JP2021095555A - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

To provide a liquid crystal composition with negative dielectric anisotropy which contains a polymerizable compound and a polar compound having a polymerizable group (or polymer thereof), and in which a vertical orientation of liquid crystal molecules is achievable by the effect of the compound, and a liquid crystal display element.SOLUTION: A nematic liquid crystal composition that contains polymerizable compound as an additive X, contains a polar compound having a polymerizable group as an additive Y, and has negative dielectric anisotropy. The composition may contain specific liquid crystalline compound as component A having negatively large dielectric anisotropy, specific liquid crystalline compound as component B having high upper limit temperature or small viscosity, and a polymerizable compound as additive Z, and a liquid crystal display element containing the composition.SELECTED DRAWING: None

Description

The present invention relates to a liquid crystal composition, a liquid crystal display element containing the composition, and the like. In particular, a liquid crystal composition having a negative dielectric anisotropy, which contains a polymerizable compound and a polar compound having a polymerizable group (or a polymer thereof), and the vertical orientation of liquid crystal molecules can be achieved by the action of this compound. , And the liquid crystal display element.

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

The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the characteristics of this composition, an AM element having good characteristics can be obtained. The relationship between the two characteristics is summarized in Table 1 below. The properties of the composition will be further described based on commercially available AM devices. The temperature range of the nematic phase is related to the temperature range in which the device can be used. The preferred upper limit temperature of the nematic phase is about 70 ° C. or higher, and the preferred lower limit temperature of the nematic phase is about −10 ° C. or lower. The viscosity of the composition is related to the response time of the device. A short response time is preferred for displaying moving images on the device. A shorter response time of even 1 millisecond is desirable. Therefore, a small viscosity in the composition is preferred. Small viscosities at low temperatures are even more preferred.

The optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large optical anisotropy or a small optical anisotropy, that is, an appropriate optical anisotropy is required. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate value of the product depends on the type of operation mode. This value ranges from about 0.30 μm to about 0.40 μm for VA mode devices and from about 0.20 μm to about 0.30 μm for IPS or FFS mode devices. In these cases, a composition having a large optical anisotropy is preferable for a device having a small cell gap. The large permittivity anisotropy in the composition contributes to the low threshold voltage, low power consumption and large contrast ratio in the device. Therefore, a large dielectric anisotropy is preferred. A large resistivity in the composition contributes to a large voltage retention and a large contrast ratio in the device. Therefore, a composition having a large specific resistance in the initial stage is preferable. A composition having a large specific resistance after long-term use is preferable. The stability of the composition against UV light and heat is related to the life of the device. When this stability is high, the life of the device is long. Such characteristics are preferable for AM elements used in liquid crystal monitors, liquid crystal televisions, and the like.

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

On the other hand, in a liquid crystal display element having no alignment film, a liquid crystal composition containing a polymer and a polar compound is used. First, a composition containing a small amount of a polymerizable compound and a small amount of a polar compound is injected into the device. Here, the polar compounds are adsorbed on the substrate surface of the device and arranged. The liquid crystal molecules are oriented according to this arrangement. Next, the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of this device. Here, the polymerizable compound polymerizes and stabilizes the orientation of the liquid crystal molecules. In this composition, the orientation of the liquid crystal molecules can be controlled by the polymer and the polar compound, so that the response time of the device is shortened and the image burn-in is improved. Further, in the device having no alignment film, the step of forming the alignment film is unnecessary. Since there is no alignment film, the interaction between the alignment film and the composition does not reduce the electrical resistance of the device. Such effects due to the combination of the polymer and the polar compound can be expected for devices having modes such as TN, ECB, OCB, IPS, VA, FFS and FPA.

In the AM device having the TN mode, a composition having a positive dielectric anisotropy is used. In the AM device having the VA mode, a composition having a negative dielectric anisotropy is used. In an AM device having an IPS mode or an FFS mode, a composition having positive or negative dielectric anisotropy is used. In the polymer support orientation type AM device, a composition having positive or negative dielectric anisotropy is used. In a device having no alignment film, a composition having positive or negative dielectric anisotropy is used. Compositions having a negative dielectric anisotropy are disclosed in the following Patent Documents 1 to 4 and the like.

International Publication No. 2014-090362 International Publication No. 2014-09949 International Publication No. 2013-004372 Japanese Unexamined Patent Publication No. 2015-168826

An object of the present invention is to provide a liquid crystal composition containing a polymerizable compound as an additive X and a polar compound (or a polymer thereof) having a polymerizable group as an additive Y, wherein the liquid crystal composition is provided. Has excellent vertical orientation and high heating VHR (voltage retention). Another object is to provide a liquid crystal composition in which vertical orientation of liquid crystal molecules can be achieved by the action of a polymer generated from the polymerizable compound and the polar compound. Another challenge is the high upper limit temperature of the nematic phase, the lower lower limit temperature of the nematic phase, small viscosity, proper optical anisotropy, negatively large dielectric anisotropy, large specific resistance, high stability to ultraviolet rays, and heat. A liquid crystal composition that satisfies at least one property in terms of properties such as high stability and a large elastic constant. Another challenge is to provide a liquid crystal composition having an appropriate balance between at least two of these properties. Another issue is a liquid crystal display device containing such a composition. Another challenge is AM devices with characteristics such as short response time, large voltage retention, low threshold voltage, large contrast ratio, and long lifetime.

ここで、Ａ^１などの記号の定義は、後述の項１を参照のこと。 In the present invention, the additive X is at least one compound selected from the polymerizable compound represented by the formula (1), and the additive Y is a polar compound (or a polar compound) having a polymerizable group represented by the formula (B). At least one compound selected from this polymer) was combined with a liquid crystal compound, and this composition was used for a liquid crystal display element having no alignment film. Specifically, at least one compound selected from the polymerizable compound represented by the formula (1) as the additive X, and a polar compound having a polymerizable group represented by the formula (B) as the additive Y ( A liquid crystal composition containing at least one compound selected from (or this polymer) and having a nematic phase and negative dielectric anisotropy, and a liquid crystal display element containing this composition.

Here, definitions of the symbols, such as A ^1, refer to the section 1 described later.

An advantage of the present invention is to provide a liquid crystal composition containing a polymerizable compound and a polar compound having a polymerizable group (or a polymer thereof), wherein the liquid crystal composition of the present invention is vertically oriented. Excellent and has high heating VHR. Another advantage is to provide a liquid crystal composition in which the vertical orientation of the liquid crystal molecules can be achieved by the action of the polymer generated from the polymerizable compound and the polar compound. Other advantages are high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, proper optical anisotropy, negatively large dielectric anisotropy, large specific resistance, high stability to ultraviolet rays, resistance to heat. A liquid crystal composition that satisfies at least one property in terms of properties such as high stability and a large elastic constant. Another advantage is to provide a liquid crystal composition having an appropriate balance between at least two of these properties. Another advantage is to provide a liquid crystal display device containing such a composition. Another advantage is to provide an AM device with characteristics such as short response time, high voltage retention, low threshold voltage, high contrast ratio, long life.

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

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

The "upper limit temperature of the nematic phase" may be abbreviated as the "upper limit temperature". The "lower limit temperature of the nematic phase" may be abbreviated as the "lower limit temperature". The expression "increase the dielectric anisotropy" means that when the composition has a positive dielectric anisotropy, its value increases positively, and the composition has a negative dielectric anisotropy. When it is a thing, it means that its value increases negatively. "Large voltage retention" means that the element has a large voltage retention not only at room temperature but also at a temperature close to the upper limit temperature at the initial stage, and after long-term use, it has a large voltage not only at room temperature but also at a temperature close to the upper limit temperature. It means having a retention rate. The properties of the composition or device may be examined by aging tests.

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

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

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

At least one compound selected from the compounds represented by the formula (1z) may be abbreviated as "Compound (1z)". "Compound (1z)" means one compound represented by the formula (1z), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas. The expression "at least one compound selected from the compounds of formula (1z) and formula (2z)" means at least one compound selected from the group of compounds (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'" is that when the number of'A's is 1, the position of the'A'is arbitrary and the number of'A's is 2. When there is more than one, their positions can be selected without limitation. The expression "at least one -CH _2- may be replaced by -O-" may be used. In this case, −CH ₂ −CH ₂ −CH ₂ − may be converted to −O—CH ₂ −O− by replacing the non-adjacent −CH _{2− with −O−.} However, the adjacent −CH ₂₋ is not replaced by −O−. This is because -O-O-CH _2- (peroxide) is produced by this replacement.

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

The same is true for divalent groups such as tetrahydropyran-2,5-diyl. The same is true for binding groups such as carbonyloxy (-COO- or -OCO-).

The present invention includes the following items.

式（１）において、
環Ａ^１および環Ａ^３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Ａ^２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のアルキルで置き換えられてもよく；
Ｚ^１およびＺ^２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_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ_３）−、または−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
Ｓｐ^１、Ｓｐ^２、および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_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
ａは、０、１、または２であり；
ｂ、ｃ、およびｄは、０、１、２、３、または４であり、そしてｂ、ｃ、およびｄの和は、１以上であり；
Ｐ^１、Ｐ^２、およびＰ^３は、重合性基であり、Ｐ^１、Ｐ^２、およびＰ^３の少なくとも１つは式（Ｐ−１）で表される重合性基であり；

式（Ｐ−１）において、
Ｍ^１は、炭素数１から５のアルキルであり；
ｎは、１から５の整数であり；

式（Ｂ）において、
Ｒ^６は、水素または炭素数１から７のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−または−Ｓ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
環Ａ^４および環Ａ^５は、１，２−シクロプロピレン、１，３−シクロブチレン、１，３−シクロペンチレン、１，４−シクロヘキシレン、１，４−シクロヘプチレン、１，４−シクロヘキセニレン、１，４−フェニレン、ナフタレン−２，６−ジイル、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−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１０のアルキル、炭素数２から１０のアルケニル、炭素数１から９のアルコキシ、または炭素数２から９のアルケニルオキシ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は、０、１、２、３、または４であり；
ｑおよびｒは、０、１、または２であり；
Ｚ^８は、単結合または炭素数１から６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−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
Ｘ^１は、窒素、酸素、硫黄、リンおよびケイ素からなる群から選択されたヘテロ原子を有する極性基である。
Ｓｐ^９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−、−ＯＣＯ−、−ＯＣＯＯ−、または式（１−ａ）で表される基で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素、塩素、式（Ａ−ｐ１）、式（Ａ−ｐ２）、式（Ａ−ｐ３）、式（Ａ−ｐ４）、または式（Ａ−ｐ５）で表される基で置き換えられてもよく；

Ｐ^１６およびＰ^１７は、式（Ａ−ｐ１）、式（Ａ−ｐ２）、式（Ａ−ｐ３）、式（Ａ−ｐ４）、および式（Ａ−ｐ５）で表される基から選択された基であり、；

式（Ａ−ｐ１）から式（Ａ−ｐ５）において、
Ｓｐ^１０は、単結合または炭素数１から１５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−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
Ｒ^７は、炭素数１から５のアルキルであり；
Ｒ^８は、炭素数１から１０のアルキルまたは炭素数３から８の環状のアルキルであり；
Ｙ^１は、塩素、フッ素、または臭素である。 Item 1. The additive X is selected from polar compounds containing at least one compound selected from the polymerizable compound represented by the formula (1), and the additive Y is selected from the polar compounds having a polymerizable group represented by the formula (B). A liquid crystal composition containing at least one compound and having a nematic phase and negative permittivity anisotropy.

