキサン、１，４－フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４－フェニレンであり；Ｘは硫黄または酸素であり；ａは、１、２、または３であり、；ｂは、０または１であり；そしてａとｂとの和は３以下である。 The present invention provides a liquid crystal composition that contains at least one compound selected from the compounds represented by formula (1) as component A, has a nematic phase and negative dielectric anisotropy, and does not have a chiral smectic phase. and a liquid crystal display element containing this composition.

In formula (1), R ¹ and R ² are hydrogen, alkyl having 1 to 5 carbon atoms, cyclic alkyl having 3 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, alkenyl having 2 to 5 carbon atoms, and 2 to 5 alkenyloxy, or alkyl of 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; Ring A and Ring B are 1,4-cyclohexylene, 1,4-cyclohexenyl, X is sulfur or oxygen; X is sulfur or oxygen; ;a is 1, 2, or 3; ;b is 0 or 1; and the sum of a and b is 3 or less.

The advantages of the present invention are a high upper limit temperature of the nematic phase, a lower lower limit temperature of the nematic phase, a small viscosity, a large optical anisotropy, a large negative dielectric anisotropy, a large elastic constant, a large specific resistance, and a high stability against light. It is an object of the present invention to provide a liquid crystal composition that satisfies at least one of the characteristics such as high stability and high stability against heat. Another advantage is to provide liquid crystal compositions that have a suitable balance between at least two of these properties. Another advantage is to provide liquid crystal display elements containing such compositions. Another advantage is to provide an AM device with characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long lifetime.

The terms used in this specification are as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "composition" and "element," respectively. "Liquid crystal display element" is a general term for liquid crystal display panels and liquid crystal display modules. "Liquid crystal compound" refers to a compound that has a liquid crystal phase such as a nematic phase or a smectic phase, and a compound that does not have a liquid crystal phase but is used for the purpose of adjusting the properties of the nematic phase such as temperature range, viscosity, and dielectric anisotropy. A general term for compounds mixed into a composition. This compound has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecules (liquid crystal molecules) are rod-like. A "polymerizable compound" is a compound added for the purpose of producing a polymer in a composition. Liquid crystalline compounds having alkenyl are not classified as polymerizable compounds in that sense. "Chiral smectic phase" has the same meaning as chiral smectic phase. The chiral smectic phase is classified into fine categories such as the chiral smectic C phase, but it is a general term that includes these.

A liquid crystal composition is prepared by mixing multiple liquid crystal compounds. Additives such as optically active compounds and polymerizable compounds are added to this liquid crystal composition as necessary. Even when additives are added, the proportion of the liquid crystal compound is expressed as a mass percentage (mass %) based on the mass of the liquid crystal composition that does not contain additives. The proportion of the additive is expressed as a mass percentage (% by mass) based on the mass of the liquid crystal composition that does not contain the additive. That is, the proportions of the liquid crystal compound and additives are calculated based on the total mass of the liquid crystal compound. Mass parts per million (ppm) may be used. The proportions of polymerization initiators and polymerization inhibitors are exceptionally expressed based on the weight of the polymerizable compound.

"Upper limit temperature of nematic phase" may be abbreviated as "upper limit temperature." The "lower limit temperature of nematic phase" may be abbreviated as "lower limit temperature." The expression "increase the dielectric anisotropy" means that for a composition with a positive dielectric anisotropy, the value increases positively, and for a composition with a negative dielectric anisotropy. When it is a thing, it means that its value increases negatively. "High voltage holding rate" means that the device has a large voltage holding rate not only at room temperature but also at temperatures close to the upper limit temperature in the initial stage, and after long-term use, it has a large voltage holding rate not only at room temperature but also at temperatures close to the upper limit temperature. It means having a retention rate. Characteristics of compositions and devices are sometimes investigated through aging tests.

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

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

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

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

The expression "at least one 'A'" means that the number of 'A's is arbitrary. The expression "at least one 'A' may be replaced by 'B'" means that when the number of 'A's is one, the position of 'A' is arbitrary, and the number of 'A's is two. If there are more than one, their positions can be selected without restriction. The expression "at least one -CH ₂ - may be replaced by -O-" is sometimes used. In this case, -CH ₂ CH ₂ -CH ₂ - may be converted to -O-CH ₂ -O- by replacing non-adjacent -CH ₂ - with -O-. However, an adjacent -CH ₂ - is never replaced with -O-. This is because -OO-CH ₂ - (peroxide) is produced in this substitution.

テトラヒドロピラン－２，５－ジイルのような二価基においても同様である。カルボニルオキシのような結合基（－ＣＯＯ－または－ＯＣＯ－）も同様である。 When the alkyl of the liquid crystal compound is simply described as "alkyl", it is linear or branched and does not include a cyclic alkyl. "Alkyl" and "cyclic alkyl" are clearly distinguished. Straight chain alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. Regarding the configuration of 1,4-cyclohexylene, trans is preferable to cis in order to increase the upper limit temperature. Since 2-fluoro-1,4-phenylene is left-right asymmetric, there are left-handed (L) and right-handed (R) orientations.

The same applies to divalent groups such as tetrahydropyran-2,5-diyl. The same applies to bonding 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、水素、炭素数１から５のアルキル、炭素数３から５の環状アルキル、炭素数１から５のアルコキシ、炭素数２から５のアルケニル、炭素数２から５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５のアルキルであり；環Ａおよび環Ｂは、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、テトラヒドロピラン－２，５－ジイル、１, ４-ジオキサン、１，４－フェニレン、または少なくとも１つの水素がフッ素または塩素で置き換えられた１，４－フェニレンであり；Ｘは硫黄または酸素であり；ａは、１、２、または３であり；ｂは、０または１であり；そしてａとｂとの和は３以下である。 Item 1. A liquid crystal composition containing at least one compound selected from the compounds represented by formula (1) as component A, having a nematic phase and negative dielectric anisotropy, and having no chiral smectic phase.

In formula (1), R ¹ and R ² are hydrogen, alkyl having 1 to 5 carbon atoms, cyclic alkyl having 3 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, alkenyl having 2 to 5 carbon atoms, and 2 to 5 alkenyloxy, or alkyl of 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; Ring A and Ring B are 1,4-cyclohexylene, 1,4-cyclohexenyl, X is sulfur or oxygen; Yes; a is 1, 2, or 3; b is 0 or 1; and the sum of a and b is 3 or less.

式（１－１）から式（１－８）において、Ｒ^１およびＲ^２は、水素、炭素数１から５のアルキル、炭素数３から５の環状アルキル、炭素数１から５のアルコキシ、炭素数２から５のアルケニル、炭素数２から５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５のアルキルであり； Ｙは水素、フッ素、または塩素である。 Item 2. Item 2. The liquid crystal composition according to item 1, which contains as component A at least one compound selected from compounds represented by formulas (1-1) to (1-8).

In formulas (1-1) to (1-8), R ¹ and R ² are hydrogen, alkyl having 1 to 5 carbon atoms, cyclic alkyl having 3 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, carbon Alkenyl having 2 to 5 carbon atoms, alkenyloxy having 2 to 5 carbon atoms, or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; Y is hydrogen, fluorine, or chlorine.

Item 3. Item 3. The liquid crystal composition according to item 1 or 2, wherein the proportion of component A is in the range of 3% by mass to 30% by mass.

式（２）において、Ｒ^３およびＲ^４は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、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Ｃおよび環Ｄは、１，４－シクロヘキシレン、１，４－フェニレン、２－フルオロ－１，４－フェニレン、または２，５－ジフルオロ－１，４－フェニレンであり；Ｚ^１は、単結合、エチレン、ビニレン、メチレンオキシ、またはカルボニルオキシであり；ｃは、１、２、または３であり；ｃが１であるとき、Ｚ^１は、単結合、エチレン、ビニレン、またはメチレンオキシである。 Item 4. Item 4. The liquid crystal composition according to any one of items 1 to 3, which contains as component B at least one compound selected from compounds represented by formula (2).

In formula (2), R ³ and R ⁴ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or carbon in which at least one hydrogen is replaced with fluorine or chlorine. Alkyl having a number of 1 to 12, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; Ring C and Ring D are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ¹ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; c is 1, 2, or 3; when c is 1, Z ¹ is a single bond, ethylene, vinylene, or methyleneoxy.

式（２－１）から式（２－１５）において、Ｒ^３およびＲ^４は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、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 5. The liquid crystal composition according to any one of Items 1 to 4, which contains as component B at least one compound selected from compounds represented by formulas (2-1) to (2-15).

In formulas (2-1) to (2-15), R ³ and R ⁴ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and at least one hydrogen is an alkyl having 1 to 12 carbon atoms in which is replaced with fluorine or chlorine, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine.

Item 6. Item 5. The liquid crystal composition according to item 4 or 5, wherein the proportion of component B is in the range of 10% by mass to 85% by mass.

式（３）において、Ｒ^５およびＲ^６は、水素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、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Ｅおよび環Ｇは、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、テトラヒドロピラン－２，５－ジイル、１，４－フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４－フェニレン、ナフタレン－２，６－ジイル、少なくとも１つの水素がフッ素または塩素で置き換えられたナフタレン－２，６－ジイル、クロマン－２，６－ジイル、または少なくとも１つの水素がフッ素または塩素で置き換えられたクロマン－２，６－ジイルであり；環Ｆ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、１，８－ジフルオロフェナントレン－２，７－ジイル、３，４，５－トリフルオロナフタレン－２，６－ジイル、７，８－ジフルオロクロマン－２，６－ジイル、３，４，５，６－テトラフルオロフルオレン－２，７－ジイル、４，６－ジフルオロジベンゾフラン－３，７－ジイル、４，６－ジフルオロジベンゾチオフェン－３，７－ジイル、または１，１，６，７－テトラフルオロインダン－２，５－ジイルであり；Ｚ^２およびＺ^３は、単結合、エチレン、ビニレン、メチレンオキシ、またはカルボニルオキシであり；ｄは０、１、２、または３であり、ｅは０または１であり；そしてｄとｅとの和は３以下である。 Section 7. Item 7. The liquid crystal composition according to any one of items 1 to 6, which contains as component C at least one compound selected from compounds represented by formula (3).