In equation (1)
Rings A ¹ and A ³ are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine-2-yl, or pyridine-. 2-yl, in these rings at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least one hydrogen is replaced with fluorine or chlorine. It may be replaced with an alkyl having 1 to 12 carbon atoms;
Ring A ² contains 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene- 2,7-Diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings. , At least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, alkenyloxy with 2 to 12 carbon atoms, or carbon in which at least one hydrogen is replaced with fluorine or chlorine. May be replaced with alkyl of equations 1-12;
Z ¹ and Z ² are single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, or -OCO-. May be replaced, at least one −CH ₂ −CH ₂₋ may be −CH = CH−, −C (CH ₃ ) = CH−, −CH = C (CH ₃ ) −, or −C (CH _3). ) = C (CH ₃ )-may be replaced, and in these groups at least one hydrogen may be replaced with fluorine or chlorine;
Sp ¹ , Sp ² , and Sp ³ are single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH ₂ − is -O-, -COO-, -OCO-, or. It may be replaced by −OCOO −, at least one −CH ₂ −CH ₂ − may be replaced by −CH = CH− or −C≡C−, and in these groups, at least one hydrogen is present. , May be replaced with fluorine or chlorine;
a is 0, 1, or 2;
b, c, and d are 0, 1, 2, 3, or 4, and the sum of b, c, and d is greater than or equal to 1.
P ^{1, P 2,} and ^{P 3} is a polymerizable ^group, at least one of P 1, ^{P 2,} and ^{P 3} is an a polymerizable group represented by the formula (P-1);

In equation (P-1)
M ¹ is an alkyl having 1 to 5 carbon atoms;
n is an integer from 1 to 5;

In formula (B)
R ⁶ is hydrogen or an alkyl having 1 to 7 carbon atoms, in which at least one −CH ₂ − may be replaced by −O − or −S−, and at least one −CH ₂ −. CH ₂ − may be replaced by −CH = CH − or −C≡C−, and in these groups at least one hydrogen may be replaced by fluorine or chlorine;
Ring ^{A 4} and ring ^{A 5} are 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-cyclohexenylene Len, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-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, carbon number. It may be replaced with an alkyl of 1 to 10, an alkenyl having 2 to 10 carbon atoms, an alkoxy having 1 to 9 carbon atoms, or an alkenyloxy having 2 to 9 carbon atoms, and in these groups, at least one hydrogen is fluorine. Or may be replaced with chlorine;
p is 0, 1, 2, 3, or 4;
q and r are 0, 1, or 2;
Z ⁸ is a single bond or an alkylene with 1 to 6 carbon atoms, in which at least one -CH ₂ − is -O-, -CO-, -COO-, -OCO-, or -OCOO-. At least one −CH ₂ −CH ₂₋ may be replaced with −CH = CH− or −C≡C−, and in these groups at least one hydrogen is fluorine or May be replaced with chlorine;
X ¹ is a polar group having a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, phosphorus and silicon.
Sp ⁹ is a single bond or an alkylene having 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, -OCO-, -OCOO-, Alternatively, it may be replaced by a group represented by the formula (1-a), and at least one −CH ₂ −CH ₂ − may be replaced by −CH = CH− or −C≡C−. Under the basis of, at least one hydrogen is fluorine, chlorine, formula (A-p1), formula (A-p2), formula (A-p3), formula (A-p4), or formula (A-p5). May be replaced by the group represented;

P ¹⁶ and P ¹⁷ are selected from the groups represented by the formulas (A-p1), (A-p2), (A-p3), (A-p4), and (A-p5). It is a base, and;

In formulas (A-p1) to (A-p5),
Sp ¹⁰ is a single bond or an alkylene with 1 to 15 carbon atoms, in which at least one -CH ₂ − is -O-, -CO-, -COO-, -OCO-, or -OCOO-. At least one −CH ₂ −CH ₂₋ may be replaced with −CH = CH− or −C≡C−, and in these groups at least one hydrogen is fluorine or May be replaced with chlorine;
R ⁷ is an alkyl with 1 to 5 carbon atoms;
R ⁸ is an alkyl with 1 to 10 carbon atoms or a cyclic alkyl with 3 to 8 carbon atoms;
Y ¹ is chlorine, fluorine, or bromine.

式（Ｐ−１）から式（Ｐ−６）において、Ｍ^１は、炭素数１から５のアルキルであり；Ｍ^２、Ｍ^３、およびＭ^４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のアルキルであり；ｎは、１から５の整数である。 Item 2. In formula (1), P ¹ , P ² , and P ³ are groups selected from the polymerizable groups represented by formula (P-6) from formula (P-1), and P ¹ , P ² , and at least one of P ³ is a polymerizable group represented by the formula (P-1), the liquid crystal composition according to claim 1.

In formulas (P-1) to (P-6), M ¹ is an alkyl having 1 to 5 carbon atoms; M ² , M ³ and M ⁴ are hydrogen, fluorine, and 1 to 5 carbon atoms. Alkyl, or an alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; n is an integer of 1 to 5.

式（１−１）から式（１−３０）において、
Ｒ^１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；
Ｓｐ^１、Ｓｐ^２、および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_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
Ｐ^５、Ｐ^６、およびＰ^７は、式（Ｐ−１）から式（Ｐ−４）で表される重合性基から選択された基であり；Ｐ^５、Ｐ^６、およびＰ^７の少なくとも１つは式（Ｐ−１）で表される重合性基であり；

式（Ｐ−１）から式（Ｐ−４）において、
Ｍ^１は、炭素数１から５のアルキルであり；
Ｍ^２、Ｍ^３、およびＭ^４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のアルキルであり；
ｎは、１から５の整数である。 Item 3. Item 2. The liquid crystal composition according to Item 1 or 2, which contains at least one compound selected from the compounds represented by the formulas (1-1) to (1-30) as the additive X.

In equations (1-1) to (1-30),
R ¹ is hydrogen, an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, an alkenyloxy having 2 to 12 carbon atoms, or at least one hydrogen being replaced with fluorine or chlorine. Alkyl with 1 to 12 carbon atoms;
Sp ¹ , Sp ² , and Sp ³ are single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH ₂ − is -O-, -COO-, -OCO-, or. It may be replaced by −OCOO −, at least one −CH ₂ −CH ₂ − may be replaced by −CH = CH− or −C≡C−, and in these groups, at least one hydrogen is present. , May be replaced with fluorine or chlorine;
P ⁵ , P ⁶ , and P ⁷ are groups selected from the polymerizable groups represented by formulas (P-1) to (P-4); at least ^{P 5} , P ⁶ , and P ^7. One is a polymerizable group represented by the formula (P-1);

In equations (P-1) to (P-4),
M ¹ is an alkyl having 1 to 5 carbon atoms;
M ² , M ³ , and M ⁴ are hydrogen, fluorine, alkyl with 1 to 5 carbon atoms, or alkyl with 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine;
n is an integer from 1 to 5.

Item 4. Item 6. The liquid crystal composition according to any one of Items 1 to 3, wherein the ratio of the additive X is in the range of 0.03% by mass to 10% by mass.

式（Ｘ−１）から式（Ｘ−２７）において、
Ｊ^１およびＪ^２は、水素、または炭素数１から５のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−で置き換えられてもよく；
Ｊ^３は、水素、または炭素数１から２０のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよく；
Ｊ^４およびＪ^５は、水素、または炭素数１から８のアルキルであり；
Ｑ^１は、メチンまたは窒素であり、ここでメチンの水素は、炭素数１から６のアルキルで置き換えられてもよく；
Ｕ^１およびＵ^２は、−ＣＨ_２−、−Ｏ−、−ＣＯ−または−Ｓ−であり；
Ｖ^１、Ｖ^２およびＶ^３は、メチンまたは窒素であり、Ｖ^１、Ｖ^２およびＶ^３のいずれかひとつは必ず窒素であり；
Ｗ^１は、酸素または硫黄であり；
Ｗ^２は、炭素、硫黄またはケイ素である。
ただし、式（Ｘ−１４）においてＱ^１がメチンの場合は、Ｕ^１およびＵ^２のうち必ず一方は−Ｏ−、−ＣＯ−、または−Ｓ−である。 Item 5. Item 4. The liquid crystal according to any one of Items 1 to 4, wherein in the formula (B), X ^{1 is a polar group represented by any one of the formulas (X-1) to (X-27).} Composition.

In formulas (X-1) to (X-27),
J ¹ and J ² are hydrogen, or alkyl having 1 to 5 carbon atoms, in which at least one −CH ₂ − may be replaced by −O −;
J ³ is hydrogen, or an alkyl having 1 to 20 carbon atoms, in which at least one -CH _2- may be replaced by -O-, -COO- or -OCO-;
J ⁴ and J ⁵ are hydrogen, or alkyl with 1 to 8 carbon atoms;
Q ¹ is a methine group or a nitrogen, wherein the hydrogen of the methine group may be replaced by alkyl having 1 to 6 carbon atoms;
U ¹ and U ² are -CH _2- , -O-, -CO- or -S-;
V ¹ , V ² and V ³ are methine or nitrogen, and ^{any one of V 1} , V ² and V ³ is always nitrogen;
W ¹ is oxygen or sulfur;
W ² is carbon, sulfur or silicon.
^{However, when Q 1} is methine in the formula (X-14), ^{one of U 1} and U ² is always -O-, -CO-, or -S-.

Item 6. Item 6. The liquid crystal composition according to any one of Items 1 to 5, wherein the ratio of the additive Y is in the range of 0.1% by mass to 10% by mass.

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

In equation (2)
R ¹ and R ² are hydrogen, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, alkenyloxy with 2 to 12 carbon atoms, or at least one hydrogen is fluorine or It is an alkyl with 1 to 12 carbon atoms replaced by chlorine;
Rings D and F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen replaced with fluorine or chlorine 1 , 4-Phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine, chromane-2,6-diyl, or at least one hydrogen is fluorine or chlorine. Chroman-2,6-jiyl replaced by;
Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4. 5-Trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran- 3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2,5-diyl;
Z ³ and Z ⁴ are single bonds, ethylene, methyleneoxy, or carbonyloxy;
e is 0, 1, 2, or 3, f is 0 or 1, and the sum of e and f is 3 or less.

式（２−１）から式（２−３５）において、Ｒ^１およびＲ^２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。 Item 8. Item 2. The liquid crystal composition according to any one of Items 1 to 7, which contains at least one compound selected from the group of compounds represented by the formulas (2-1) to (2-35) as the component A. ..

In formulas (2-1) to (2-35), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and carbon number of carbon atoms. 2 to 12 alkenyloxy, or 1 to 12 carbon alkyl in which at least one hydrogen is replaced with fluorine or chlorine.

Item 9. The liquid crystal composition according to claim 7 or 8, wherein the proportion of the component A is in the range of 10% by mass to 90% by mass.

式（３）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Ｇおよび環Ｉ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^５は、単結合、エチレン、またはカルボニルオキシであり；
ｇは、１、２、または３である。 Item 10. Item 6. The liquid crystal composition according to any one of Items 1 to 9, which contains at least one compound selected from the compounds represented by the formula (3) as the component B.

In equation (3)
R ³ and R ⁴ are alkyls having 1 to 12 carbon atoms, alkoxys having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. , Or an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine;
Rings G and I are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene;
Z ⁵ is a single bond, ethylene, or carbonyloxy;
g is 1, 2, or 3.

式（３−１）から式（３−１３）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 11. The liquid crystal composition according to any one of claims 1 to 10, which contains at least one compound selected from the compounds represented by the formulas (3-1) to (3-13) as the component B.

In formulas (3-1) to (3-13), 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 an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine.

Item 12. The liquid crystal composition according to claim 10 or 11, wherein the proportion of the component B is in the range of 10% by mass to 90% 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^６およびＺ^７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_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ_３）−、または−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
Ｓｐ^５、Ｓｐ^６、およびＳｐ^７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_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
ｈは、０、１、または２であり；
ｉ、ｊ、およびｋは、０、１、２、３、または４であり、ｉ、ｊ、およびｋの和は、１以上であり；
Ｐ^９、Ｐ^１０、およびＰ^１１は、式（Ｐ−７）から式（Ｐ−１１）で表される重合性基から選択された基であり；

式（Ｐ−７）から式（Ｐ−１１）において、Ｍ^５、Ｍ^６、およびＭ^７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 13. Item 6. The liquid crystal composition according to any one of Items 1 to 12, which contains at least one compound selected from the polymerizable compounds represented by the formula (4) as the additive Z.

In equation (4)
Rings I and K are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine-2-yl, or pyridine-2-yl. In these rings, at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, or at least one hydrogen with fluorine or chlorine. May be replaced with 1 to 12 alkyl;
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 these rings. At least one hydrogen is replaced with fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, or alkyl with 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. Well;
Z ⁶ and Z ⁷ are single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, or -OCO-. May be replaced, at least one −CH ₂ −CH ₂₋ may be −CH = CH−, −C (CH ₃ ) = CH−, −CH = C (CH ₃ ) −, or −C (CH _3). ) = C (CH ₃ )-may be replaced, and in these groups at least one hydrogen may be replaced with fluorine or chlorine;
Sp ⁵ , Sp ⁶ , and Sp ⁷ are single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH ₂ − is -O-, -COO-, -OCO-, or. It may be replaced by −OCOO −, at least one −CH ₂ −CH ₂ − may be replaced by −CH = CH− or −C≡C−, and in these groups, at least one hydrogen , May be replaced with fluorine or chlorine;
h is 0, 1, or 2;
i, j, and k are 0, 1, 2, 3, or 4, and the sum of i, j, and k is greater than or equal to 1.
P ⁹ , P ¹⁰ , and P ¹¹ are groups selected from the polymerizable groups represented by the formulas (P-7) to (P-11);

In formulas (P-7) to (P-11), M ⁵ , M ⁶ , and M ⁷ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen replaced with fluorine or chlorine. It is an alkyl having 1 to 5 carbon atoms.

式（４−１）から式（４−２９）において、
Ｓｐ^５、Ｓｐ^６、およびＳｐ^７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_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
Ｐ^１２、Ｐ^１３、およびＰ^１４は、式（Ｐ−７）から式（Ｐ−９）で表される基から選択された重合性基であり；

式（Ｐ−７）から式（Ｐ−９）において、Ｍ^５、Ｍ^６、およびＭ^７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 14. Item 6. The liquid crystal composition according to any one of Items 1 to 13, which contains at least one compound selected from the compounds represented by the formulas (4-1) to (4-29) as the additive Z.

In equations (4-1) to (4-29),
Sp ⁵ , Sp ⁶ , and Sp ⁷ are single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH ₂ − is -O-, -COO-, -OCO-, Alternatively, it may be replaced by −OCOO −, and at least one −CH ₂ −CH ₂ − may be replaced by −CH = CH − or −C≡C−, and at least one hydrogen in these groups. May be replaced with fluorine or chlorine;
P ¹² , P ¹³ and P ¹⁴ are polymerizable groups selected from the groups represented by the formulas (P-7) to (P-9);

In formulas (P-7) to (P-9), M ⁵ , M ⁶ , and M ⁷ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen replaced with fluorine or chlorine. It is an alkyl having 1 to 5 carbon atoms.