In formula (3), R ⁵ and R ⁶ are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkenyloxy having 2 to 12 carbon atoms, or at least is an alkyl having 1 to 12 carbon atoms in which one hydrogen is replaced with fluorine or chlorine; Ring E and Ring G are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5- diyl, 1,4-phenylene, 1,4-phenylene with at least one hydrogen replaced by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2 with at least one hydrogen replaced with fluorine or chlorine, 6-diyl, chroman-2,6-diyl, or chroman-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine; Ring F is 2,3-difluoro-1,4-phenylene , 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 1,8-difluorophenanthrene-2,7-diyl, 3,4,5- Trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3, 7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoroindan-2,5-diyl; Z ² and Z ³ are a single bond, ethylene , vinylene, methyleneoxy, or carbonyloxy; d is 0, 1, 2, or 3; e is 0 or 1; and the sum of d and e is 3 or less.

式（３－１）から式（３－３６）において、Ｒ^５およびＲ^６は、水素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、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。 Section 8. Item 8. The liquid crystal composition according to any one of Items 1 to 7, which contains as component C at least one compound selected from compounds represented by formulas (3-1) to (3-36).

In formulas (3-1) to (3-36), R ⁵ and R ⁶ are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and 2 to 12 alkenyloxy, or C1 to C12 alkyl in which at least one hydrogen is replaced with fluorine or chlorine.

Item 9. Item 8. The liquid crystal composition according to item 7 or 8, wherein the proportion of component C is in the range of 10% by mass to 85% by mass.

式（４）において、環Ｉおよび環Ｋは、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Ｊ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^４およびＺ^５は、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_２ＣＨ_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からＰ^３は、重合性基であり；Ｓｐ^１からＳｐ^３は、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_２ＣＨ_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；ｆは、０、１、または２であり；ｇ、ｈ、およびｉは、０、１、２、３、または４であり；そしてｇ、ｈ、およびｉの和は、１以上である。 Item 10. Item 10. The liquid crystal composition according to any one of Items 1 to 9, which contains as additive X at least one compound selected from polymerizable compounds represented by formula (4).

In formula (4), ring I and ring K are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl , or pyridin-2-yl, in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or at least one hydrogen is fluorine or chlorine. may be substituted with alkyl having 1 to 12 carbon atoms; Ring J 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 having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is It may be substituted with a C1-C12 alkyl substituted with fluorine or chlorine; Z ⁴ and Z ⁵ are a single bond or a C1-C10 alkylene, in which at least one -CH ₂ - may be replaced with -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 )-, in which at least one hydrogen is replaced by fluorine or chlorine. P ¹ to P ³ are polymerizable groups; Sp ¹ to Sp ³ are single bonds or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one -CH ₂ - may be replaced with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ - may be replaced with -CH=CH- or -C≡C- and in these groups at least one hydrogen may be replaced by fluorine or chlorine; f is 0, 1, or 2; g, h, and i are 0, 1, 2 , 3, or 4; and the sum of g, h, and i is 1 or more.

式（Ｐ－１）から式（Ｐ－５）において、Ｍ^１からＭ^３は、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のアルキルである。 Item 11. Item 11. The liquid crystal composition according to item 10, wherein in formula (4), P ¹ to P ³ are groups selected from polymerizable groups represented by formulas (P-1) to (P-5).

In formulas (P-1) to (P-5), M ¹ to M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or 1-carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. to 5 alkyl.

式（４－１）から式（４－２９）において、Ｓｐ^１からＳｐ^３は、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_２ＣＨ_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；Ｐ^４からＰ^６は、式（Ｐ－１）から式（Ｐ－３）で表される基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からＭ^３は、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のアルキルである。 Item 12. Item 12. The liquid crystal composition according to any one of Items 1 to 11, which contains as additive X at least one compound selected from polymerizable compounds represented by formulas (4-1) to (4-29). thing.

In formulas (4-1) to (4-29), Sp ¹ to Sp ³ are single bonds or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one -CH ₂ - is -O -, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ - may be replaced with -CH=CH- or -C≡C-, In these groups, at least one hydrogen may be replaced by fluorine or chlorine; P ⁴ to P ⁶ are selected from the groups represented by formulas (P-1) to (P-3) is a polymerizable group;

In formulas (P-1) to (P-3), M ¹ to M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or 1-carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. to 5 alkyl.

Item 13. 13. The liquid crystal composition according to any one of Items 10 to 12, wherein the proportion of additive X is in the range of 0.03% by mass to 10% by mass.

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

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

Section 16. 14. A polymer-supported alignment type liquid crystal display element containing the liquid crystal composition according to any one of Items 10 to 13, in which a polymerizable compound in the liquid crystal composition is polymerized.

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

Section 18. Use of the liquid crystal composition according to any one of Items 10 to 13 in a polymer supported alignment type liquid crystal display element.

The present invention also includes the following sections. (a) one compound selected from additives such as optically active compounds, antioxidants, ultraviolet absorbers, quenchers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, and polymerization inhibitors; A composition as described above containing a compound, or three or more compounds. (b) An AM element containing the above composition. (c) The above composition further containing a polymerizable compound, and a polymer supported alignment (PSA) type AM element containing this composition. (d) A polymer supported alignment (PSA) type AM element containing the above composition and in which a 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 transmission type element containing the above composition. (g) Use of the above compositions as compositions having a nematic phase. (h) Use of an optically active composition obtained by adding an optically active compound to the above composition.

The composition of the present invention will be explained in the following order. First, the structure of the composition will be explained. Second, the main properties of the component compounds and the main effects that these compounds have on the compositions and devices will be explained. Third, the combinations of component compounds in the composition, their preferred ratios, and their basis will be explained. Fourth, preferred forms of the component compounds will be explained. Fifth, preferred component compounds are shown. Sixth, additives that may be added to the composition will be explained. Seventh, the method of synthesizing the component compounds will be explained. Finally, the uses of the composition will be explained.

First, the structure of the composition will be explained. This composition contains multiple liquid crystal compounds. The composition may also contain additives. Additives include optically active compounds, antioxidants, ultraviolet absorbers, quenchers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. This composition is classified into composition (a) and composition (b) from the viewpoint of the liquid crystal compound. Composition (a) may further contain other liquid crystal compounds, additives, etc. in addition to the liquid crystal compound selected from compound (1), compound (2), and compound (3). "Other liquid crystal compounds" are liquid crystal compounds different from compound (1), compound (2), and compound (3). Such compounds are mixed into the composition for the purpose of further adjusting its properties.

Composition (b) consists essentially only of a liquid crystalline compound selected from compound (1), compound (2), and compound (3). "Substantially" means that the composition (b) may contain additives but does not contain other liquid crystal compounds. Composition (b) has fewer components than composition (a). Composition (b) is preferred over composition (a) from the viewpoint of lowering costs. Composition (a) is preferable to composition (b) from the viewpoint that the properties can be further adjusted by mixing other liquid crystal compounds.

Second, the main properties of the component compounds and the main effects that these compounds have on the compositions and devices will be explained. 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 component compounds, with 0 (zero) meaning less than S.

The main effects of the component compounds are as follows. Compound (1) increases optical anisotropy and dielectric anisotropy. Compound (2) increases the upper limit temperature or lowers the viscosity. Compound (3) Increases dielectric anisotropy or lowers the lower limit temperature. Compound (4) gives a polymer by polymerization. This polymer stabilizes the alignment of liquid crystal molecules, thereby shortening the response time of the device and improving image sticking.

Third, the combinations of component compounds in the composition, their preferred ratios, and their basis will be explained. Preferred combinations of component compounds in the composition are compound (1) + compound (2), compound (1) + compound (3), compound (1) + compound (2) + compound (3), and compound (1) + Compound (2) + compound (4), compound (1) + compound (3) + compound (4), or compound (1) + compound (2) + compound (3) + compound (4). More preferred combinations are compound (1) + compound (2), compound (1) + compound (3), or compound (1) + compound (2) + compound (3).

A preferable proportion of compound (1) is about 3% by mass or more in order to increase optical anisotropy and dielectric anisotropy, and about 30% by mass or less in order to lower the minimum temperature. More preferred proportions range from about 5% to about 20% by weight. Particularly preferred proportions range from about 5% to about 15% by weight.

A preferable proportion of compound (2) is about 10% by mass or more in order to increase the upper limit temperature or lower the viscosity, and is about 85% by mass or less in order to increase the dielectric anisotropy. More preferred proportions range from about 20% to about 75% by weight. Particularly preferred proportions range from about 30% to about 70% by weight.

The preferred proportion of compound (3) is about 10% by mass or more in order to increase the dielectric anisotropy or lower the minimum temperature, and is about 85% by mass or less in order to decrease the viscosity. More preferred proportions range from about 20% to about 75% by weight. Particularly preferred proportions range from about 30% to about 60% by weight.

Compound (4) is added to the composition for the purpose of making it compatible with polymer-supported alignment type elements. The preferred proportion of compound (4) is about 0.03% by mass or more in order to orient the liquid crystal molecules, and about 10% by mass or less in order to prevent display defects in the device. A more preferred proportion ranges from about 0.1% to about 2% by weight. Particularly preferred proportions range from about 0.2% to about 1.0% by weight.

Fourth, preferred forms of the component compounds will be explained. In formula (1), formula (2), and formula (3), R ¹ and R ² are hydrogen, alkyl having 1 to 5 carbon atoms, cyclic alkyl having 3 to 5 carbon atoms, and alkoxy having 1 to 5 carbon atoms. , alkenyl having 2 to 5 carbon atoms, alkenyloxy having 2 to 5 carbon atoms, or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. Preferably R ¹ or R ² is alkyl having 1 to 5 carbon atoms in order to increase stability.
R ³ and R ⁴ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; , or a C2-C12 alkenyl in which at least one hydrogen is replaced with fluorine or chlorine. Preferred R ³ or R ⁴ is alkyl having 1 to 12 carbon atoms to increase stability, and alkenyl having 2 to 12 carbon atoms to decrease viscosity. R ⁵ and R ⁶ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or at least one hydrogen is fluorine or It is an alkyl having 1 to 12 carbon atoms substituted with chlorine. Preferred R ⁵ or R ⁶ is alkyl having 1 to 12 carbon atoms to increase stability, alkenyl having 2 to 12 carbon atoms to lower viscosity, and alkenyl having 2 to 12 carbon atoms to increase dielectric anisotropy. 1 to 12 alkoxy.

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

Preferred cyclic alkyls are cyclopropyl, cyclobutyl, or cyclopentyl.

Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. More preferred alkoxy to reduce viscosity is methoxy or ethoxy.

Preferred alkenyls are 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 alkenyls are vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl to reduce viscosity. The preferred configuration of -CH=CH- in these alkenyls depends on the position of the double bond. Trans is preferable for alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl in order to lower the viscosity. Cis is preferred in alkenyl such as 2-butenyl, 2-pentenyl, and 2-hexenyl.

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

Preferred examples of alkyl in which at least one hydrogen is replaced by 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 in order to increase the dielectric anisotropy.

Preferred examples of alkenyl in which at least one hydrogen is replaced by fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro -4-pentenyl or 6,6-difluoro-5-hexenyl. Further preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl to reduce viscosity.

Ring A and Ring B are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-dioxane, 1,4-phenylene, at least one hydrogen is fluorine or It is 1,4-phenylene replaced with chlorine. Preferred ring A or ring B is 1,4-phenylene in order to increase optical anisotropy, and 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine in order to increase dielectric anisotropy. It is.

Ring C and Ring D are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. Preferred ring C or ring D is 1,4-cyclohexylene in order to lower the viscosity, and 1,4-phenylene or 2-fluoro-1,4-phenylene in order to increase the optical anisotropy.

または

であり、好ましくは

である。 Ring E and Ring G are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1 in which at least one hydrogen is replaced with fluorine or chlorine. ,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl with at least one hydrogen replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen with fluorine or chlorine chroman-2,6-diyl substituted with Preferred examples of "1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine" are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene or 2-chloro- It is 3-fluoro-1,4-phenylene. Preferred ring E or ring G is 1,4-cyclohexylene to lower the viscosity, tetrahydropyran-2,5-diyl to increase the dielectric anisotropy, and preferred ring E or ring G to increase the optical anisotropy. It is 1,4-phenylene. Tetrahydropyran-2,5-diyl in ring E and ring G is

or

and preferably

It is.

好ましい環Ｆは、粘度を下げるために２，３－ジフルオロ－１，４－フェニレンであり、誘電率異方性を上げるために１，８－ジフルオロフェナントレン－２，７－ジイルまたは４，６－ジフルオロジベンゾチオフェン－３，７－ジイルである。 Ring F is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 1,8- Difluorophenanthrene-2,7-diyl, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene- 2,7-diyl (FLF4), 4,6-difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2), or 1,1,6,7 -tetrafluoroindan-2,5-diyl (InF4).

Preferred ring F is 2,3-difluoro-1,4-phenylene to lower the viscosity, and 1,8-difluorophenanthrene-2,7-diyl or 4,6-diyl to increase the dielectric anisotropy. It is difluorodibenzothiophene-3,7-diyl.

Z ¹ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Preferably Z ¹ is a single bond in order to lower the viscosity. Z ² and Z ³ are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Preferred Z ² or Z ³ is a single bond to lower the viscosity, ethylene to lower the minimum temperature, and methyleneoxy to increase the dielectric anisotropy.

Divalent groups such as methyleneoxy are asymmetric. In methyleneoxy, -CH ₂ O- is more preferred than -OCH ₂ -. In carbonyloxy, -COO- is more preferred than -OCO-.

X is sulfur or oxygen. Preferably, X is sulfur in order to increase the upper limit temperature and optical anisotropy.

Y is hydrogen, fluorine, or chlorine. Preferred Y is hydrogen to lower the viscosity and fluorine to increase the dielectric anisotropy.

a is 1, 2, or 3, b is 0 or 1, and the sum of a and b is 3 or less. Preferably a or b is 1 in order to increase optical anisotropy and decrease viscosity. c is 1, 2, or 3. Preferably c is 1 in order to lower the viscosity, and 2 or 3 in order to increase the upper limit temperature. d is 0, 1, 2, or 3, e is 0 or 1, and the sum of d and e is 3 or less. Preferably, d is 0 or 1 in order to lower the viscosity, and 2 is preferable in order to increase the upper limit temperature. Preferably e is 0 in order to lower the viscosity and 1 in order to increase the upper limit temperature.

In formula (2), when c is 1, Z ¹ is a single bond, ethylene, vinylene, or methyleneoxy.

In formula (4), ring I and ring K are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl , or pyridin-2-yl, in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or at least one hydrogen is fluorine or chlorine. may be replaced with alkyl having 1 to 12 carbon atoms. Preferred ring I or ring K is phenyl. Ring J 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, and in these rings, At least one hydrogen is replaced with fluorine, chlorine, C1-12 alkyl, C1-12 alkoxy, or C1-12 alkyl in which at least one hydrogen is replaced with fluorine or chlorine. Good too. Preferred ring J is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁴ and Z ⁵ are a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one -CH ₂ - is -O-, -CO-, -COO-, or -OCO-. Optionally, 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 )- and in these groups at least one hydrogen may be replaced by fluorine or chlorine. Preferable Z ⁴ or Z ⁵ is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, or -OCO-. More preferably Z ⁴ or Z ⁵ is a single bond.

Sp ¹ to Sp ³ are a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one -CH ₂ - is -O-, -COO-, -OCO-, or -OCOO-. and at least one -CH ₂ CH ₂ - may be replaced by -CH=CH- or -C≡C-, in which at least one hydrogen is replaced by fluorine or chlorine. May be replaced. Preferred Sp ¹ to Sp ³ are a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CO-CH=CH-, or -CH=CH -CO-. More preferred Sp ¹ to Sp ³ are single bonds.

f is 0, 1, or 2. Preferably f is 0 or 1. g, h, and i are 0, 1, 2, 3, or 4, and the sum of g, h, and i is 1 or more. Preferably g, h, or i is 1 or 2.

P ¹ to P ³ are polymerizable groups. Preferred P ¹ to P ³ are polymerizable groups selected from the groups represented by formulas (P-1) to (P-5). More preferable P ¹ to P ³ are groups represented by formula (P-1), formula (P-2), or formula (P-3). Particularly preferred P ¹ to P ³ are groups represented by formula (P-1) or formula (P-2). The most preferred group from P ¹ to P ³ is a group represented by formula (P-1). A preferred group represented by formula (P-1) is -OCO-CH=CH ₂ or -OCO-C(CH ₃ )=CH ₂ . The wavy lines in formulas (P-1) to (P-5) indicate binding sites.

In formulas (P-1) to (P-5), M ¹ to M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or 1-carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. to 5 alkyl. Preferred M ¹ to M ³ are hydrogen or methyl in order to increase reactivity. More preferred M ¹ is hydrogen or methyl, and even more preferred M ² or M ³ is hydrogen.

In formulas (4-1) to (4-29), P ⁴ to P ⁶ are groups represented by formulas (P-1) to (P-3). Preferred P ⁴ to P ⁶ are formula (P-1) or formula (P-2). More preferred formula (P-1) is -OCO-CH=CH ₂ or -OCO-C(CH ₃ )=CH ₂ . The wavy lines in formulas (P-1) to (P-3) indicate bonding sites.

Fifth, preferred component compounds are shown. Preferred compounds (1) are compounds (1-1) to (1-8) described in item 2. In these compounds, at least one component A is preferably represented by formula (1-2).

Preferred compounds (2) are compounds (2-1) to (2-15) described in Item 5. In these compounds, at least one of component B is compound (2-1), compound (2-3), formula (2-7), formula (2-8), or formula (2-12). is preferred. It is particularly preferred that at least one component B is compound (2-1). The proportion of compound (2-1) is preferably 30% by mass or more, particularly preferably 35% by mass or more. Formula (2-1) in which at least one of R ³ and R ⁴ is alkenyl having 2 or 3 carbon atoms is preferred, and the proportion thereof is preferably 30% by mass or more. At least two of component B are compound (2-1) and compound (2-3), formula (2-1) and formula (2-8), or formula (2-1) and formula (2-12). It is preferable that there be.

Preferred compounds (3) are compounds (3-1) to (3-36) described in Item 8. In these compounds, at least one of component C is compound (3-1), compound (3-2), compound (3-3), compound (3-6), formula (3-8), formula (3 -9), formula (3-10), formula (3-14), formula (3-19), or formula (3-36). At least two of the components C are compound (3-1) and compound (3-2), compound (3-1) and compound (3-6), compound (3-1) and compound (3-8), compound (3-1) and compound (3-14), compound (3-6) and compound (3-8), compound (3-6) and compound (3-9), compound (3-6) and compound ( 3-10), compound (3-6) and compound (3-36), compound (3-8) and compound (3-14), or a combination of compound (3-8) and compound (3-36) It is preferable that there be.

Preferred compounds (4) are compounds (4-1) to (4-29) described in Item 12. In these compounds, at least one of the additives X is compound (4-1), compound (4-2), compound (4-24), compound (4-25), compound (4-26), or compound (4-27) is preferred. At least two of the additives X 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 A combination of compounds (4-24) is preferred.