Item 15. Item 3. The liquid crystal composition according to Item 13 or 14, wherein the ratio of the additive Z is in the range of 0.03% by mass to 10% by mass.

Item 16. A liquid crystal display device containing the liquid crystal composition according to any one of Items 1 to 15.

Item 17. Item 16. The liquid crystal display element according to Item 16, wherein the operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and the drive method of the liquid crystal display element is an active matrix method.

Item 18. A polymer-supported oriented liquid crystal display element containing the liquid crystal composition according to any one of Items 1 to 15 or having a polymerizable compound in the liquid crystal composition polymerized.

Item 19. Use of the liquid crystal composition according to any one of Items 1 to 15 in a liquid crystal display element.

Item 20. Use of the liquid crystal composition according to any one of Items 1 to 15 in a polymer-supported orientation type liquid crystal display device.

The present invention also includes the following sections. (A) The above liquid crystal composition is placed between two substrates, and light is applied to the composition while a voltage is applied to polymerize the polar compound having a polymerizable group contained in the composition. The method for manufacturing the above-mentioned liquid crystal display element. (B) The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C.) is 0.08 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C.). ) Is -2 or less, the above liquid crystal composition.

The present invention also includes the following sections. (C) Compounds (5) to (7) described in JP-A-2006-199941 are liquid crystal compounds having a positive dielectric anisotropy, but at least selected from the group of these compounds. The above composition containing one compound. (D) The above composition containing at least two compounds selected from the above polar compound (B). (E) The above composition further containing a polar compound different from the above polar compound (B). (F) Additions such as optically active compounds, antioxidants, ultraviolet absorbers, light-dissipating agents, dyes, defoaming agents, polymerizable compounds different from the above-mentioned polymerizable compounds (4), polymerization initiators, and polymerization inhibitors. The above composition comprising one, two, or at least three of the same. (G) AM device containing the above composition. (H) A device containing the above composition and having a mode of TN, ECB, OCB, IPS, FFS, VA, or FPA. (I) A transmissive device containing the above composition. (J) The above composition is used as a composition having a nematic phase. (K) A composition prepared by adding an optically active compound to the above composition is used as the optically active composition.

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

First, the composition of the composition will be described. This composition contains a plurality of liquid crystal compounds. This composition may contain additives. Additives include optically active compounds, antioxidants, UV absorbers, light extinguishing agents, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. This composition is classified into composition A and composition B from the viewpoint of liquid crystal compounds. The composition A may further contain other liquid crystal compounds, additives and the like in addition to the liquid crystal compound selected from the compound (2) and the compound (3). The "other liquid crystal compound" is a liquid crystal compound different from the compound (2) and the compound (3). Such compounds are mixed into the composition for the purpose of further adjusting the properties.

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

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

The main effects of the constituent compounds on the properties of the composition are: Compound (1) and compound (4) give a polymer by polymerization, which reduces the response time of the device and improves image burn-in. Compound (2) increases the dielectric anisotropy and lowers the lower limit temperature. Compound (3) lowers the viscosity or raises the upper limit temperature. Compound (B) is adsorbed on the substrate surface by the action of polar groups to control the orientation of liquid crystal molecules. In order to obtain the desired effect, the compound (B) is required to have high compatibility with the liquid crystal compound. Compound (B) has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, has a rod-like molecular structure, and is considered to be capable of improving compatibility. Ideal for. Compound (B) gives a polymer by polymerization together with compound (1) and compound (4). This polymer stabilizes the orientation of the liquid crystal molecules, thus shortening the response time of the device and improving image burn-in. From the viewpoint of the orientation of the liquid crystal molecules, it is presumed that the polymer of compound (B) is more effective than the polymer of compound (4) because it has an interaction with the surface of the substrate.

Thirdly, the combination of the components in the composition, the preferable ratio of the components, and the rationale thereof will be described. Preferred combinations of components in the composition are compound (1) + compound (B) + compound (2), compound (1) + compound (B) + compound (2) + compound (3), compound (1) + compound. (B) + compound (2) + compound (4), or compound (1) + compound (B) + compound (2) + compound (3) + compound (4).

Polymerizable compounds such as compound (1) are added to the composition for the purpose of adapting to polymer support oriented devices. The preferable ratio of the polymerizable compound is about 0.03% by mass or more in order to shorten the response time, and about 10% by mass or less in order to prevent display defects of the device. A more preferable ratio is in the range of about 0.1% by mass to about 1.0% by mass. A particularly preferable ratio is in the range of about 0.3% by mass to about 0.8% by mass.

Compound (B) is added to the composition for the purpose of controlling the orientation of the liquid crystal molecules. The preferable ratio of the compound (B) is about 0.1% by mass or more for aligning the liquid crystal molecules, and about 10% by mass or less for preventing display defects of the device. A more preferable ratio is in the range of about 0.1% by mass to about 7% by mass. A particularly preferable ratio is in the range of about 0.5% by mass to about 5% by mass.

The preferable ratio of the compound (2) is about 10% by mass or more in order to increase the dielectric anisotropy, and about 90% by mass or less in order to lower the lower limit temperature. A more preferable ratio is in the range of about 20% by mass to about 85% by mass. A particularly preferable ratio is in the range of about 30% by mass to about 85% by mass.

The preferable ratio of the compound (3) is about 10% by mass or more in order to raise the upper limit temperature or lower the viscosity, and about 90% by mass or less in order to raise the dielectric anisotropy. A more preferable ratio is in the range of about 15% by mass to about 75% by mass. A particularly preferable ratio is in the range of about 15% by mass to about 60% by mass.

The preferable ratio of the compound (4) is about 0.03% by mass or more in order to improve the long-term stability of orientation, and about 10% by mass or less in order to prevent display defects of the device. A more preferable ratio is in the range of about 0.1% by mass to about 2% by mass. A particularly preferable ratio is in the range of about 0.2% by mass to about 1.0% by mass.

Fourth, preferable forms of the component compounds will be described. First, the two liquid crystal compounds will be described together. Next, additive X, additive Y, and additive Z will be described in this order.

(A) a liquid crystal compound (2) and in formula (3), ^{R 1} and ^{R 2} is hydrogen, alkyl of 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, An alkenyloxy having 2 to 12 carbon atoms, or an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. Preferred R ¹ or R ² is an alkyl having 1 to 12 carbon atoms to increase stability, an alkoxy having 1 to 12 carbon atoms to increase dielectric anisotropy, and a low frequency to reduce viscosity. It is an alkenyl having 2 to 12 carbon atoms due to the threshold voltage. R ³ and R ⁴ are alkyls having 1 to 12 carbon atoms, alkoxys having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. , Or an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. Preferred R ³ or R ⁴ is an alkenyl having 2 to 12 carbon atoms to reduce the viscosity and an alkyl having 1 to 12 carbon atoms to increase stability.

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

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

Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More preferred alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl to reduce the viscosity. The preferred configuration of -CH = CH- in these alkenyl depends on the position of the double bond. Trans is preferable in alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl for the purpose of lowering the viscosity. Sis is preferred for alkenyl such as 2-butenyl, 2-pentenyl, 2-hexenyl.

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

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

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

Rings D and F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen replaced with fluorine or chlorine 1 , 4-Phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine, chromane-2,6-diyl, or at least one hydrogen is fluorine or chlorine. Chroman-2,6-jiyl replaced by. 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. -3-Fluoro-1,4-phenylene. Preferred ring D or ring F is 1,4-cyclohexylene to reduce viscosity, tetrahydropyran-2,5-diyl to increase dielectric anisotropy, and to increase optical anisotropy. It is 1,4-phenylene.

Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4. 5-Trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl (FLF4), 4,6- Difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2), or 1,1,6,7-tetrafluoroindane-2,5-diyl (InF4) Is.

好ましい環Ｅは、誘電率異方性を上げるために２，３−ジフルオロ−１，４−フェニレンである。

The preferred ring E is 2,3-difluoro-1,4-phenylene to increase the dielectric anisotropy.

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

Z ³ and Z ⁴ are single bonds, ethylene, vinylene, methyleneoxy, or carbonyloxy. Preferred Z ³ or Z ⁴ is a single bond to reduce the viscosity and methyleneoxy to increase the dielectric anisotropy. Z ⁵ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Preferred Z ⁵ is a single bond to reduce viscosity.

e is 0, 1, 2, or 3, f is 0 or 1, and the sum of e and f is less than or equal to 3. The preferred e is 1 for lowering the viscosity and 2 or 3 for raising the upper temperature limit. The preferred f is 0 to lower the viscosity and 1 to lower the lower limit temperature. g is 1, 2, or 3. The preferred g is 1 for lowering the viscosity and 2 or 3 for raising the upper temperature limit.

(B) Additive X
In formula (1), ring A ¹ and ring A ³ are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine-2. -Il or pyridin-2-yl, in these rings, at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkenyl with 2 to 12 carbons, alkenyl with 2 to 12 carbons. Oxy, or at least one hydrogen, may be replaced with an alkyl having 1 to 12 carbon atoms in which fluorine or chlorine has been replaced. Preferred rings A ¹ and A ³ are phenyl. Ring A ² contains 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene- 2,7-Diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings. , At least one hydrogen is replaced with fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, or alkyl with 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. You may. The preferred ring A ² is 1,4-phenylene or 2-fluoro-1,4-phenylene.

P ^{1, P 2,} and ^{P 3} is a polymerizable ^group, at least one of P 1, ^{P 2,} and ^{P 3} is a polymerizable group represented by the formula (P-1). Preferred P ¹ , P ² , or P ³ is a group selected from the polymerizable groups represented by the formulas (P-1) to (P-6).
The wavy lines of the formulas (P-1) to (P-6) indicate the sites to be combined.

In formulas (P-1) to (P-6), M ¹ is an alkyl having 1 to 5 carbon atoms. Preferred M ¹ is methyl to increase reactivity. M ² , M ³ , and M ⁴ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. Preferred M ² , M ³ , or M ⁴ is hydrogen or methyl to increase reactivity. The more preferred M ² is hydrogen or methyl, and the more preferred M ³ or M ⁴ is hydrogen. n is an integer from 1 to 5. The preferred n is 1.

Z ¹ and Z ² are single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, or -OCO-. May be replaced, at least one −CH ₂ −CH ₂₋ may be −CH = CH−, −C (CH ₃ ) = CH−, −CH = C (CH ₃ ) −, or −C (CH _3). ) = C (CH ₃ )-may be replaced, and in these groups at least one hydrogen may be replaced with fluorine or chlorine. Preferred Z ¹ and Z ² are single bonds, -CH _2- CH _{2- , -CH 2} O-, -OCH _2- , -COO-, or -OCO-. More preferred Z ¹ and Z ² are single bonds.

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

a is 0, 1, or 2. Preferred a is 1 or 2. b, c, and d are 0, 1, 2, 3, or 4. Preferred b, c, or d is 0, 1 or 2.

(C) Additive Y
Compound (B) is preferably stable against ultraviolet rays and heat. When compound (B) is added to the composition, it is preferable that this compound does not lower the voltage retention of the device. Compound (1) preferably has low volatility. The preferred molar mass is 130 g / mol or more. A more preferred molar mass is in the range of 150 g / mol to 700 g / mol. Preferred compounds (B) are such as acryloyloxy (-OCO-CH = CH ₂ ), fluoroacryloyloxy (-OCO-CF = CH ₂ ), methacryloyloxy (-OCO- (CH ₃ ) C = CH ₂ ). It has a polymerizable group.

R ⁶ is hydrogen or an alkyl having 1 to 7 carbon atoms, in which at least one −CH ₂ − may be replaced by −O − or −S−, and at least one −CH ₂ −. CH ₂ − may be replaced by −CH = CH − or −C≡C−, and in these groups at least one hydrogen may be replaced by fluorine or chlorine. Preferred R ⁶ is hydrogen, an alkyl having 1 to 5 carbon atoms, an alkoxy having 1 to 5 carbon atoms, or an alkoxy alkyl having 1 to 5 carbon atoms. A more preferred R ⁶ is an alkyl having 1 to 5 carbon atoms.

Ring ^{A 4} and ring ^{A 5} are 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-cyclohexenylene Len, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-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, carbon number. It may be replaced with an alkyl of 1 to 10, an alkenyl having 2 to 10 carbon atoms, an alkoxy having 1 to 9 carbon atoms, or an alkenyloxy having 2 to 9 carbon atoms, and in these groups, at least one hydrogen is fluorine. Alternatively, it may be replaced with chlorine. Preferred rings A ⁴ and A ⁵ are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, or 3-ethyl-1,4-phenylene. Yes, in these rings, at least one hydrogen may be replaced with fluorine, an alkyl having 1 to 7 carbon atoms, an alkenyl having 2 to 7 carbon atoms, and an alkoxy having 1 to 7 carbon atoms. Particularly preferred ring A ¹ or ring A ² is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, naphthalene-2,6-diyl, or 3-ethyl-1,4. -Phenylene.

p is 0, 1, 2, 3, or 4. Particularly preferred p is 1, 2, or 3.

q and r are 0, 1, or 2. Particularly preferred r is 0, 1 or 2.

Z ⁸ is a single bond or an alkylene with 1 to 6 carbon atoms, in which at least one -CH ₂ − is -O-, -CO-, -COO-, -OCO-, or -OCOO-. At least one −CH ₂ −CH ₂₋ may be replaced with −CH = CH− or −C≡C−, and in these groups at least one hydrogen is fluorine or It may be replaced with chlorine. Preferred ^{Z 8} represents a single _{bond, -CH 2 -CH 2 -, -} CH 2 -O -, - OCH 2 -, - COO-, or -OCO-. A more preferred Z ⁸ is a single bond.

P ¹⁶ and P ¹⁷ were selected from the groups represented by the formulas (A-p1), (A-p2), (A-p3), (A-p4) and (A-p5). Is the basis. Preferred P ¹⁶ and P ¹⁷ are groups selected from the groups represented by the formulas (A-p1), (A-p2), and (A-p5).

In formulas (A-p1) to (A-p5), Sp ¹⁰ is a single bond or an alkylene with 1 to 15 carbon atoms, in which at least one -CH _2- is -O-,-. It may be replaced by CO-, -COO-, -OCO-, or -OCOO-, and at least one -CH _2- CH _2- may be replaced by -CH = CH- or -C≡C-. Often, in these groups, at least one hydrogen may be replaced with fluorine or chlorine. Preferred Sp ¹⁰ is a single bond or an alkylene with 1 to 10 carbon atoms to increase vertical orientation. Preferred Sp ¹⁰ is a single bond or an alkylene having 1 to 5 carbon atoms.

R ⁷ is an alkyl having 1 to 5 carbon atoms. Preferred R ⁷ is an alkyl having 1 to 3 carbon atoms to increase the reactivity.

R ⁸ is a linear or branched alkyl having 1 to 10 carbon atoms or a cyclic alkyl having 3 to 8 carbon atoms. Preferred R ⁸ is 3 alkyl carbon number of 1 to increase the reactivity.

Y ¹ is chlorine, fluorine, or bromine. Preferred Y ¹ is fluorine.

Sp ⁹ is a single bond or an alkylene with 1 to 10 carbon atoms, in which at least one -CH ₂ − is -O-, -CO-, -COO-, -OCO-, -OCOO- or. It may be replaced by the group represented by the formula (1-a), and at least one −CH ₂ −CH ₂ − may be replaced by −CH = CH− or −C≡C−. In a group, at least one hydrogen is represented by fluorine, chlorine, formula (A-p1), formula (A-p2), formula (A-p3), formula (A-p4) or formula (A-p5). May be replaced with a base. Preferred Sp ⁹ is an alkylene having 1 to 5 carbon atoms in order to improve the electrical characteristics, and at least one hydrogen in this alkylene is a formula (A-p1), a formula (A-p2), a formula (A-p3). , Replaced by a group represented by the formula (A-p4) or the formula (A-p5).

X ¹ is a polar group having a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, phosphorus and silicon, and is represented by any one of the formulas (X-1) to (X-27). It is a polar group. Preferred X ¹ is the formula (X-1), the formula (X-5), the formula (X-11), the formula (X-20), the formula (X-22), the formula (X) in order to increase the vertical orientation. -24), and equation (X-27). Particularly preferred X ^1s are formula (X-1), formula (X-5), formula (X-22), and formula (X-24).

In formulas (X-1) to (X-27), J ¹ and J ² are hydrogen, or linear alkyl having 1 to 5 carbon atoms or branched alkyl having 3 to 5 carbon atoms. In, at least one −CH ₂₋ may be replaced by −O−. Preferred J ¹ and J ² are hydrogen or linear alkyl having 1 to 3 carbon atoms to increase solubility.

J ³ is hydrogen, or a linear alkyl having 1 to 20 carbon atoms or a branched alkyl having 3 to 20 carbon atoms, in which at least one -CH ₂ − is -O-, -COO-. Alternatively, it may be replaced with −OCO−. Preferred J ³ is a straight-chain alkyl hydrogen, or from 1 to 3 carbon atoms in order to increase the solubility.

J ⁴ and J ⁵ are hydrogen or alkyl having 1 to 8 carbon atoms. Preferred J ⁴ and J ⁵ are linear alkyls having 1 to 3 carbon atoms to increase solubility.

Q ¹ is methine or nitrogen, where the hydrogen of methine may be replaced by an alkyl having 1 to 6 carbon atoms. Preferred Q ¹ is methine in which methine or hydrogen is replaced with an alkyl having 1, 2, or 4 carbon atoms.

U ¹ and U ² are -CH _2- , -O-, -CO- or -S-. Preferred U ¹ and U ² are -CH _2- , -O- or -CO-.

V ¹ , V ² and V ³ are methine or nitrogen, and ^{any one of V 1} , V ² and V ³ is always nitrogen. Preferred V ¹ , V ² and V ³ are methines.

W ¹ is oxygen or sulfur.

W ² is carbon, sulfur or silicon. Preferred W ² is carbon or sulfur.
^{However, when Q 1} is methine in the formula (X-14), ^{one of U 1} and U ² is always -O-, -CO- or -S-.

(D) Additive Z
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 Pyridine-2-yl, in these rings at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least one hydrogen is fluorine or chlorine. It may be replaced with an alkyl having 1 to 12 carbon atoms replaced with. 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, in these rings. At least one hydrogen is replaced with fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, or alkyl with 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. May be good. The preferred ring J is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁶ and Z ⁷ are single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, or -OCO-. May be replaced, 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 )-may be replaced, and in these groups at least one hydrogen may be replaced with fluorine or chlorine. Preferred Z ⁶ or Z ⁷ are single bonds, -CH ₂ CH _{2- , -CH 2} O-, -OCH _2- , -COO-, or -OCO-. A more preferred Z ⁶ or Z ⁷ is a single bond.

P ⁹ , P ¹⁰ , and P ¹¹ are polymerizable groups. Preferred P ⁹ , P ¹⁰ , or P ¹¹ are polymerizable groups selected from the group of groups represented by formulas (P-7) to (P-11). More preferred P ⁹ , P ¹⁰ , or P ¹¹ is a group represented by formula (P-7), formula (P-8), or formula (P-9). Particularly preferred P ⁹ , P ¹⁰ , or P ¹¹ is a group represented by the formula (P-7) or the formula (P-8). The most preferred P ⁹ , P ¹⁰ , or P ¹¹ is a group represented by the formula (P-7). The preferred group represented by the formula (P-7) is -OCO-CH = CH ₂ or -OCO-C (CH ₃ ) = CH ₂ . The wavy lines of equations (P-7) to (P-11) indicate the sites to be combined.

In formulas (P-7) to (P-11), M ⁵ , M ⁶ , and M ⁷ are hydrogen, fluorine, or alkyl having 1 to 5 carbon atoms, and at least one -CH in this alkyl. ₂ − may be replaced by −O −, and at least one hydrogen may be replaced by fluorine or chlorine. Preferred M ⁵ , M ⁶ or M ⁷ are hydrogen or methyl to increase reactivity. A more preferred M ⁵ is hydrogen or methyl, and a more preferred M ⁶ or M ⁷ is hydrogen.

Sp ⁵ , Sp ⁶ , and Sp ⁷ are single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH ₂ − is -O-, -COO-, -OCO-, or. It may be replaced by −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 present. , Fluorine or chlorine may be replaced. Preferred Sp ⁵ , Sp ⁶ , or Sp ⁷ are single bonds, -CH ₂ CH _{2- , -CH 2} O-, -OCH _2- , -COO-, -OCO-, -CO-CH = CH-, or. -CH = CH-CO-. More preferred Sp ⁵ , Sp ⁶ , or Sp ⁷ are single bonds.

h is 0, 1, or 2. Preferred h is 0 or 1. i, j, and k are 0, 1, 2, 3, or 4, and the sum of i, j, and k is greater than or equal to 1. Preferred i, j, or k is 1 or 2.

Fifth, preferred component compounds are shown. Preferred compounds (1) are compounds (1-1) to compounds (1-30) according to Item 3. In these compounds, at least one of the additives X is compound (1-1), compound (1-2), compound (1-4), compound (1-5), compound (1-7), compound (1-7). 1-8), compound (1-10) and compound (1-11) are preferred. At least two of the additives X are compound (1-2), compound (1-3), compound (1-5), compound (1-6), compound (1-8), compound (1-9), It is preferably a combination selected from compound (1-11), compound (1-12), and compound (1-26).

Preferred compounds (2) are compounds (2-1) to compounds (2-35) according to Item 8. In these compounds, at least one of the components A is compound (2-1), compound (2-2), compound (2-3), compound (2-6), compound (2-7), compound (2). −8), compound (2-9), compound (2-10), compound (2-13), compound (2-14), or compound (2-18) is preferred. At least two of the components A are compound (2-1) and compound (2-8), compound (2-1) and compound (2-14), compound (2-3) and compound (2-8), compound. (2-3) and compound (2-10), compound (2-3) and compound (2-14), compound (2-6) and compound (2-8), compound (2-6) and compound ( 2-10), compound (2-6) and compound (2-18), compound (2-7) and compound (2-8), compound (2-7) and compound (2-9), compound (2) -7) and compound (2-10), compound (2-7) and compound (2-8), compound (2-7) and compound (2-14), or compound (2-10) and compound (2). The combination of -14) is preferable.

Preferred compounds (3) are compounds (3-1) to compounds (3-13) according to Item 11. In these compounds, at least one of the components B is compound (3-1), compound (3-2), compound (3-3), compound (3-5), compound (3-6), compound (3). −8) or compound (3-9) is preferable. At least two of components B are compound (3-1) and compound (3-3), compound (3-1) and compound (3-5), or a combination of compound (3-1) and compound (3-6). Is preferable.

Preferred compounds (4) are compounds (4-1) to compounds (4-29) according to Item 14. In these compounds, at least one of the additives Z is compound (4-1), compound (4-2), compound (4-24), compound (4-25), compound (4-26), compound ( It is preferably 4-27) or compound (4-29). At least two of Addendum Z are compound (4-1) and compound (4-2), compound (4-1) and compound (4-18), compound (4-2) and compound (4-24), Compound (4-2) and compound (4-25), compound (4-2) and compound (4-26), compound (4-25) and compound (4-26), or compound (4-18) and It is preferably a combination of compound (4-24).

Sixth, additives that may be added to the composition will be described. Such additives include optically active compounds, antioxidants, UV absorbers, light extinguishing agents, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules to give a helix angle. Examples of such compounds are compound (6-1) to compound (6-5). The preferred proportion of the optically active compound is about 5% by mass or less. A more preferable ratio is in the range of about 0.01% by mass to about 2% by mass.

Antioxidants are composed to prevent a decrease in resistivity due to heating in the atmosphere, or to maintain a large voltage retention not only at room temperature but also at temperatures close to the upper limit temperature after long-term use of the device. It is added to the thing. Preferred examples of the antioxidant are compounds (7-1) to compounds (7-3) and the like.

Since the compound (7-2) has low volatility, it is effective in maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after the device has been used for a long time. The preferable ratio of the antioxidant is about 50 ppm or more in order to obtain the effect, and is about 600 ppm or less so as not to lower the upper limit temperature or raise the lower limit temperature. A more preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferred examples of UV absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as sterically hindered amines are also preferred. Preferred examples of the light stabilizer are compounds (8-1) to compounds (8-16) and the like. The preferable ratio of these absorbents and stabilizers is about 50 ppm or more in order to obtain the effect, and about 10,000 ppm or less so as not to lower the upper limit temperature or raise the lower limit temperature. A more preferred ratio is in the range of about 100 ppm to about 10000 ppm.

The quencher is a compound that prevents the decomposition of the liquid crystal compound by receiving the light energy absorbed by the liquid crystal compound and converting it into heat energy. Preferred examples of the quencher are compounds (9-1) to compounds (9-7) and the like. The preferable ratio of these quenchers is about 50 ppm or more in order to obtain the effect, and about 20000 ppm or less in order not to raise the lower limit temperature. A more preferred ratio is in the range of about 100 ppm to about 10000 ppm.

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

Polymerizable compounds are used to adapt to polymer support orientation (PSA) type devices. Compound (1), compound (4), compound (5-1), compound (5-2), and compound (5-3) are suitable for this purpose. Along with compound (1), compound (4), compound (5-1), compound (5-2), and compound (5-3), compound (1), compound (4), compound (5-1), Compound (5-2) and other polymerizable compounds different from compound (5-3) may be added to the composition. Preferred examples of such polymerizable compounds are compounds such as acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxylane, oxetane), vinyl ketones and the like. More preferred examples are acrylates or methacrylates. By changing the type of compound (1), compound (4), compound (5-1), compound (5-2), and compound (5-3), or by changing the type of compound (1), compound (4), compound. By combining (5-1), compound (5-2), and compound (5-3) with other polymerizable compounds in an appropriate ratio, the reactivity of the polymerizable compound and the pretilt angle of the liquid crystal molecule are adjusted. can do. By optimizing the pre-tilt angle, a short response time of the device can be achieved. Since the orientation of the liquid crystal molecules is stabilized, a large contrast ratio and a long life can be achieved.