Sixth, additives that may be added to the composition will be explained. Such additives include optically active compounds, antioxidants, ultraviolet absorbers, quenchers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules and giving a twist angle. Examples of such compounds are compounds (5-1) to (5-5). The preferred proportion of optically active compound is about 5% by weight or less. More preferred proportions range from about 0.01% to about 2% by weight.

In order to prevent the specific resistance from decreasing due to heating in the atmosphere, or to maintain a large voltage holding rate not only at room temperature but also at temperatures close to the upper limit temperature after using the device for a long time, the compound (6-1 ) may further add an antioxidant such as compound (6-3) to the composition.

Since compound (6-2) has low volatility, it is effective in maintaining a high voltage holding rate not only at room temperature but also at temperatures close to the upper limit temperature after the device has been used for a long time. The preferred proportion of the antioxidant is about 50 ppm or more to obtain the effect, and about 600 ppm or less so as not to lower the upper limit temperature or increase the lower limit temperature. More preferred proportions range from about 100 ppm to about 300 ppm.

Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, and triazole derivatives. Light stabilizers such as sterically hindered amines are also preferred. Preferred examples of the light stabilizer include compounds (7-1) to (7-16). The preferable proportion of these absorbers 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 increase the lower limit temperature. More preferred proportions range from about 100 ppm to about 10,000 ppm.

A quencher is a compound that prevents decomposition of a liquid crystal compound by receiving light energy absorbed by the liquid crystal compound and converting it into thermal energy. Preferred examples of the quencher include compounds (8-1) to (8-7). The preferred proportion of these quenchers is about 50 ppm or more to obtain the effect, and about 20,000 ppm or less so as not to raise the lower limit temperature. More preferred proportions range from about 100 ppm to about 10,000 ppm.

Dichroic dyes such as azo dyes, anthraquinone dyes, etc. are added to the composition in order to make it compatible with a guest host (GH) mode device. Preferred proportions of dye range from about 0.01% to about 10% by weight. Antifoaming agents such as dimethyl silicone oil, methylphenyl silicone oil are added to the composition to prevent foaming. The preferred proportion of the antifoaming agent is about 1 ppm or more to obtain its effect, and about 1000 ppm or less to prevent display defects. More preferred proportions range from about 1 ppm to about 500 ppm.

Polymerizable compounds are used to make them compatible with polymer supported alignment (PSA) type devices. Compound (4) is suitable for this purpose. A polymerizable compound different from compound (4) may be added to the composition together with compound (4). Preferred examples of such polymerizable compounds are compounds such as acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxirane, oxetane), and vinyl ketones. Further preferred examples are acrylate or methacrylate derivatives. A preferable proportion of compound (4) is 10% by mass or more based on the total mass of the polymerizable compound. A more preferable ratio is 50% by mass or more. A particularly preferable ratio is 80% by mass or more. The most preferred proportion is 100% by weight.

A polymerizable compound such as compound (4) is polymerized by ultraviolet irradiation. The polymerization may be carried out in the presence of a suitable initiator such as a photopolymerization initiator. Suitable conditions for polymerization, suitable types of initiators, and suitable amounts are known to those skilled in the art and are described in the literature. For example, the photoinitiators Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF) or Darocur 1173 (registered trademark; BASF) are suitable for radical polymerization. A preferred proportion of photoinitiator ranges from about 0.1% to about 5% by weight, based on the total weight of the polymerizable compound. More preferred proportions range from about 1% 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-t-butylcatechol, 4-methoxyphenol, phenothiazine, and the like.

Seventh, the method of synthesizing the component compounds will be explained. These compounds can be synthesized by known methods. The synthesis method will be illustrated. A synthesis example of compound (1) is described in the Examples section. Compound (2-1) is synthesized by the method described in JP-A-9-77692. Compound (3-1) is synthesized by the method described in Japanese Patent Publication No. 2-503441. Compound (4-18) is synthesized by the method described in JP-A-7-101900. Antioxidants are commercially available. Compound (6-1) is available from Aldrich (Sigma-Aldrich Corporation). Compound (6-2) and the like are synthesized by the method described in US Pat. No. 3,660,505.

Compounds for which the synthesis method was not described are provided by Organic Syntheses, John Wiley & Sons, Inc., Organic Reactions, John Wiley & Sons, Inc., Comprehensive Organic Syntheses, Organic Reactions, John Wiley & Sons, Inc. Synthesis, Pergamon Press), New Experimental Chemistry Course (Maruzen), and other books. Compositions are prepared from the compounds thus obtained by known methods. For example, the component compounds may be mixed and dissolved together by heating.

Finally, the uses of the composition will be explained. This composition primarily has a lower temperature limit of about -10°C or less, an upper temperature limit of about 70°C or more, and an optical anisotropy in the range of about 0.07 to about 0.20. A composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the proportions of the component compounds or by mixing other liquid crystalline compounds. By trial and error, compositions having optical anisotropy ranging from about 0.10 to about 0.30 may be prepared. A device containing this composition has a high voltage holding ratio. This composition is suitable for AM devices. This composition is particularly suitable for transmission type AM devices. This composition can be used as a composition having a nematic phase, or as an optically active composition by adding an optically active compound.

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

The composition of the present invention is a composition that does not have a chiral smectic phase. Chiral smectic C phase is one of the chiral smectic phases and is known to exhibit ferroelectricity. Since the composition of the present invention does not have such a liquid crystal phase, it does not exhibit ferroelectricity. From this, the composition of the present invention is clearly distinguished from ferroelectric liquid crystals.

The present invention will be explained in more detail with reference to Examples. The invention is not limited by these examples. The invention includes a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes mixtures of at least two of the compositions of the examples. The synthesized compounds were identified by methods such as NMR analysis. Properties of the compounds, compositions, and devices were measured by the methods described below.

NMR analysis: DRX-500 manufactured by Bruker Biospin was used for measurement. In ^{the 1} H-NMR measurement, the sample was dissolved in a deuterated solvent such as CDCl ₃ , and the measurement was performed at room temperature, at 500 MHz, and with 16 integrations. Tetramethylsilane was used as an internal standard. ¹⁹ F-NMR measurements were carried out using CFCl ₃ as an internal standard and with 24 integrations. In the description of nuclear magnetic resonance spectra, 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 chromatography analysis: A GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for measurement. The carrier gas is helium (2 mL/min). The sample vaporization chamber was set at 280°C, and the detector (FID) was set at 300°C. A capillary column DB-1 manufactured by Agilent Technologies Inc. (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm; stationary liquid phase is dimethylpolysiloxane; nonpolar) was used to separate the component compounds. This column was held at 200°C for 2 minutes and then raised to 280°C at a rate of 5°C/min. After preparing the sample as an acetone solution (0.1% by mass), 1 μL of the solution was injected into the sample vaporization chamber. The recorder was a C-R5A Chromatopac manufactured by Shimadzu Corporation or an equivalent product. The resulting gas chromatogram showed the retention times and peak areas of the peaks corresponding to the component compounds.

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

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

Measurement sample: When measuring the characteristics of a composition or an element, the composition was used as it was as a sample. When measuring the properties of a compound, a sample for measurement was prepared by mixing this compound (15% by mass) with a mother liquid crystal (85% by mass). Characteristic values of the compound were calculated by extrapolation from the values obtained by measurement. (Extrapolated value) = {(measured value of sample)-0.85×(measured value of mother liquid crystal)}/0.15. When the smectic phase (or crystals) precipitates at 25°C with this ratio, the ratio of the compound to the mother liquid crystal is 10% by mass: 90% by mass, 5% by mass: 95% by mass, and 1% by mass: 99% by mass. changed. By this extrapolation method, the upper limit temperature, optical anisotropy, viscosity, and dielectric anisotropy values for the compound were determined.

The following mother liquid crystal was used. The proportions of component compounds are expressed in mass %.

Measurement method: Characteristics were measured using the following method. Many of these are methods described in the JEITA standard (JEITA ED-2521B), which is deliberated and established by the Japan Electronics and Information Technology Industries Association (JEITA), or methods modified from this. Met. A thin film transistor (TFT) was not attached to the TN element used in 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 at which a portion of the sample changed from a nematic phase to an isotropic liquid was measured. The upper limit temperature of the nematic phase is sometimes abbreviated as "upper limit temperature."

(2) Lower limit temperature of nematic phase (TC; ° _C ): Place a sample having a nematic phase in a glass bottle and place it in a freezer at 0 °C, -10 °C, -20 °C, -30 °C, and -40 °C for 10 days. After storage, the liquid crystal phase was observed. For example, when a sample remained in a nematic phase at -20°C and changed to a crystalline or smectic phase at -30°C, T _C was written as <-20°C. The lower limit temperature of the nematic phase is sometimes abbreviated as "lower limit temperature."

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

(4) Viscosity (rotational viscosity; γ1; measured at 25° C.; mPa·s): A rotational viscosity measurement system LCM-2 model manufactured by Toyo Technica Co., Ltd. was used for the measurement. A sample was injected into a VA element in which the distance between two glass substrates (cell gap) was 10 μm. A rectangular wave (55 V, 1 ms) was applied to this element. The peak current and peak time of the transient current generated by this application were measured. Using these measured values and dielectric anisotropy, values of rotational viscosity were obtained. The dielectric anisotropy was measured by the method described in Measurement (6).

(5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25° C.): Measurement was performed using light with a wavelength of 589 nm 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 formula Δn=n∥−n⊥.

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

(7) Threshold voltage (Vth; measured at 25° C.; V): An LCD5200 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. A sample was placed in a normally black mode VA element in which the cell gap between two glass substrates was 4 μm and the rubbing direction was antiparallel, and an adhesive that was cured by ultraviolet light was applied to the element. It was sealed using. The voltage (60 Hz, rectangular wave) applied to this element was increased in steps of 0.02 V from 0 V to 20 V. At this time, the element was irradiated with light from the perpendicular direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was created in which the transmittance is 100% when the amount of light is maximum and the transmittance is 0% when this amount of light is the minimum. The threshold voltage was expressed as the voltage when the transmittance reached 10%.

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

(9) Voltage holding rate (VHR-2; measured at 80°C; %): The voltage holding rate was measured using the same procedure as above, except that the measurement was performed at 80°C instead of 25°C. The obtained value was expressed in VHR-2.

(10) Voltage holding rate (VHR-3; measured at 25°C; %): After irradiation with ultraviolet rays, voltage holding rate was measured to evaluate stability against ultraviolet rays. The TN device used in the measurements had a polyimide alignment film and a cell gap of 5 μm. A sample was injected into this element, and light was irradiated 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. The VHR-3 measurement measured a voltage that decayed over 16.7 milliseconds. Compositions with large VHR-3 have greater stability to ultraviolet light. VHR-3 is preferably 90% or more, more preferably 95% or more.

(11) Voltage holding rate (VHR-4; measured at 25°C; %): After heating the TN element injected with the sample in a thermostat at 80°C for 500 hours, the voltage holding rate was measured and the stability against heat was measured. was evaluated. The VHR-4 measurement measured a voltage that decayed over 16.7 milliseconds. Compositions with large VHR-4 have greater thermal stability.

(12) Response time (τ; measured at 25°C; ms): An LCD5200 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. The low-pass filter was set at 5kHz. A sample was placed in a normally black mode VA element in which the distance between two glass substrates (cell gap) was 4 μm and the rubbing direction was antiparallel. The device was sealed using an adhesive that cures with ultraviolet light. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to this element. At this time, the element was irradiated with light from the perpendicular direction, and the amount of light transmitted through the element was measured. The transmittance was considered to be 100% when this amount of light was at its maximum, and the transmittance was considered to be 0% when this amount of light was at its minimum. The response time was expressed as the time required for the transmittance to change from 90% to 10% (fall time; milliseconds).

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

(14) Line afterimage (Line Image Sticking Parameter; LISP; %): Line afterimage was generated by applying electrical stress to the liquid crystal display element. The brightness of the area with the line afterimage and the brightness of the remaining area were measured. The rate at which the brightness decreased due to the line afterimage was calculated, and the size of the line afterimage was expressed by this rate.
14a) Measurement of brightness: An image of the device was taken using an imaging colorimeter (PM-1433F-0, manufactured by Radiant Zemax). The brightness of each region of the element was calculated by analyzing this image using software (Prometric 9.1, manufactured by Radiant Imaging). The light source used was an LED backlight with an average brightness of 3500 cd/m ² .

14b) Stress voltage setting: A sample was placed in an FFS element (16 cells: 4 cells vertically x 4 cells horizontally) with a cell gap of 3.5 μm and a matrix structure, and this element was bonded using an adhesive that cures with ultraviolet light. It was sealed tightly. Polarizing plates were placed on the top and bottom surfaces of this element so that the polarization axes were perpendicular to each other. This element was irradiated with light and a voltage (square wave, 60 Hz) was applied. The voltage was increased in steps of 0.1 V in the range of 0 V to 7.5 V, and the brightness of transmitted light at each voltage was measured. The voltage at which the brightness reached its maximum was abbreviated as V255. The voltage when the luminance reached 21.6% of V255 (that is, 127th gradation) was abbreviated as V127.

14c) Stress conditions: V255 (rectangular wave, 30 Hz) and 0.5 V (rectangular wave, 30 Hz) were applied to the device at 60° C. for 23 hours to display a checker pattern. Next, V127 (rectangular wave, 0.25 Hz) was applied, and the brightness was measured under the conditions of an exposure time of 4000 milliseconds.

14d) Calculation of line afterimage: Among the 16 cells, 4 cells in the center (2 cells vertically x 2 cells horizontally) were used for calculation. These 4 cells were divided into 25 areas (5 cells vertically x 5 cells horizontally). The average brightness of four areas (2 cells vertically x 2 cells horizontally) at the four corners was abbreviated as brightness A. The area obtained by excluding the four corner areas from the 25 areas was in the shape of a cross. The minimum value of brightness in four areas excluding the central intersection area from this cross-shaped area was abbreviated as brightness B. The line afterimage was calculated using the following formula. (Line afterimage) = (Brightness A - Brightness B) / Brightness A x 100.

(15) Spreadability: The spreadability of the additive was qualitatively evaluated by applying a voltage to the element and measuring the brightness. The measurement of brightness was performed in the same manner as in Section 14a above. The voltage (V127) was set in the same manner as in Section 14b above. However, a VA element was used instead of the FFS element. Luminance was measured as follows. First, a DC voltage (2V) was applied to the device for 2 minutes. Next, V127 (rectangular wave, 0.05 Hz) was applied, and the brightness was measured under the conditions of an exposure time of 4000 milliseconds. Spreadability was evaluated from this result.

(16) Response time (τ-2; measured at -20°C; ms): An LCD5200 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. The low-pass filter was set at 5kHz. A sample was placed in a normally black mode VA element in which the distance between two glass substrates (cell gap) was 4 μm and the rubbing direction was antiparallel. The device was sealed using an adhesive that cures with ultraviolet light. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to this element. At this time, the element was irradiated with light from the perpendicular direction, and the amount of light transmitted through the element was measured. The transmittance was considered to be 100% when this amount of light was at its maximum, and the transmittance was considered to be 0% when this amount of light was at its minimum. The response time was expressed as the time required for the transmittance to change from 90% to 10% (fall time; milliseconds).

(17) Response time (τ-3; measured at -30°C; ms): An LCD5200 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. The low-pass filter was set at 5kHz. A sample was placed in a normally black mode VA element in which the distance between two glass substrates (cell gap) was 4 μm and the rubbing direction was antiparallel. The device was sealed using an adhesive that cures with ultraviolet light. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to this element. At this time, the element was irradiated with light from the perpendicular direction, and the amount of light transmitted through the element was measured. The transmittance was considered to be 100% when this amount of light was at its maximum, and the transmittance was considered to be 0% when this amount of light was at its minimum. The response time was expressed as the time required for the transmittance to change from 90% to 10% (fall time; milliseconds).

(18) Elastic constant (K11: splay elastic constant, K33: bend elastic constant; measured at 25°C; pN): For measurement, use an EC-1 elastic constant measuring device manufactured by Toyo Technica Co., Ltd. Using. A sample was placed in a vertically aligned cell in which the distance between two glass substrates (cell gap) was 20 μm. A charge of 20 volts to 0 volts was applied to this cell, and the capacitance and applied voltage were measured. Fitting the measured capacitance (C) and applied voltage (V) using equations (2.98) and (2.101) in "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), page 75. Then, the value of the elastic constant was obtained from equation (2.100).

Compound (1-2) was synthesized by the following route.

First step: Synthesis of compound (b) Compound (a) (150 g, 0.91 mol) was suspended in thionyl chloride (100 mL), DMF (5 mL) was added, and the mixture was heated under reflux for 3 hours. After cooling, thionyl chloride was removed under reduced pressure to obtain compound (b) (164 g, 0.90 mol, yield 98.0%).

2nd step: Synthesis of compound (d) Compound (c) (100 g, 0.61 mol) was dissolved in THF (100 mL), hydrazine monohydrate (100 mL) was added, and the mixture was heated under reflux for 7 hours. After cooling, it was poured into water (500 mL), and the precipitated solid was filtered off. The obtained solid was recrystallized from ethanol (150 mL) to obtain compound (d) (52.4 g, 0.35 mol, yield 57.3%).

3rd step: Synthesis of compound (e) Compound (d) (120.0 g, 0.80 mol) and compound (b) (131.4 g, 0.72 mol) were suspended in THF (320 mL), and pyridine (120 mL) was added. was added and heated under reflux for 5 hours. After cooling, it was poured into water (4 L), and the precipitated solid matter was filtered off. The obtained solid was recrystallized from ethanol (5 L) to obtain compound (e) (159 g, 0.54 mol, yield 74.6%).

4th step: Synthesis of compound (1-2) Compound (e) (74.0 g, 0.25 mol) and Lawesson's reagent (100 g, 0.25 mol) were suspended in THF (500 mL) and heated under reflux for 8 hours. did. After cooling, the mixture was poured into water (500 mL), toluene (500 mL) was added to separate the organic layer, and magnesium sulfate and sodium sulfate were added as drying agents. Furthermore, solid matter was filtered off, and the filtrate was concentrated under reduced pressure. The obtained solid was purified by column chromatography (toluene) and recrystallized from ethanol (80 mL) to obtain compound (1-2) (26.5 g, 0.09 mol, yield 36.0%). .

¹ H-NMR (CDCl3) δ 7.90 (t, J = 8.5 Hz, 4H), 7.29 (dd, J = 8.5 Hz, 2.0 Hz, 4H), 2.65 (t, J = 7 .5Hz, 2H), 2.42 (s, 3H), 1.68 (sext, 2H), 0.97 (t, J=7.2Hz, 3H).

Upper limit temperature (NI) = 162.6°C; dielectric anisotropy (Δε) = -5.67; optical anisotropy (Δn) = 0.320; viscosity (η) = 45.1 mPa·s.

Examples of compositions are shown below. Component compounds were represented by symbols based on the definitions in Table 3 below. In Table 3, the configuration for 1,4-cyclohexylene is trans. The number in parentheses after the symbol corresponds to the compound number. The symbol (-) means other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is the mass percentage (mass %) based on the mass of the liquid crystal composition. Finally, the characteristic values of the composition were summarized.

As Comparative Example 1, Composition Example 4 of International Publication No. 1997/012275 was used. The lower temperature limit and rotational viscosity were measured according to the methods described herein.
[Comparative example 1]
3-HTdaB-3 (1) 10%
2-HTdaB-4 (1) 10%
3-BTdaB-6 (-) 10%
2-BTdaB-8 (-) 10%
1O1-HH-3 (-) 6%
1O1-HH-5 (-) 4%
3-HH-E1 (-) 9%
3-HEB-O1 (-) 5%
3-HEB-O2 (-) 4%
4-HEB-O1 (-) 9%
4-HEB-O2 (-) 9%
5-HEB-O1 (-) 8%
5-HEB-5 (-) 6%
NI=87.0°C; Tc<0°C;Δn=0.123;Δε=−1.4; η=31.5 mPa·s; γ1=266.3 mPa·s.