This polymerizable compound is polymerized by irradiation with ultraviolet rays. Polymerization may be carried out in the presence of a suitable initiator, such as a photopolymerization initiator. Appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those of skill in the art and are described in the literature. For example, the photopolymerization initiators Irgacure651®, Irgacure184® (registered trademark; BASF), or Darocur1173® are suitable for radical polymerization. The preferred proportion of photopolymerization initiator is in the range of about 0.1% by mass to about 5% by mass based on the mass of the polymerizable compound. A more preferable ratio is in the range of about 1% by mass to about 3% by mass.

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

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

Seventh, a method for synthesizing a component compound will be described. These compounds can be synthesized by known methods. An example of the synthesis method. The method for synthesizing compound (1) is described in the section of Examples. Compound (2-1) is synthesized by the method described in JP-A-2-503441. Compound (3-5) is synthesized by the method described in JP-A-57-165328. Compound (4-18) is synthesized by the method described in JP-A-7-101900. Compound (7-1) is available from Sigma-Aldrich Corporation. Compound (7-2) and the like are synthesized by the method described in US Pat. No. 3,660,505.

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

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

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

An example of a method for manufacturing a polymer-supported orientation type device is as follows. An element having two substrates called an array substrate and a color filter substrate is prepared. This substrate has an alignment film. At least one of the substrates has an electrode layer. Liquid crystal compounds are mixed to prepare a liquid crystal composition. A polymerizable compound is added to this composition. Additional additives may be added as needed. This composition is injected into the device. Light is irradiated while a voltage is applied to this element. Ultraviolet rays are preferred. The polymerizable compound is polymerized by light irradiation. This polymerization produces a composition containing the polymer. The polymer support orientation type device is manufactured by such a procedure.

In this procedure, when a voltage is applied, the liquid crystal molecules are oriented by the action of the alignment film and the electric field. The molecules of the polymerizable compound are also oriented according to this orientation. Since the polymerizable compound is polymerized by ultraviolet rays in this state, a polymer that maintains this orientation is produced. Due to the effect of this polymer, the response time of the device is shortened. Since the burn-in of the image is a malfunction of the liquid crystal molecules, the burn-in is also improved at the same time by the effect of this polymer. It is also possible to prepolymerize the polymerizable compound in the composition and arrange the composition between the substrates of the liquid crystal display element.

When a polar compound having a polymerizable group (that is, a polymerizable compound) such as compound (A) is used, an alignment film is not required on the substrate of the device. Devices without an alignment film are manufactured from a substrate without an alignment film according to the procedure described in the previous paragraph.

In this procedure, compound (A) is arranged on the substrate because the polar groups interact with the surface of the substrate. The liquid crystal molecules are oriented according to this arrangement. When a voltage is applied, the orientation of the liquid crystal molecules is further promoted. Since the polymerizable group is polymerized by ultraviolet rays in this state, a polymer that maintains this orientation is produced. Due to the effect of this polymer, the orientation of the liquid crystal molecules is additionally stabilized, and the response time of the device is shortened. Since the burn-in of the image is a malfunction of the liquid crystal molecules, the burn-in is also improved at the same time by the effect of this polymer.

The present invention will be described in more detail by way of examples. The present invention is not limited by these examples. The present invention includes a mixture of composition M1 and composition M2. The present invention also includes a mixture of at least two of the compositions of the Examples. The synthesized compound was identified by a method such as NMR analysis. The properties of the compound, composition and device were measured by the following methods.

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

Gas chromatograph analysis: A GC-14B type gas chromatograph manufactured by Shimadzu Corporation was used for the measurement. The carrier gas is helium (2 mL / min). The sample vaporization chamber was set to 280 ° C. and the detector (FID) was set to 300 ° C. For the separation of the component compounds, a capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm; fixed liquid phase was dimethylpolysiloxane; non-polar) manufactured by Agilent Technologies Inc. was used. The column was held at 200 ° C. for 2 minutes and then warmed to 280 ° C. at a rate of 5 ° C./min. The sample was prepared in an acetone solution (0.1% by mass), and then 1 μL thereof was injected into the sample vaporization chamber. The recorder is a C-R5A type Chromatopac manufactured by Shimadzu Corporation, or an equivalent product thereof. The obtained gas chromatogram showed the peak retention time and peak area corresponding to the constituent compounds.

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

The proportion of the liquid crystal compound contained in the composition may be calculated by the following method. A mixture of liquid crystal compounds is analyzed by gas chromatography (FID). The area ratio of peaks in the gas chromatogram corresponds to the proportion of liquid crystal compounds. When the capillary column described above is used, the correction coefficient of each liquid crystal compound may be regarded as 1. Therefore, the proportion (mass%) of the liquid crystal compound can be calculated from the area ratio of the peak.

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

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

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

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

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

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

(4) Viscosity (rotational viscosity; γ1; measured at 25 ° C.; mPa · s): The rotational viscosity rate measuring system LCM-2 of Toyo Technica Co., Ltd. was used for the measurement. The sample was injected into a VA element having a distance (cell gap) of 10 μm between the two glass substrates. A square wave (55V, 1ms) was applied to this device. The peak current and peak time of the transient current generated by this application were measured. Using these measured values and dielectric anisotropy, rotational viscosity values 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.): The measurement was performed using light having a wavelength of 589 nm and using an Abbe refractometer with a polarizing plate attached to the eyepiece. After rubbing the surface of the main prism in one direction, the sample was dropped onto the main prism. The refractive index n‖ was measured when the direction of polarization was parallel to the direction of rubbing. The refractive index n⊥ was measured when the direction of polarization was perpendicular to the direction of rubbing. The value of optical anisotropy was calculated from the equation of Δn = n ‖ −n ⊥.

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

(7) Threshold voltage (Vth; measured at 25 ° C.; V): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. A sample is placed in a VA element in normally black mode in which the distance (cell gap) between two glass substrates is 4 μm and the rubbing direction is anti-parallel, and an adhesive that cures this element with ultraviolet rays is applied. Sealed using. The voltage (60 Hz, square wave) applied to this device was gradually increased by 0.02 V from 0 V to 20 V. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the amount of light was maximum and the transmittance was 0% when the amount of light was minimum. The threshold voltage is expressed as the voltage when the transmittance reaches 10%.

(8) Voltage retention rate (initial VHR; measured at 60 ° C.;%): The sample was sealed in a VA element of a glass substrate having no alignment film. The distance (cell gap) between the two glass substrates was 3.5 μm. This device was sealed with an adhesive that cures with UV light after injecting the sample. A pulse voltage (60 microseconds at 1 V) was applied to the VA element to charge it. The decaying voltage was measured with a high-speed voltmeter for 1667 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit period was determined. Area B was the area when there was no attenuation. The voltage holding ratio is expressed as a percentage of the area A with respect to the area B.

(9) Voltage retention rate (UV-VHR; measured at 60 ° C.;%): After irradiating the VA element into which the sample was injected with ultraviolet rays, the voltage retention rate was measured to evaluate the stability against ultraviolet rays. For the measurement, a VA element of a glass substrate having no alignment film was used, and the distance (cell gap) between the two glass substrates was 3.5 μm. A sample was injected into this device, UV2 was used as a light source, and 5 mmW of light was irradiated at 15 J. Then, UV-VHR was measured under the same measurement conditions as the initial VHR. Compositions with large UV-VHR have great stability to UV light. UV-VHR is preferably 90% or more, and more preferably 95% or more.

(10) Voltage retention rate (heated VHR; measured at 60 ° C.;%): After heating the VA element into which the sample was injected, the voltage retention rate was measured to evaluate the stability against heat. For the measurement, a VA element of a glass substrate having no alignment film was used, and the distance (cell gap) between the two glass substrates was 3.5 μm. A sample was injected into this device, ^{UV light having an intensity of 7.0 mW / cm 2} at 365 nm was irradiated for 90 minutes, and the device was heated in a constant temperature bath at 60 ° C. for 12 hours. Then, the heated VHR was measured under the same measurement conditions as the initial VHR. Compositions with large heating VHRs have great stability to heat. The heating VHR is preferably 90% or more, more preferably 95% or more.

(11) Response time (τ; measured at 25 ° C.; ms): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The low-pass filter was set to 5 kHz. The sample was placed in a VA element having a distance (cell gap) between two glass substrates of 3.5 μm and having no alignment film. This element was sealed with an adhesive that cures with UV light. ^{This device was irradiated with ultraviolet rays of 78 mW / cm 2} (405 nm) for 449 seconds (35 J) while applying a voltage of 30 V. For the irradiation of ultraviolet rays, a multi-metal lamp M04-L41 for ultraviolet curing manufactured by Eye Graphics Co., Ltd. was used. A square wave (120 Hz) was applied to this device. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. It was considered that the transmittance was 100% when the amount of light was maximum, and the transmittance was 0% when the amount of light was minimum. The maximum voltage of the square wave was set so that the transmittance was 90%. The minimum voltage of the square wave was set to 2.5V where the transmittance was 0%. The response time was expressed as the time required for the transmittance to change from 10% to 90% (rise time; rise time; millisecond).

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

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

(14) Pre-tilt angle stability (ΔPt angle; degree): The change in the pre-tilt angle of the liquid crystal display element was evaluated. The pre-tilt angle Pt angle (before) before stress application was measured, then a rectangular wave of 7.0 V, 60 Hz was applied to the device for 24 hours, and then the pre-tilt angle Pt angle (after) after stress application was measured again. From these values, the change ΔPt angle (deg.) Of the pretilt angle was calculated using the following formula.
ΔPt angle = Pt angle (after) -Pt angle (before)
Optipro (manufactured by Shintech) was used to measure the pretilt angle. It can be said that the smaller the ΔPt angle, the smaller the change in the pretilt angle, and the better the pretilt angle stability. In particular, the ΔPt angle is preferably 0.1 ° or less.

(15) Orientation stability (liquid crystal alignment axis stability): Changes in the liquid crystal alignment axis on the electrode side of the liquid crystal display element were evaluated. The liquid crystal orientation angle φ (before) on the electrode side before applying stress was measured, and then a square wave of 4.5 V, 60 Hz was applied to the element for 20 minutes, shorted for 1 second, and again after 1 second and 5 minutes. The liquid crystal orientation angle φ (after) on the side was measured. From these values, the change Δφ (deg.) Of the liquid crystal orientation angle after 1 second and 5 minutes was calculated using the following formula.
Δφ (deg.) ＝ φ (after) −φ (before)
These measurements were made with reference to J. Hilfiker, B. Johs, C. Herzinger, JF Elman, E. Montbach, D. Bryant, and PJ Bos, Thin Solid Films, 455-456, (2004) 596-600. .. It can be said that the smaller Δφ, the smaller the rate of change of the liquid crystal alignment axis, and the better the stability of the liquid crystal alignment axis.

(16) Low-temperature solubility of polar compound: A polar compound was added to the composition (M1) having a nematic phase as an additive X at an arbitrary ratio. Subsequently, this sample was placed in a glass bottle and stored in a freezer at −20 ° C. for 10 days, and then the liquid crystal phase was observed. From the viewpoint of transporting and storing the liquid crystal material, it is preferable that the added polar compound retains the nematic phase without precipitating at −10 ° C. for 10 days. Furthermore, it is preferable to maintain the nematic phase at −20 ° C. for 10 days.

[Synthesis Example 1]
Synthesis of polymerizable compound (RM-1)

First step Under a nitrogen atmosphere, compound (T-1) (3 g, 14.69 mmol) and dichloromethane (300 ml) synthesized by a known method were placed in a reactor and cooled to 0 ° C. Compound (T-2) (5.63 g, 48.48 mmol), 1- (3-dimethylaminopropyl) carbodiimide (9.29 g, 48.48 mmol), and triethylamine (9.01 ml) synthesized therein by a known method. , 64.64 mmol) was added and the temperature was raised to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (dichloromethane / ethyl acetate = 19/1, volume ratio) and recrystallization to purify the polymerizable compound (RM-1) (4.13 g, yield). 70%) was obtained.

^{1 1} H-NMR (ppm; CDCl ₃ ): δ7.81-7.76 (m, 3H), 7.60 (d, J = 8.3Hz, 1H), 7.45 (t, J = 8.4Hz) , 1H), 7.30 (d, J = 8.4Hz, 1H), 6.54 (s, 1H), 6.48 (s, 1H), 6.15 (s, 1H), 6.08 ( s, 1H), 4.21 (s, 4H), 3.36 (s, 6H).
Transition temperature: C 105.3 I.

It is possible to synthesize (RM-9) from the polymerizable compound (RM-2) with reference to the method described in the synthesis example.

It is possible to synthesize (A-32) from the polar compound (A-1) with reference to the method described in the synthesis example of International Publication No. 2016/12949.

The compounds in the examples are 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 proportion (percentage) of the liquid crystal compound is a mass percentage (mass%) based on the mass of the liquid crystal composition. Finally, the characteristic values of the composition are summarized.

Example of element 1. A liquid crystal composition to which a polar compound was added was injected into an element having no raw material alignment film. After irradiating with ultraviolet rays, the vertical orientation of the liquid crystal molecules in this device was examined. First, the raw materials will be described. The raw materials are compositions M1 to M28, polymerizable compounds (RM-1) to (RM-9), and polar compounds (A-1) to (A-32), which are listed in this order.