[Example 1]
5-BTdaB-1 (1-2) 5%
3-HH-V (2-1) 35%
3-HH-V1 (2-1) 5%
3-HHEBH-3 (2-13) 5%
5-HBB(F)B-3 (2-15) 5%
3-HB(F,F)-O2 (3-1) 5%
3-H2B(F,F)-O2 (3-2) 5%
3-BB(F,F)-O2 (3-6) 5%
3-HHB(F,F)-O2 (3-8) 10%
3-HH2B(F,F)-O2 (3-9) 10%
3-HH1OB(F,F)-O2 (3-10) 10%
NI=102.6°C; Tc<-30°C;Δn=0.099;Δε=-2.9; γ1=109.8 mPa·s; Vth=2.86V; K11=19.6pN; K33=20. 4pN.

[Example 2]
5-BTdaB-1 (1-2) 5%
3-HH-V (2-1) 35%
3-HHB-1 (2-7) 10%
V-HHB-1 (2-7) 5%
3-HB(F,F)-O2 (3-1) 5%
3-H2B(F,F)-O2 (3-2) 5%
3-BB(F,F)-O2 (3-6) 5%
3-HHB(F,F)-O2 (3-8) 5%
3-HH2B(F,F)-O2 (3-9) 10%
3-HH1OB(F,F)-O2 (3-10) 10%
3-HBB(F,F)-O2 (3-14) 5%
NI=94.1°C; Tc<-20°C;Δn=0.097;Δε=-2.8; γ1=90.6 mPa·s; Vth=2.82V; K11=19.1 pN; K33=19. 1 pN.

[Example 3]
5-BTdaB-1 (1-2) 5%
3-HH-V (2-1) 35%
3-HB(F,F)-O2 (3-1) 5%
3-H2B(F,F)-O2 (3-2) 5%
3-BB(F,F)-O2 (3-6) 5%
3-HHB(F,F)-O2 (3-8) 5%
3-HH2B(F,F)-O2 (3-9) 10%
3-HH1OB(F,F)-O2 (3-10) 10%
3-HBB(F,F)-O2 (3-14) 5%
3-HB(2F)B(F,F)-O2 (3-18) 5%
2-BB(F,F)B-3 (3-19) 10%
NI=86.1°C; Tc<-30°C;Δn=0.114;Δε=-3.5; γ1=95.6 mPa·s; Vth=2.36V; K11=17.0 pN; K33=16. 9pN.

[Example 4]
5-BTdaB-1 (1-2) 5%
3-HH-V (2-1) 35%
3-HH-V1 (2-1) 5%
1V2-HH-3 (2-1) 5%
3-HB(F,F)-O2 (3-1) 5%
3-H2B(F,F)-O2 (3-2) 5%
3-BB(F,F)-O2 (3-6) 5%
3-HHB(F,F)-O2 (3-8) 5%
3-HH2B(F,F)-O2 (3-9) 10%
3-HH1OB(F,F)-O2 (3-10) 10%
3-HBB(F,F)-O2 (3-14) 5%
2-BB(F,F)B-3 (3-19) 5%
NI=83.6°C; Tc<-30°C;Δn=0.099;Δε=-3.0; γ1=78.0 mPa·s; Vth=2.63V; K11=17.9pN; K33=17. 6pN.

[Example 5]
3-BTdaB-1 (1-2) 5%
3-HH-V (2-1) 41%
1-BB-3 (2-3) 1.5%
3-HBB-2 (2-8) 9%
V-HHBB-2 (2-12) 4.5%
2-BB(F,F)-O2 (3-6) 10%
3-BB(F,F)-O2 (3-6) 10%
V2-BB(F,F)-O2 (3-6) 2%
3-HHB(F,F)-O2 (3-8) 4%
3-HBB(F,F)-O2 (3-14) 10%
2-BB(F,F)B-3 (3-19) 3%
NI=73.9°C; Tc<-20°C;Δn=0.120;Δε=-2.1; γ1=51.5 mPa·s; Vth=2.69V; K11=13.6pN; K33=12. 8pN.

[Example 6]
3-BTdaB-1 (1-2) 7%
3-HH-V (2-1) 44%
1-BB-3 (2-3) 1%
3-HBB-2 (2-8) 6.5%
V-HHBB-2 (2-12) 3%
3-HB(F,F)-O2 (3-1) 2%
2-BB(F,F)-O2 (3-6) 8%
3-BB(F,F)-O2 (3-6) 10%
3-HBB(F,F)-O2 (3-14) 10%
V-HBB(F,F)-O2 (3-14) 7.5%
2-BB(F,F)B-3 (3-19) 1%
NI=72.2°C; Tc<-20°C;Δn=0.120;Δε=-2.3; γ1=51.2 mPa·s; Vth=2.55V; K11=13.9pN; K33=12. 6pN.

[Example 7]
5-BTdaB-1 (1-2) 7%
3-HH-V (2-1) 44%
1-BB-3 (2-3) 1%
3-HBB-2 (2-8) 6.5%
V-HHBB-2 (2-12) 3%
3-HB(F,F)-O2 (3-1) 2%
2-BB(F,F)-O2 (3-6) 8%
3-BB(F,F)-O2 (3-6) 10%
3-HBB(F,F)-O2 (3-14) 10%
V-HBB(F,F)-O2 (3-14) 7.5%
2-BB(F,F)B-3 (3-19) 1%
NI=72.7°C; Tc<-20°C;Δn=0.119;Δε=-2.1; γ1=48.6 mPa·s; Vth=2.57V; K11=13.3pN; K33=11. 8pN.

[Example 8]
3-BTdaB-1 (1-2) 5%
3-HH-V (2-1) 36%
3-HBB-2 (2-8) 3%
V-HHBB-2 (2-12) 3%
2-BB(F,F)-O2 (3-6) 6%
3-BB(F,F)-O2 (3-6) 10%
V2-BB(F,F)-O2 (3-6) 5%
V-HHB(F,F)-O2 (3-8) 9%
3-HDhB(F,F)-O2 (3-13) 7%
3-HBB(F,F)-O2 (3-14) 6%
3O-Phe (1F, 8F)-O2 (3-36) 5%
4O-Phe (1F, 8F)-O2 (3-36) 5%
NI=75.2°C; Tc<-20°C;Δn=0.124;Δε=-3.7; γ1=69.6 mPa·s; Vth=1.93V; K11=15.7pN; K33=11. 8pN.

[Example 9]
3-BTdaB-1 (1-2) 7%
3-HH-V (2-1) 15%
1V2-HH-3 (2-1) 12%
V-HH-V1 (2-1) 9%
3-HHH-V (2-4) 5%
3-HHVH-V (2-5) 7%
V2-HHB-1 (2-7) 7%
V2-BB(F,F)-O2 (3-6) 7%
3-HH1OB(F,F)-O2 (3-10) 18%
2-HH1OB(F,F)-O2 (3-10) 13%
NI=118.6°C; Tc<-20°C;Δn=0.102;Δε=-3.1; γ1=147.1 mPa·s; Vth=2.85V; K11=23.6pN; K33=22. 6pN.

[Example 10]
3-BTdaB-1 (1-2) 7%
3-HH-V (2-1) 23%
1V2-HH-3 (2-1) 7%
3-HH-V1 (2-1) 10%
3-HHH-V (2-4) 5%
V2-HHB-1 (2-7) 8%
2-HHB(F,F)-O2 (3-8) 2%
3-HHB(F,F)-O2 (3-8) 10%
3-HHB(F,F)-O1 (3-8) 5%
3-HH1OB(F,F)-O2 (3-10) 18%
3O-Phe (1F, 8F)-O2 (3-36) 5%
NI=122.3°C; Tc<-20°C;Δn=0.103;Δε=-3.1; γ1=162.5 mPa·s; Vth=2.95V; K11=25.8pN; K33=24. 2pN.

[Example 11]
3-BTdaB-1 (1-2) 7%
3-HH-V (2-1) 10%
1V2-HH-1 (2-1) 7%
1V2-HH-3 (2-1) 12%
3-HH-V1 (2-1) 10%
3-HHH-V (2-4) 5%
V2-HHB-1 (2-7) 8%
V2-BB(F,F)-O2 (3-6) 3%
3-HHB(F,F)-O2 (3-8) 10%
3-HH2B(F,F)-O2 (3-9) 10%
3-HH1OB(F,F)-O2 (3-10) 18%
NI=123.4°C; Tc<-20°C;Δn=0.101;Δε=-3.0; γ1=193.1 mPa·s; Vth=3.22V; K11=28.2pN; K33=27. 9pN.

[Example 12]
3-BTdaB-1 (1-2) 7%
3-HH-V (2-1) 19%
1V2-HH-3 (2-1) 9%
V-HH-V1 (2-1) 9%
3-HHH-V (2-4) 3%
V2-HHB-1 (2-7) 7%
2-BB(F)B-2V (2-10) 5%
3-BB (2F, 5F) B-3 (2) 3%
V2-BB(F,F)-O2 (3-6) 7%
3-HH1OB(F,F)-O2 (3-10) 18%
2-HH1OB(F,F)-O2 (3-10) 13%
NI=106.5°C; Tc<-20°C;Δn=0.115;Δε=-3.0; γ1=136.2 mPa·s; Vth=2.73V; K11=20.2pN; K33=20. 4pN.

[Example 13]
3-BTdaB-1 (1-2) 7%
3-HH-V (2-1) 19%
1V2-HH-3 (2-1) 9%
V-HH-V1 (2-1) 9%
3-HHH-V (2-4) 3%
V2-HHB-1 (2-7) 7%
2-BB(F)B-2V (2-10) 5%
3-BB (2F, 5F) B-3 (2) 3%
V2-BB(F,F)-O2 (3-6) 7%
3-HH1OB(F,F)-O2 (3-10) 13%
2-HH1OB(F,F)-O2 (3-10) 13%
3-HB(2F)B(F,F)-O2 (3-18) 5%
NI=105.4°C; Tc<-20°C;Δn=0.119;Δε=-3.0; γ1=134.3 mPa·s; Vth=2.77V; K11=19.8pN; K33=20. 3pN.

[Example 14]
3-BTdaB-1 (1-2) 7%
3-HH-V (2-1) 30%
3-HHH-V (2-4) 3%
3-HHB-1 (2-7) 3%
V-HHB-1 (2-7) 7%
V2-HHB-1 (2-7) 4%
2-BB(F)B-2V (2-10) 5%
3-BB (2F, 5F) B-3 (2) 3%
3-HHB(F,F)-O2 (3-8) 5%
3-HH2B(F,F)-O2 (3-9) 10%
3-HH1OB(F,F)-O2 (3-10) 15%
3-HDhB(F,F)-O2 (3-13) 3%
3-HBB(F,F)-O2 (3-14) 5%
NI=123.8°C; Tc<-20°C;Δn=0.117;Δε=-2.7; γ1=170.3 mPa·s; Vth=3.16V; K11=23.5pN; K33=24. 0pN.

[Example 15]
3-BTdaB-1 (1-2) 7%
3-HH-V (2-1) 30%
1-BB-2 (2-3) 5%
3-HHH-V (2-4) 3%
V-HHB-1 (2-7) 5%
V-HBB-2 (2-8) 3%
2-BB(F)B-2V (2-10) 5%
3-HHEBH-3 (2-13) 3%
3-HHB(F,F)-O2 (3-8) 5%
3-HH1OB(F,F)-O2 (3-10) 13%
2-HH1OB(F,F)-O2 (3-10) 13%
3-HBB(F,F)-O2 (3-14) 5%
3O-Phe (1F, 8F)-O2 (3-36) 3%
NI=113.1°C; Tc<-20°C;Δn=0.122;Δε=-3.1; γ1=145.7 mPa·s; Vth=2.69V; K11=20.8pN; K33=20. 1 pN.

[Example 16]
3-BTdaB-1 (1-2) 7%
3-HH-V (2-1) 30%
V-HHB-1 (2-7) 5%
V-HBB-2 (2-8) 3%
2-BB(F)B-2V (2-10) 5%
V-HHBB-2 (2-12) 3%
3-HHEBH-3 (2-13) 3%
5-HBB(F)B-2 (2-15) 5%
3-HHB(F,F)-O2 (3-8) 5%
3-HH1OB(F,F)-O2 (3-10) 13%
2-HH1OB(F,F)-O2 (3-10) 13%
3-HBB(F,F)-O2 (3-14) 5%
3O-Phe (1F, 8F)-O2 (3-36) 3%
NI=130.4°C; Tc<-20°C;Δn=0.129;Δε=-3.1; γ1=195.2 mPa·s; Vth=2.80V; K11=21.6pN; K33=21. 7pN.

[Example 17]
3-BTdaB-1 (1-2) 7%
3-HH-V (2-1) 30%
V-HHB-1 (2-7) 5%
V-HBB-2 (2-8) 3%
2-BB(F)B-2V (2-10) 5%
3-HHB(F,F)-O2 (3-8) 10%
3-HH2B(F,F)-O2 (3-9) 11%
3-HH1OB(F,F)-O2 (3-10) 13%
3-HDhB(F,F)-O2 (3-13) 5%
3-HBB(F,F)-O2 (3-14) 5%
3O-Phe (1F, 8F)-O2 (3-36) 3%
4O-Phe (1F, 8F)-O2 (3-36) 3%
NI=117.8°C; Tc<-20°C;Δn=0.123;Δε=-3.8; γ1=175.6 mPa·s; Vth=2.55V; K11=22.2pN; K33=21. 9pN.

[Example 18]
3-BTdaB-1 (1-2) 7%
3-HH-V (2-1) 30%
V-HHB-1 (2-7) 5%
V-HBB-2 (2-8) 3%
2-BB(F)B-2V (2-10) 5%
3-HHB(F,F)-O2 (3-8) 10%
3-HH2B(F,F)-O2 (3-9) 11%
3-HH1OB(F,F)-O2 (3-10) 13%
3-HDhB(F,F)-O2 (3-13) 5%
3-HBB(F,F)-O2 (3-14) 6%
2O-DBTF2-O4 (3-34) 5%
NI=118.0°C; Tc<-20°C;Δn=0.123;Δε=-4.0; γ1=182.4 mPa·s; Vth=2.45V; K11=22.6pN; K33=21. 3pN.

[Example 19]
3-BTdaB-1 (1-2) 7%
3-HH-V (2-1) 28%
3-HH-V1 (2-1) 10%
1V2-HH-1 (2-1) 2%
1V2-HH-3 (2-1) 5%
V2-HHB-1 (2-7) 8%
3-HHB(F,F)-O2 (3-8) 10%
3-HHB(F,F)-O1 (3-8) 4%
3-HH1OB(F,F)-O2 (3-10) 18%
2O-DBTF2-O4 (3-34) 3%
3O-Phe (1F, 8F)-O2 (3-36) 5%
NI=109.2°C; Tc<-20°C;Δn=0.104;Δε=-3.1; γ1=130.2 mPa·s; Vth=2.74V; K11=22.8pN; K33=21. 0pN.

[Example 20]
3-BTdaB-1 (1-2) 7%
3-HH-V (2-1) 30%
V-HHB-1 (2-7) 5%
V2-HHB-1 (2-7) 10%
3-H1OB(F,F)-O2 (3-3) 15%
2-BB(F,F)-O2 (3-6) 5%
3-HHB(F,F)-O2 (3-8) 5%
3-HH2B(F,F)-O2 (3-9) 10%
3-HH1OB(F,F)-O2 (3-10) 13%
NI=91.9°C; Tc<-20°C;Δn=0.100;Δε=-3.9; γ1=120.7 mPa·s; Vth=2.30V; K11=18.1 pN; K33=18. 6pN.

[Example 21]
3-BTdaB-1 (1-2) 7%
3-HH-V (2-1) 30%
V-HHB-1 (2-7) 5%
V2-HHB-1 (2-7) 10%
3-H1OB(F,F)-O2 (3-3) 15%
3-HHB(F,F)-O2 (3-8) 5%
3-HH2B(F,F)-O2 (3-9) 10%
3-HH1OB(F,F)-O2 (3-10) 13%
3-HBB(F,F)-O2 (3-14) 5%
NI=101.4°C; Tc<-20°C;Δn=0.102;Δε=-3.9; γ1=137.4 mPa·s; Vth=2.43V; K11=18.9pN; K33=20. 4pN.

[Example 22]
3-BTdaB-1 (1-2) 7%
3-HH-V (2-1) 30%
1-BB-2 (2-3) 5%
3-HHH-V (2-4) 3%
V-HHB-1 (2-7) 5%
V-HBB-2 (2-8) 3%
3-HHB(F,F)-O2 (3-8) 5%
3-HH1OB(F,F)-O2 (3-10) 13%
2-HH1OB(F,F)-O2 (3-10) 13%
3-HBB(F,F)-O2 (3-14) 5%
2-BB(F,F)B-3 (3-19) 8%
3O-Phe (1F, 8F)-O2 (3-36) 3%
NI=104.6°C; Tc<-20°C;Δn=0.124;Δε=-3.3; γ1=127.3 mPa·s; Vth=2.49V; K11=18.7pN; K33=18. 1 pN.

[Example 23]
3-BTdaB-1 (1-2) 7%
3-HH-V (2-1) 19%
V-HH-V1 (2-1) 9%
1V2-HH-3 (2-1) 9%
3-HHH-V (2-4) 3%
V2-HHB-1 (2-7) 7%
V2-BB(F,F)-O2 (3-6) 5%
3-HH1OB(F,F)-O2 (3-10) 18%
2-HH1OB(F,F)-O2 (3-10) 13%
2-BB(F,F)B-3 (3-19) 10%
NI=106.7°C; Tc<-20°C;Δn=0.116;Δε=-3.3; γ1=136.0 mPa·s; Vth=2.64V; K11=20.4pN; K33=20. 6pN.

[Example 24]
2-BTdaB-1 (1-2) 5%
3-HH-V (2-1) 41%
1-BB-3 (2-3) 1.5%
3-HBB-2 (2-8) 9%
V-HHBB-2 (2-12) 4.5%
2-BB(F,F)-O2 (3-6) 10%
3-BB(F,F)-O2 (3-6) 10%
V2-BB(F,F)-O2 (3-6) 2%
3-HHB(F,F)-O2 (3-8) 4%
3-HBB(F,F)-O2 (3-14) 10%
2-BB(F,F)B-3 (3-19) 3%
NI=73.4°C; Tc<-20°C;Δn=0.120;Δε=-2.1; γ1=52.5 mPa·s; Vth=2.69V; K11=13.6pN; K33=12. 8pN.

[Example 25]
3-BTda-1 (1-1) 5%
3-HH-V (2-1) 41%
1-BB-3 (2-3) 1.5%
3-HBB-2 (2-8) 9%
V-HHBB-2 (2-12) 4.5%
2-BB(F,F)-O2 (3-6) 10%
3-BB(F,F)-O2 (3-6) 10%
V2-BB(F,F)-O2 (3-6) 2%
3-HHB(F,F)-O2 (3-8) 4%
3-HBB(F,F)-O2 (3-14) 10%
2-BB(F,F)B-3 (3-19) 3%
NI=66.9°C; Tc<-20°C;Δn=0.112;Δε=-1.8; γ1=31.5 mPa·s; Vth=2.62V; K11=12.6pN; K33=11. 3pN.