[Composition M1]
3-HB (2F, 3F) -O2 (2-1) 10%
5-HB (2F, 3F) -O2 (2-1) 7%
2-BB (2F, 3F) -O2 (2-6) 7%
3-BB (2F, 3F) -O2 (2-6) 7%
2-HHB (2F, 3F) -O2 (2-8) 5%
3-HHB (2F, 3F) -O2 (2-8) 10%
2-HBB (2F, 3F) -O2 (2-14) 8%
3-HBB (2F, 3F) -O2 (2-14) 10%
3-B (2F, 3F) B (2F, 3F) -O2 (2) 3%
2-HH-3 (3-1) 14%
3-HB-O1 (3-2) 5%
3-HHB-1 (3-5) 3%
3-HHB-O1 (3-5) 3%
3-HHB-3 (3-5) 4%
2-BB (F) B-3 (3-8) 4%
NI = 73.2 ° C; Tc <-20 ° C; Δn = 0.113; Δε = -4.0; Vth = 2.18V; η = 22.6 mPa · s.

[Composition M2]
3-HB (2F, 3F) -O4 (2-1) 6%
3-H2B (2F, 3F) -O2 (2-2) 8%
3-H1OB (2F, 3F) -O2 (2-3) 4%
3-BB (2F, 3F) -O2 (2-6) 7%
2-HHB (2F, 3F) -O2 (2-8) 7%
3-HHB (2F, 3F) -O2 (2-8) 7%
3-HH2B (2F, 3F) -O2 (2-9) 7%
5-HH2B (2F, 3F) -O2 (2-9) 4%
2-HBB (2F, 3F) -O2 (2-14) 5%
3-HBB (2F, 3F) -O2 (2-14) 5%
4-HBB (2F, 3F) -O2 (2-14) 6%
2-HH-3 (3-1) 12%
1-BB-5 (3-3) 12%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 3%
3-HBB-2 (3-6) 3%
NI = 82.8 ° C; Tc <-30 ° C; Δn = 0.118; Δε = -4.4; Vth = 2.13V; η = 22.5 mPa · s.

[Composition M3]
3-HB (2F, 3F) -O2 (2-1) 7%
5-HB (2F, 3F) -O2 (2-1) 7%
3-BB (2F, 3F) -O2 (2-6) 8%
3-HHB (2F, 3F) -O2 (2-8) 5%
5-HHB (2F, 3F) -O2 (2-8) 4%
3-HH1OB (2F, 3F) -O2 (2-10) 4%
2-HBB (2F, 3F) -O2 (2-14) 3%
3-HBB (2F, 3F) -O2 (2-14) 8%
4-HBB (2F, 3F) -O2 (2-14) 5%
5-HBB (2F, 3F) -O2 (2-14) 8%
2-BB (2F, 3F) B-3 (2-19) 5%
3-HH-V (3-1) 27%
3-HH-V1 (3-1) 6%
V-HHB-1 (3-5) 3%
NI = 78.1 ° C.; Tc <-30 ° C.; Δn = 0.107; Δε = -3.2; Vth = 2.02V; η = 15.9 mPa · s.

[Composition M4]
3-HB (2F, 3F) -O2 (2-1) 10%
5-HB (2F, 3F) -O2 (2-1) 10%
3-H2B (2F, 3F) -O2 (2-2) 8%
5-H2B (2F, 3F) -O2 (2-2) 8%
3-HDhB (2F, 3F) -O2 (2-13) 5%
2-HBB (2F, 3F) -O2 (2-14) 6%
3-HBB (2F, 3F) -O2 (2-14) 8%
4-HBB (2F, 3F) -O2 (2-14) 7%
5-HBB (2F, 3F) -O2 (2-14) 7%
3-HH-4 (3-1) 14%
V-HHB-1 (3-5) 10%
3-HBB-2 (3-6) 7%
NI = 88.5 ° C; Tc <-30 ° C; Δn = 0.108; Δε = -3.8; Vth = 2.25V; η = 24.6mPa · s; VHR-1 = 99.1%; VHR -2 = 98.2%; VHR-3 = 97.8%.

[Composition M5]
3-HB (2F, 3F) -O2 (2-1) 7%
3-HB (2F, 3F) -O4 (2-1) 8%
3-H2B (2F, 3F) -O2 (2-2) 8%
3-BB (2F, 3F) -O2 (2-6) 10%
2-HHB (2F, 3F) -O2 (2-8) 4%
3-HHB (2F, 3F) -O2 (2-8) 7%
3-HHB (2F, 3F) -1 (2-8) 6%
3-HDhB (2F, 3F) -O2 (2-13) 5%
2-HBB (2F, 3F) -O2 (2-14) 6%
3-HBB (2F, 3F) -O2 (2-14) 6%
4-HBB (2F, 3F) -O2 (2-14) 5%
5-HBB (2F, 3F) -O2 (2-14) 4%
3-H1OCro (7F, 8F) -5 (2-26) 3%
3-HEB (2F, 3F) B (2F, 3F) -O2 (2) 3%
3-HH-O1 (3-1) 5%
1-BB-5 (3-3) 4%
V-HHB-1 (3-5) 4%
5-HB (F) BH-3 (3-12) 5%
NI = 81.1 ° C; Tc <-30 ° C; Δn = 0.119; Δε = −4.5; Vth = 1.69V; η = 31.4mPa · s.

[Composition M6]
3-HB (2F, 3F) -O4 (2-1) 15%
3-chB (2F, 3F) -O2 (2-5) 7%
2-HchB (2F, 3F) -O2 (2-12) 8%
3-HBB (2F, 3F) -O2 (2-14) 8%
4-HBB (2F, 3F) -O2 (2-14) 5%
5-HBB (2F, 3F) -O2 (2-14) 7%
3-dhBB (2F, 3F) -O2 (2-16) 5%
5-HH-V (3-1) 18%
7-HB-1 (3-2) 5%
V-HHB-1 (3-5) 7%
V2-HHB-1 (3-5) 7%
3-HBB (F) B-3 (3-13) 8%
NI = 98.8 ° C; Tc <-30 ° C; Δn = 0.111; Δε = -3.2; Vth = 2.47V; η = 23.9mPa · s.

[Composition M7]
3-H2B (2F, 3F) -O2 (2-2) 18%
5-H2B (2F, 3F) -O2 (2-2) 17%
3-HHB (2F, 3Cl) -O2 (2-11) 5%
3-HDhB (2F, 3F) -O2 (2-13) 5%
3-HBB (2F, 3Cl) -O2 (2-15) 8%
5-HBB (2F, 3Cl) -O2 (2-15) 7%
3-HH-V (3-1) 11%
3-HH-VFF (3-1) 7%
F3-HH-V (3-1) 10%
3-HHEH-3 (3-4) 4%
3-HB (F) HH-2 (3-10) 4%
3-HHEBH-3 (3-11) 4%
NI = 77.5 ° C; Tc <-30 ° C; Δn = 0.084; Δε = -2.6; Vth = 2.43V; η = 22.8 mPa · s.

[Composition M8]
3-HB (2F, 3F) -O2 (2-1) 8%
3-H2B (2F, 3F) -O2 (2-2) 10%
3-BB (2F, 3F) -O2 (2-6) 10%
2O-BB (2F, 3F) -O2 (2-6) 3%
2-HHB (2F, 3F) -O2 (2-8) 4%
3-HHB (2F, 3F) -O2 (2-8) 7%
2-HHB (2F, 3F) -1 (2-8) 5%
3-HDhB (2F, 3F) -O2 (2-13) 6%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 7%
3-dhBB (2F, 3F) -O2 (2-16) 4%
2-BB (2F, 3F) B-3 (2-19) 6%
2-BB (2F, 3F) B-4 (2-19) 6%
3-HH1OCro (7F, 8F) -5 (2-27) 4%
3-HH-V (3-1) 11%
1-BB-5 (3-3) 5%
NI = 70.6 ° C; Tc <-20 ° C; Δn = 0.129; Δε = -4.3; Vth = 1.69V; η = 27.0 mPa · s.

[Composition M9]
3-HB (2F, 3F) -O4 (2-1) 14%
3-H1OB (2F, 3F) -O2 (2-3) 3%
3-BB (2F, 3F) -O2 (2-6) 10%
2-HHB (2F, 3F) -O2 (2-8) 7%
3-HHB (2F, 3F) -O2 (2-8) 7%
3-HH1OB (2F, 3F) -O2 (2-10) 6%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 6%
4-HBB (2F, 3F) -O2 (2-14) 4%
3-HH-V (3-1) 14%
1-BB-3 (3-3) 3%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 4%
V-HBB-2 (3-6) 4%
1-BB (F) B-2V (3-8) 6%
5-HBBH-1O1 (-) 4%
NI = 93.0 ° C; Tc <-30 ° C; Δn = 0.123; Δε = -4.0; Vth = 2.27V; η = 29.6 mPa · s.

[Composition M10]
3-HB (2F, 3F) -O4 (2-1) 6%
3-H2B (2F, 3F) -O2 (2-2) 8%
3-H1OB (2F, 3F) -O2 (2-3) 5%
3-BB (2F, 3F) -O2 (2-6) 10%
2-HHB (2F, 3F) -O2 (2-8) 7%
3-HHB (2F, 3F) -O2 (2-8) 7%
5-HHB (2F, 3F) -O2 (2-8) 7%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 7%
5-HBB (2F, 3F) -O2 (2-14) 6%
3-HH-V (3-1) 11%
1-BB-3 (3-3) 6%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 4%
3-HBB-2 (3-6) 4%
3-B (F) BB-2 (3-7) 4%
NI = 87.6 ° C; Tc <-30 ° C; Δn = 0.126; Δε = −4.5; Vth = 2.21V; η = 25.3 mPa · s.

[Composition M11]
3-HB (2F, 3F) -O4 (2-1) 6%
3-H2B (2F, 3F) -O2 (2-2) 8%
3-H1OB (2F, 3F) -O2 (2-3) 4%
3-BB (2F, 3F) -O2 (2-6) 7%
2-HHB (2F, 3F) -O2 (2-8) 6%
3-HHB (2F, 3F) -O2 (2-8) 10%
5-HHB (2F, 3F) -O2 (2-8) 8%
2-HBB (2F, 3F) -O2 (2-14) 5%
3-HBB (2F, 3F) -O2 (2-14) 7%
5-HBB (2F, 3F) -O2 (2-14) 5%
2-HH-3 (3-1) 12%
1-BB-3 (3-3) 6%
3-HHB-1 (3-5) 3%
3-HHB-O1 (3-5) 4%
3-HBB-2 (3-6) 6%
3-B (F) BB-2 (3-7) 3%
NI = 93.0 ° C; Tc <-20 ° C; Δn = 0.124; Δε = −4.5; Vth = 2.22V; η = 25.0 mPa · s.

[Composition M12]
3-HB (2F, 3F) -O2 (2-1) 7%
5-HB (2F, 3F) -O2 (2-1) 7%
3-BB (2F, 3F) -O2 (2-6) 8%
3-HHB (2F, 3F) -O2 (2-8) 4%
5-HHB (2F, 3F) -O2 (2-8) 5%
3-HH1OB (2F, 3F) -O2 (2-10) 5%
2-HBB (2F, 3F) -O2 (2-14) 3%
3-HBB (2F, 3F) -O2 (2-14) 8%
4-HBB (2F, 3F) -O2 (2-14) 5%
5-HBB (2F, 3F) -O2 (2-14) 8%
2-BB (2F, 3F) B-3 (2-19) 4%
3-HH-V (3-1) 33%
V-HHB-1 (3-5) 3%
NI = 76.4 ° C; Tc <-30 ° C; Δn = 0.104; Δε = -3.2; Vth = 2.06V; η = 15.6 mPa · s.

[Composition M13]
2-H1OB (2F, 3F) -O2 (2-3) 6%
3-H1OB (2F, 3F) -O2 (2-3) 4%
3-BB (2F, 3F) -O2 (2-6) 3%
2-HH1OB (2F, 3F) -O2 (2-10) 14%
2-HBB (2F, 3F) -O2 (2-14) 7%
3-HBB (2F, 3F) -O2 (2-14) 11%
5-HBB (2F, 3F) -O2 (2-14) 9%
2-HH-3 (3-1) 5%
3-HH-VFF (3-1) 30%
1-BB-3 (3-3) 5%
3-HHB-1 (3-5) 3%
3-HBB-2 (3-6) 3%
NI = 78.3 ° C; Tc <-20 ° C; Δn = 0.103; Δε = -3.2; Vth = 2.17V; η = 17.7mPa · s.

[Composition M14]
3-HB (2F, 3F) -O2 (2-1) 5%
5-HB (2F, 3F) -O2 (2-1) 7%
3-BB (2F, 3F) -O2 (2-6) 8%
3-HHB (2F, 3F) -O2 (2-8) 5%
5-HHB (2F, 3F) -O2 (2-8) 4%
3-HH1OB (2F, 3F) -O2 (2-10) 5%
2-HBB (2F, 3F) -O2 (2-14) 3%
3-HBB (2F, 3F) -O2 (2-14) 9%
4-HBB (2F, 3F) -O2 (2-14) 4%
5-HBB (2F, 3F) -O2 (2-14) 8%
2-BB (2F, 3F) B-3 (2-19) 4%
3-HH-V (3-1) 27%
3-HH-V1 (3-1) 6%
V-HHB-1 (3-5) 5%
NI = 81.2 ° C; Tc <-20 ° C; Δn = 0.107; Δε = -3.2; Vth = 2.11V; η = 15.5 mPa · s.