[Example 26]
1-BBTda-3 (1-3) 5%
3-HH-V (2-1) 41%
1-BB-3 (2-3) 1.5%
3-HBB-2 (2-8) 9%
V-HHBB-2 (2-12) 4.5%
2-BB(F,F)-O2 (3-6) 10%
3-BB(F,F)-O2 (3-6) 10%
V2-BB(F,F)-O2 (3-6) 2%
3-HHB(F,F)-O2 (3-8) 4%
3-HBB(F,F)-O2 (3-14) 10%
2-BB(F,F)B-3 (3-19) 3%
NI=74.4°C; Tc<-20°C;Δn=0.120;Δε=-1.8; γ1=51.5 mPa·s; Vth=2.72V; K11=13.6pN; K33=12. 8pN.

[Example 27]
1-HBTdaB-3 (1-6) 5%
3-HH-V (2-1) 41%
1-BB-3 (2-3) 1.5%
3-HBB-2 (2-8) 9%
V-HHBB-2 (2-12) 4.5%
2-BB(F,F)-O2 (3-6) 10%
3-BB(F,F)-O2 (3-6) 10%
V2-BB(F,F)-O2 (3-6) 2%
3-HHB(F,F)-O2 (3-8) 4%
3-HBB(F,F)-O2 (3-14) 10%
2-BB(F,F)B-3 (3-19) 3%
NI=77.4°C; Tc<-20°C;Δn=0.121;Δε=-1.8; γ1=71.5 mPa·s; Vth=2.74V; K11=14.2pN; K33=13. 7pN.

[Example 28]
1-BTdaB(F,F)-3 (1-2) 5%
3-HH-V (2-1) 41%
1-BB-3 (2-3) 1.5%
3-HBB-2 (2-8) 9%
V-HHBB-2 (2-12) 4.5%
2-BB(F,F)-O2 (3-6) 10%
3-BB(F,F)-O2 (3-6) 10%
V2-BB(F,F)-O2 (3-6) 2%
3-HHB(F,F)-O2 (3-8) 4%
3-HBB(F,F)-O2 (3-14) 10%
2-BB(F,F)B-3 (3-19) 3%
NI=72.4°C; Tc<-20°C;Δn=0.119;Δε=-2.1; γ1=66.5 mPa·s; Vth=2.69V; K11=13.6pN; K33=12. 8pN.

[Example 29]
1-BTdaB(F,F)-O2 (1-2) 5%
3-HH-V (2-1) 41%
1-BB-3 (2-3) 1.5%
3-HBB-2 (2-8) 9%
V-HHBB-2 (2-12) 4.5%
2-BB(F,F)-O2 (3-6) 10%
3-BB(F,F)-O2 (3-6) 10%
V2-BB(F,F)-O2 (3-6) 2%
3-HHB(F,F)-O2 (3-8) 4%
3-HBB(F,F)-O2 (3-14) 10%
2-BB(F,F)B-3 (3-19) 3%
NI=74.4°C; Tc<-20°C;Δn=0.119;Δε=-2.2; γ1=71.5 mPa·s; Vth=2.67V; K11=13.7pN; K33=12. 9pN.

The rotational viscosity and dielectric anisotropy of the composition of Comparative Example 1 were 266.3 mPa·s and −1.4, respectively, and the nematic phase could not be maintained at −10° C. and the composition crystallized. On the other hand, the rotational viscosity and dielectric anisotropy of the compositions of Examples 1 to 29 are 31.5 mPa·s to 195.2 mPa·s and −1.8 to −4.0, respectively, and the lower limit Regarding the temperature, crystallization did not occur at least at -20°C. Therefore, it is concluded that the liquid crystal composition of the present invention has excellent properties.

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

Claims (17)

Contains at least one compound selected from the compounds represented by formula (1) as component A and at least one compound selected from the compounds represented by formula (2) as component B, and has a nematic phase and a negative phase. A liquid crystal composition that has dielectric anisotropy and does not have a chiral smectic phase.

In formula (1), R ¹ and R ² are hydrogen, alkyl having 1 to 5 carbon atoms, cyclic alkyl having 3 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, alkenyl having 2 to 5 carbon atoms, and 2 to 5 alkenyloxy, or alkyl of 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; Ring A and Ring B are 1,4-cyclohexylene, 1,4-cyclohexenyl, X is sulfur or oxygen; Yes; a is 1, 2, or 3; b is 0 or 1; and the sum of a and b is 3 or less;
In formula (2), R ³ and R ⁴ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or carbon in which at least one hydrogen is replaced with fluorine or chlorine. Alkyl having a number of 1 to 12, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; Ring C and Ring D are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ¹ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; c is 1, 2, or 3; when c is 1, Z ¹ is a single bond, ethylene, vinylene, or methyleneoxy. The liquid crystal composition according to claim 1, containing as component A at least one compound selected from compounds represented by formulas (1-1) to (1-8).

In formulas (1-1) to (1-8), R ¹ and R ² are hydrogen, alkyl having 1 to 5 carbon atoms, cyclic alkyl having 3 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, carbon Alkenyl having 2 to 5 carbon atoms, alkenyloxy having 2 to 5 carbon atoms, or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; Y is hydrogen, fluorine, or chlorine. The liquid crystal composition according to claim 1 or 2, wherein the proportion of component A is in the range of 3% by mass to 30% by mass. The liquid crystal composition according to claim 1 or 2, containing as component B at least one compound selected from compounds represented by formulas (2-1) to (2-15).

In formulas (2-1) to (2-15), R ³ and R ⁴ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and at least one hydrogen is an alkyl having 1 to 12 carbon atoms in which is replaced with fluorine or chlorine, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. The liquid crystal composition according to claim 1 or 2, wherein the proportion of component B is in the range of 10% by mass to 85% by mass. The liquid crystal composition according to claim 1 or 2, containing as component C at least one compound selected from compounds represented by formula (3).

In formula (3), R ⁵ and R ⁶ are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkenyloxy having 2 to 12 carbon atoms, or at least is an alkyl having 1 to 12 carbon atoms in which one hydrogen is replaced with fluorine or chlorine; Ring E and Ring G are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5- diyl, 1,4-phenylene, 1,4-phenylene with at least one hydrogen replaced by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2 with at least one hydrogen replaced with fluorine or chlorine, 6-diyl, chroman-2,6-diyl, or chroman-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine; Ring F is 2,3-difluoro-1,4-phenylene , 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 1,8-difluorophenanthrene-2,7-diyl, 3,4,5- Trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3, 7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoroindan-2,5-diyl; Z ² and Z ³ are a single bond, ethylene , vinylene, methyleneoxy, or carbonyloxy; d is 0, 1, 2, or 3; e is 0 or 1; and the sum of d and e is 3 or less. The liquid crystal composition according to claim 1 or 2, containing as component C at least one compound selected from compounds represented by formulas (3-1) to (3-36).

In formulas (3-1) to (3-36), R ⁵ and R ⁶ are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and 2 to 12 alkenyloxy, or C1 to C12 alkyl in which at least one hydrogen is replaced with fluorine or chlorine. 7. The liquid crystal composition according to claim 6, wherein the proportion of component C is in the range of 10% by mass to 85% by mass. The liquid crystal composition according to claim 1 or 2, containing as additive X at least one compound selected from polymerizable compounds represented by formula (4).

In formula (4), ring I and ring K are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl , or pyridin-2-yl, in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or at least one hydrogen is fluorine or chlorine. may be substituted with alkyl having 1 to 12 carbon atoms; Ring J 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 having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is It may be substituted with a C1-C12 alkyl substituted with fluorine or chlorine; Z ⁴ and Z ⁵ are a single bond or a C1-C10 alkylene, in which at least one -CH ₂ - may be replaced with -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 )-, in which at least one hydrogen is replaced by fluorine or chlorine. P ¹ to P ³ are polymerizable groups; Sp ¹ to Sp ³ are single bonds or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one -CH ₂ - may be replaced with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ - may be replaced with -CH=CH- or -C≡C- and in these groups at least one hydrogen may be replaced by fluorine or chlorine; f is 0, 1, or 2; g, h, and i are 0, 1, 2 , 3, or 4; and the sum of g, h, and i is 1 or more. The liquid crystal composition according to claim 9, wherein in formula (4), P ¹ to P ³ are groups selected from polymerizable groups represented by formulas (P-1) to (P-5).

In formulas (P-1) to (P-5), M ¹ to M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or 1-carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. to 5 alkyl. The liquid crystal composition according to claim 1 or 2, containing as additive X at least one compound selected from polymerizable compounds represented by formulas (4-1) to (4-29).

In formulas (4-1) to (4-29), Sp ¹ to Sp ³ are single bonds or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one -CH ₂ - is -O -, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ - may be replaced with -CH=CH- or -C≡C-, In these groups, at least one hydrogen may be replaced by fluorine or chlorine; P ⁴ to P ⁶ are selected from the groups represented by formulas (P-1) to (P-3) is a polymerizable group;

In formulas (P-1) to (P-3), M ¹ to M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or 1-carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. to 5 alkyl. The liquid crystal composition according to claim 9, wherein the proportion of additive X is in the range of 0.03% by mass to 10% by mass. A liquid crystal display element comprising the liquid crystal composition according to claim 1 or 2. 14. The liquid crystal display element according to claim 13, wherein the operation mode is an IPS mode, VA mode, FFS mode, or FPA mode, and the driving method is an active matrix method. A polymer-supported alignment type liquid crystal display element containing the liquid crystal composition according to claim 9, wherein the polymerizable compound in the liquid crystal composition is polymerized. Use of the liquid crystal composition according to claim 1 or 2 in a liquid crystal display element. Use of the liquid crystal composition according to claim 9 in a polymer supported alignment type liquid crystal display element.