[Composition M15]
3-H2B (2F, 3F) -O2 (2-2) 7%
3-HHB (2F, 3F) -O2 (2-8) 8%
3-HH1OB (2F, 3F) -O2 (2-10) 5%
2-HchB (2F, 3F) -O2 (2-12) 8%
3-HDhB (2F, 3F) -O2 (2-13) 3%
5-HDhB (2F, 3F) -O2 (2-13) 4%
2-BB (2F, 3F) B-3 (2-19) 7%
2-BB (2F, 3F) B-4 (2-19) 7%
4-HH-V (3-1) 15%
3-HH-V1 (3-1) 6%
1-HH-2V1 (3-1) 6%
3-HH-2V1 (3-1) 4%
V2-BB-1 (3-3) 5%
1V2-BB-1 (3-3) 5%
3-HHB-1 (3-5) 6%
3-HB (F) BH-3 (3-12) 4%
NI = 88.7 ° C; Tc <-30 ° C; Δn = 0.115; Δε = -1.9; Vth = 2.82V; η = 17.3mPa · s.

[Composition M16]
V2-H2B (2F, 3F) -O2 (2-2) 8%
V2-H1OB (2F, 3F) -O4 (2-3) 4%
3-BB (2F, 3F) -O2 (2-6) 7%
2-HHB (2F, 3F) -O2 (2-8) 7%
3-HHB (2F, 3F) -O2 (2-8) 7%
3-HH2B (2F, 3F) -O2 (2-9) 7%
5-HH2B (2F, 3F) -O2 (2-9) 4%
V-HH2B (2F, 3F) -O2 (2-9) 6%
V2-HBB (2F, 3F) -O2 (2-14) 5%
V-HBB (2F, 3F) -O2 (2-14) 5%
V-HBB (2F, 3F) -O4 (2-14) 6%
2-HH-3 (3-1) 12%
1-BB-5 (3-3) 12%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 3%
3-HBB-2 (3-6) 3%
NI = 89.9 ° C; Tc <-20 ° C; Δn = 0.122; Δε = -4.2; Vth = 2.16V; η = 23.4 mPa · s.

[Composition M17]
3-HB (2F, 3F) -O2 (2-1) 3%
V-HB (2F, 3F) -O2 (2-1) 3%
V2-HB (2F, 3F) -O2 (2-1) 5%
5-H2B (2F, 3F) -O2 (2-2) 5%
V2-BB (2F, 3F) -O2 (2-6) 3%
1V2-BB (2F, 3F) -O2 (2-6) 3%
3-HHB (2F, 3F) -O2 (2-8) 6%
V-HHB (2F, 3F) -O2 (2-8) 6%
V-HHB (2F, 3F) -O4 (2-8) 5%
V2-HHB (2F, 3F) -O2 (2-8) 4%
V-HHB (2F, 3Cl) -O2 (2-11) 3%
V2-HBB (2F, 3F) -O2 (2-14) 5%
V-HBB (2F, 3F) -O2 (2-14) 4%
V-HBB (2F, 3F) -O4 (2-14) 5%
V2-BB (2F, 3F) B-1 (2-19) 4%
3-HH-V (3-1) 27%
3-HH-V1 (3-1) 6%
V-HHB-1 (3-5) 3%
NI = 77.1 ° C; Tc <-20 ° C; Δn = 0.101; Δε = −3.0; Vth = 2.04V; η = 13.9 mPa · s.

[Composition M18]
V-HB (2F, 3F) -O2 (2-1) 10%
V2-HB (2F, 3F) -O2 (2-1) 10%
2-H1OB (2F, 3F) -O2 (2-3) 3%
3-H1OB (2F, 3F) -O2 (2-3) 3%
2O-BB (2F, 3F) -O2 (2-6) 3%
V2-BB (2F, 3F) -O2 (2-6) 8%
V2-HHB (2F, 3F) -O2 (2-8) 5%
V-HHB (2F, 3Cl) -O2 (2-11) 7%
2-HBB (2F, 3F) -O2 (2-14) 3%
3-HBB (2F, 3F) -O2 (2-14) 3%
V-HBB (2F, 3F) -O2 (2-14) 6%
V-HBB (2F, 3F) -O4 (2-14) 8%
3-HH-4 (3-1) 14%
V-HHB-1 (3-5) 10%
3-HBB-2 (3-6) 7%
NI = 75.9 ° C; Tc <-20 ° C; Δn = 0.114; Δε = -3.9; Vth = 2.20V; η = 24.7mPa · s.

[Composition M19]
3-HB (2F, 3F) -O2 (2-1) 12%
5-BB (2F, 3F) -O2 (2-6) 4%
3-BB (2F, 3F) -O2 (2-6) 10%
3-HDhB (2F, 3F) -O2 (2-13) 12%
3-dhBB (2F, 3F) -O2 (2-16) 8%
2-HH-3 (3-1) 20%
3-HH-4 (3-1) 6%
3-HB-O2 (3-2) 3%
3-HHB-O1 (3-5) 3%
3-HHB-3 (3-5) 6%
3-HHB-1 (3-5) 6%
3-HBB-2 (3-6) 10%
NI = 75.9 ° C.; Δn = 0.101; Δε = -2.7.

[Composition M20]
2-H1OB (2F, 3F) -O2 (2-3) 7%
3-H1OB (2F, 3F) -O2 (2-3) 7%
3-HHB (2F, 3F) -O2 (2-8) 4%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 8%
4-HBB (2F, 3F) -O2 (2-14) 4%
5-HBB (2F, 3F) -O2 (2-14) 9%
3-dhBB (2F, 3F) -O2 (2-16) 4%
2-HH-3 (3-1) 18%
3-HH-4 (3-1) 3%
3-HH-5 (3-1) 3%
2-HH-5 (3-1) 2%
3-HB-O2 (3-2) 17%
3-HBB-2 (3-6) 10%
NI = 78.4 ° C; Tc <-30 ° C; Δn = 0.105; Δε = -2.7; Vth = 2.43V; η = 16.2 mPa · s.

[Composition M21]
2-H1OB (2F, 3F) -O2 (2-3) 10%
3-H1OB (2F, 3F) -O2 (2-3) 10%
2-HHB (2F, 3F) -O2 (2-8) 3%
3-HHB (2F, 3F) -O2 (2-8) 9%
5-HHB (2F, 3F) -O2 (2-8) 3%
2-HBB (2F, 3F) -O2 (2-14) 3%
3-HBB (2F, 3F) -O2 (2-14) 8%
4-HBB (2F, 3F) -O2 (2-14) 4%
2-HH-3 (3-1) 22%
3-HH-4 (3-1) 4%
3-HB-O2 (3-2) 10%
3-HBB-2 (3-6) 14%
NI = 76.0 ° C; Tc <-20 ° C; Δn = 0.097; Δε = −3.0; Vth = 2.20 V.

[Composition M22]
3-H1OB (2F, 3F) -O2 (2-3) 10.5%
3-HHB (2F, 3F) -O2 (2-8) 6%
V-HHB (2F, 3F) -O2 (2-8) 12%
3-HBB (2F, 3F) -O2 (2-14) 10%
V-HBB (2F, 3F) -O2 (2-14) 8%
V-HBB (2F, 3F) -O4 (2-14) 7%
2-HH-3 (3-1) 21%
3-HH-4 (3-1) 5%
3-HH-5 (3-1) 6%
1-BB-3 (3-3) 4%
1-BB-5 (3-3) 10.5%
NI = 75.3 ° C.; Δn = 0.109; Δε = -3.1; Vth = 2.29V.

[Composition M23]
3-H1OB (2F, 3F) -O2 (2-3) 8%
3-HHB (2F, 3F) -O2 (2-8) 8%
3-HH1OB (2F, 3F) -O2 (2-10) 26%
2-HH-3 (3-1) 25%
1-BB-2 (3-3) 15%
1-BB-3 (3-3) 4%
3-HHB-1 (3-5) 6%
3-HBB-2 (3-6) 8%
NI = 73.5 ° C; Tc <-20 ° C; Δn = 0.100; Δε = -2.6.

[Composition M24]
3-DhB (2F, 3F) -O2 (2-4) 7%
2-HHB (2F, 3F) -O2 (2-8) 3%
3-HHB (2F, 3F) -O2 (2-8) 9%
5-HHB (2F, 3F) -O2 (2-8) 9%
3-HDhB (2F.3F) -O2 (2-13) 10%
2-HBB (2F, 3F) -O2 (2-14) 3%
3-HBB (2F, 3F) -O2 (2-14) 8%
5-HFLF4-3 (2-28) 3%
2-HH-3 (3-1) 22%
3-HH-4 (3-1) 4%
3-HH-5 (3-1) 4%
1-BB-3 (3-3) 4%
1-BB-5 (3-3) 12%
3-HHB-1 (3-5) 2%
NI = 74.8 ° C; Tc <-20 ° C; Δn = 0.099; Δε = -3.2.

[Composition M25]
2-H1OB (2F, 3F) -O2 (2-3) 7%
3-H1OB (2F, 3F) -O2 (2-3) 7%
3-HHB (2F, 3F) -O2 (2-8) 4%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 8% 4-HBB (2F, 3F) -O2 (2-14) 4%
3-dhBB (2F, 3F) -O2 (2-16) 4%
3-HB (2F) B (2F, 3F) -O2 (2-18) 9%
2-HH-3 (3-1) 18%
V-HH-V (3-1) 8%
3-HB-O2 (3-2) 17%
3-HBB-2 (3-6) 10%
NI = 71.1 ° C; Tc <-20 ° C; Δn = 0.105; Δε = -2.7.

[Composition M26]
3-H1OB (2F, 3F) -O2 (2-3) 8%
3-HHB (2F, 3F) -O2 (2-8) 7.5%
3-HH1OB (2F, 3F) -O2 (2-10) 20%
3-dhBB (2F, 3F) -O2 (2-16) 6%
2-HH-3 (3-1) 19%
3-HH-4 (3-1) 5%
3-HH-5 (3-1) 4%
1-BB-3 (3-3) 4%
1-BB-5 (3-3) 16%
3-HHB-1 (3-5) 2.5%
3-HBB-2 (3-6) 8%
NI = 75.6 ° C.; Δn = 0.104; Δε = -2.4.

[Composition M27]
3-HB (2F, 3F) -O2 (2-1) 12%
5-HB (2F, 3F) -O2 (2-1) 8%
2O-B (2F) B (2F, 3F) -O2 (2-7) 5%
3-HH2B (2F, 3F) -O2 (2-9) 9%
3-HDhB (2F, 3F) -O2 (2-13) 9%
3-dhBB (2F, 3F) -O2 (2-16) 7%
3-HH-V (3-1) 29%
2-HH-3 (3-1) 2%
V-HHB-1 (3-5) 5%
V-HBB-2 (3-6) 14%
NI = 76.5 ° C; Tc <-20 ° C; Δn = 0.098; Δε = −3.0; Vth = 2.15V; η = 16.2 mPa · s.

[Composition M28]
2OB (2F) B (2F, 3F) -O2 (2-7) 7%
2O-B (2F) B (2F, 3F) -O4 (2-7) 7%
2-HHB (2F, 3F) -O2 (2-8) 3%
3-HHB (2F, 3F) -O2 (2-8) 6%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 10%
3-HH2B (2F, 3F) -O2 (2-9) 9%
3-HH-V (3-1) 20%
2-HH-3 (3-1) 10%
3-HH-4 (3-1) 6%
3-HB-O2 (3-2) 7%
1-BB-3 (3-3) 4%
5-B (F) BB-2 (3-7) 7%
NI = 75.3 ° C; Tc <-20 ° C; Δn = 0.102; Δε = -2.6; Vth = 2.41V; η = 17.5 mPa · s.

The following polymerizable compounds (RM-1) to (RM-9) were used as the additive X. The numbers in parentheses after them correspond to the compound numbers.

The following polar compounds (A-1) to (A-32) were used as the additive Y.

[Example 1]
A polymerizable compound (RM-1) was added to the composition M1 as an additive X at a ratio of 0.3% by mass, and a polar compound (A-6) was added as an additive Y at a ratio of 3.0% by mass. Added. This composition showed a nematic phase at room temperature, and when NI (° C.) was measured, it was 71.1 ° C.

When this composition was encapsulated in a VA element of a glass substrate having no alignment film and the vertical orientation of the composition on the substrate was confirmed, the vertical orientation was shown. This VA element was irradiated with UV light having an intensity of 7.0 mW / cm ² at 365 nm for 90 minutes and heated in a constant temperature bath at 60 ° C. for 12 hours. After that, when the heating VHR was measured under the same measurement conditions as the initial VHR, it was 91.3%.

[Comparative Example 1]
For comparison, the compound represented by the following formula (S) was added to the composition M1 at a ratio of 0.3% by mass. When NI (° C.) was confirmed by the same method as in Example 1, it was 73.1 ° C.

When this composition was encapsulated in a VA element of a glass substrate having no alignment film and the vertical orientation of the composition on the substrate was confirmed, no vertical orientation was exhibited. Moreover, when the heating VHR was measured under the same measurement conditions as in Example 1, it was 19.8%.

[Comparative Example 2]
The polar compound (A-6) was added to the composition M1 as an additive Y at a ratio of 3.0% by mass. When NI (° C.) was confirmed by the same method as in Example 1, it was 71.2 ° C.

When this composition was encapsulated in a VA element of a glass substrate having no alignment film and the vertical orientation of the composition on the substrate was confirmed, no vertical orientation was exhibited. Moreover, when the heating VHR was measured under the same measurement conditions as in Example 1, it was 48.6%.
[Comparative Example 3]
Compound (S) was added to the composition M1 in a proportion of 0.3% by mass, and polar compound (A-6) was added in a proportion of 3.0% by mass. When NI (° C.) was confirmed by the same method as in Example 1, it was 71.2 ° C.

When this composition was encapsulated in a VA element of a glass substrate having no alignment film and the vertical orientation of the composition on the substrate was confirmed, no vertical orientation was exhibited. Moreover, when the heating VHR was measured under the same measurement conditions as in Example 1, it was 70.5%.

[Examples 2 to 30]
A liquid crystal composition to which the additive X and the additive Y were added was prepared by changing the type of the composition and the concentration of the polar compound, and the orientation and the heated VHR were measured by the same method as in Example 1. The results are summarized in Table 4 with the case of vertical orientation as ◯ and the case of no vertical orientation as ×.

[Example 31]
A polymerizable compound (RM-1) was added to the composition M1 as an additive X at a ratio of 0.6% by mass, and a polar compound (A-11) was added as an additive Y at a ratio of 0.3% by mass. , Polar compound (A-13) was added in a proportion of 0.3% by mass. This composition showed a nematic phase at room temperature, and NI (° C.) was measured to be 72.2 ° C.

When this composition was encapsulated in a VA element of a glass substrate having no alignment film and the vertical orientation of the composition on the substrate was confirmed, the vertical orientation was shown. Moreover, when the heating VHR was measured under the same measurement conditions as in Example 1, it was 93.5%.

[Examples 32 to 50]
A liquid crystal composition to which the additive X and the additive Y were added was prepared by changing the type of the composition and the concentration of the polar compound, and the orientation and the heated VHR were measured by the same method as in Example 1. The results are summarized in Table 5 with the case of vertical orientation as ◯ and the case of no vertical orientation as ×.

From the results of Tables 4 and 5, the liquid crystal composition to which the additive X and the additive Y were added showed good vertical orientation, and the heated VHR was 90% or more. On the other hand, the liquid crystal composition to which the additive Y was not added did not show vertical orientation, and the heated VHR was 90% or less. The liquid crystal composition to which the additive X was not added showed good vertical orientation, but the heated VHR was 90% or less. Further, the liquid crystal composition in which the compound (S) was added instead of the polymerizable compound (RM-1) and the polar compound (A-6) was added as the additive Y showed good vertical orientation. The heating VHR was 90% or less. This result shows that the liquid crystal composition of the present invention has excellent vertical orientation and heated VHR.

The liquid crystal composition of the present invention can impart excellent vertical orientation and heated VHR. A liquid crystal display element containing this composition has characteristics such as a short response time, a large voltage retention rate, a low threshold voltage, a large contrast ratio, and a long life, and therefore can be used in liquid crystal projectors, liquid crystal televisions, and the like. ..

Claims (20)

The additive X is selected from polar compounds containing at least one compound selected from the polymerizable compound represented by the formula (1), and the additive Y is selected from the polar compounds having a polymerizable group represented by the formula (B). A liquid crystal composition containing at least one compound and having a nematic phase and negative permittivity anisotropy.

In equation (1)
Ring ^{A 1} and ring ^{A 3} is cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl or pyridine, - 2-Il, in these rings, at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkenyl with 2 to 12 carbons, alkenyloxy with 2 to 12 carbons, or at least one. Hydrogen may be replaced with 1 to 12 carbon alkyl replaced with fluorine or chlorine;
Ring A ² contains 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene- 2,7-Diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings. , At least one hydrogen is replaced with fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, or alkyl with 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. May;
Z ¹ and Z ² are single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, or -OCO-. May be replaced, at least one −CH ₂ −CH ₂₋ may be −CH = CH−, −C (CH ₃ ) = CH−, −CH = C (CH ₃ ) −, or −C (CH _3). ) = C (CH ₃ )-may be replaced, and in these groups at least one hydrogen may be replaced with fluorine or chlorine;
Sp ¹ , Sp ² , and Sp ³ are single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH ₂ − is -O-, -COO-, -OCO-, or. It may be replaced by −OCOO −, at least one −CH ₂ −CH ₂ − may be replaced by −CH = CH− or −C≡C−, and in these groups, at least one hydrogen is present. , May be replaced with fluorine or chlorine;
a is 0, 1, or 2;
b, c, and d are 0, 1, 2, 3, or 4, and the sum of b, c, and d is greater than or equal to 1.
P ^{1, P 2,} and ^{P 3} is a polymerizable ^group, at least one of P 1, ^{P 2,} and ^{P 3} is an a polymerizable group represented by the formula (P-1);

In equation (P-1)
M ¹ is an alkyl having 1 to 5 carbon atoms;
n is an integer from 1 to 5;

In formula (B)
R ⁶ is hydrogen or an alkyl having 1 to 7 carbon atoms, in which at least one −CH ₂ − may be replaced by −O − or −S−, and at least one −CH ₂ −. CH ₂ − may be replaced by −CH = CH − or −C≡C−, and in these groups at least one hydrogen may be replaced by fluorine or chlorine;
Ring ^{A 4} and ring ^{A 5} are 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-cyclohexenylene Len, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-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, carbon number. It may be replaced with an alkyl of 1 to 10, an alkenyl having 2 to 10 carbon atoms, an alkoxy having 1 to 9 carbon atoms, or an alkenyloxy having 2 to 9 carbon atoms, and in these groups, at least one hydrogen is fluorine. Or may be replaced with chlorine;
p is 0, 1, 2, 3, or 4;
q and r are 0, 1, or 2;
Z ⁸ is a single bond or an alkylene with 1 to 6 carbon atoms, in which at least one -CH ₂ − is -O-, -CO-, -COO-, -OCO-, or -OCOO-. At least one −CH ₂ −CH ₂₋ may be replaced with −CH = CH− or −C≡C−, and in these groups at least one hydrogen is fluorine or May be replaced with chlorine;
X ¹ is a polar group having a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, phosphorus and silicon.
Sp ⁹ is a single bond or an alkylene having 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, -OCO-, -OCOO-, Alternatively, it may be replaced by a group represented by the formula (1-a), and at least one −CH ₂ −CH ₂ − may be replaced by −CH = CH− or −C≡C−. Under the basis of, at least one hydrogen is fluorine, chlorine, formula (A-p1), formula (A-p2), formula (A-p3), formula (A-p4), or formula (A-p5). May be replaced by the group represented;

P ¹⁶ and P ¹⁷ are selected from the groups represented by the formulas (A-p1), (A-p2), (A-p3), (A-p4), and (A-p5). It is a base, and;

In formulas (A-p1) to (A-p5),
Sp ¹⁰ is a single bond or an alkylene with 1 to 15 carbon atoms, in which at least one -CH ₂ − is -O-, -CO-, -COO-, -OCO-, or -OCOO-. At least one −CH ₂ −CH ₂₋ may be replaced with −CH = CH− or −C≡C−, and in these groups at least one hydrogen is fluorine or May be replaced with chlorine;
R ⁷ is an alkyl with 1 to 5 carbon atoms;
R ⁸ is an alkyl with 1 to 10 carbon atoms or a cyclic alkyl with 3 to 8 carbon atoms;
Y ¹ is chlorine, fluorine, or bromine. In formula (1), P ¹ , P ² , and P ³ are groups selected from the polymerizable groups represented by formula (P-6) from formula (P-1), and P ¹ , P ² , and at least one of P ³ is a polymerizable group represented by the formula (P-1), the liquid crystal composition according to claim 1.

In formulas (P-1) to (P-6), M ¹ is an alkyl having 1 to 5 carbon atoms; M ² , M ³ and M ⁴ are hydrogen, fluorine, and 1 to 5 carbon atoms. Alkyl, or an alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; n is an integer of 1 to 5. The liquid crystal composition according to claim 1 or 2, which contains at least one compound selected from the compounds represented by the formulas (1-1) to (1-30) as the additive X.

In equations (1-1) to (1-30),
R ¹ is hydrogen, an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, an alkenyloxy having 2 to 12 carbon atoms, or at least one hydrogen being replaced with fluorine or chlorine. Alkyl with 1 to 12 carbon atoms;
Sp ¹ , Sp ² , and Sp ³ are single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH ₂ − is -O-, -COO-, -OCO-, or. It may be replaced by −OCOO −, at least one −CH ₂ −CH ₂ − may be replaced by −CH = CH− or −C≡C−, and in these groups, at least one hydrogen is present. , May be replaced with fluorine or chlorine;
P ⁵ , P ⁶ , and P ⁷ are groups selected from the polymerizable groups represented by formulas (P-1) to (P-4); at least ^{P 5} , P ⁶ , and P ^7. One is a polymerizable group represented by the formula (P-1);

In equations (P-1) to (P-4),
M ¹ is an alkyl having 1 to 5 carbon atoms;
M ² , M ³ , and M ⁴ are hydrogen, fluorine, alkyl with 1 to 5 carbon atoms, or alkyl with 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine;
n is an integer from 1 to 5. The liquid crystal composition according to any one of claims 1 to 3, wherein the ratio of the additive X is in the range of 0.03% by mass to 10% by mass. The invention according to any one of claims 1 to 4, wherein in the formula (B), X ¹ is a polar group represented by any one of the formulas (X-1) to (X-27). Liquid crystal composition.

In formulas (X-1) to (X-27),
J ¹ and J ² are hydrogen, or alkyl having 1 to 5 carbon atoms, in which at least one −CH ₂ − may be replaced by −O −;
J ³ is hydrogen, or an alkyl having 1 to 20 carbon atoms, in which at least one -CH _2- may be replaced by -O-, -COO- or -OCO-;
J ⁴ and J ⁵ are hydrogen, or alkyl with 1 to 8 carbon atoms;
Q ¹ is a methine group or a nitrogen, wherein the hydrogen of the methine group may be replaced by alkyl having 1 to 6 carbon atoms;
U ¹ and U ² are -CH _2- , -O-, -CO- or -S-;
V ¹ , V ² and V ³ are methine or nitrogen, and ^{any one of V 1} , V ² and V ³ is always nitrogen;
W ¹ is oxygen or sulfur;
W ² is carbon, sulfur or silicon.
^{However, when Q 1} is methine in the formula (X-14), ^{one of U 1} and U ² is always -O-, -CO-, or -S-. The liquid crystal composition according to any one of claims 1 to 5, wherein the ratio of the additive Y is in the range of 0.1% by mass to 10% by mass. The liquid crystal composition according to any one of claims 1 to 6, which contains at least one compound selected from the compounds represented by the formula (2) as the component A.

In equation (2)
R ¹ and R ² are hydrogen, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, alkenyloxy with 2 to 12 carbon atoms, or at least one hydrogen is fluorine or It is an alkyl with 1 to 12 carbon atoms replaced by chlorine;
Rings D and F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen replaced with fluorine or chlorine 1 , 4-Phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine, chromane-2,6-diyl, or at least one hydrogen is fluorine or chlorine. Chroman-2,6-jiyl replaced by;
Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4. 5-Trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran- 3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2,5-diyl;
Z ³ and Z ⁴ are single bonds, ethylene, methyleneoxy, or carbonyloxy;
e is 0, 1, 2, or 3, f is 0 or 1, and the sum of e and f is 3 or less. The liquid crystal composition according to any one of claims 1 to 7, which contains at least one compound selected from the group of compounds represented by the formulas (2-1) to (2-35) as the component A. Stuff.

In formulas (2-1) to (2-35), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and carbon number of carbon atoms. 2 to 12 alkenyloxy, or 1 to 12 carbon alkyl in which at least one hydrogen is replaced with fluorine or chlorine. The liquid crystal composition according to claim 7 or 8, wherein the proportion of the component A is in the range of 10% by mass to 90% by mass. The liquid crystal composition according to any one of claims 1 to 9, which contains at least one compound selected from the compounds represented by the formula (3) as the component B.

In equation (3)
R ³ and R ⁴ are alkyls having 1 to 12 carbon atoms, alkoxys having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. , Or an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine;
Rings G and I are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene;
Z ⁵ is a single bond, ethylene, or carbonyloxy;
g is 1, 2, or 3. The liquid crystal composition according to any one of claims 1 to 10, which contains at least one compound selected from the compounds represented by the formulas (3-1) to (3-13) as the component B.

In formulas (3-1) to (3-13), 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 an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. The liquid crystal composition according to claim 10 or 11, wherein the proportion of the component B is in the range of 10% by mass to 90% by mass. The liquid crystal composition according to any one of claims 1 to 12, which contains at least one compound selected from the polymerizable compounds represented by the formula (4) as the additive Z.

In equation (4)
Rings I and K are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine-2-yl, or pyridine-2-yl. In these rings, at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, or at least one hydrogen with fluorine or chlorine. May be replaced with 1 to 12 alkyl;
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 these rings. At least one hydrogen is replaced with fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, or alkyl with 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. Well;
Z ⁶ and Z ⁷ are single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, or -OCO-. May be replaced, at least one −CH ₂ −CH ₂₋ may be −CH = CH−, −C (CH ₃ ) = CH−, −CH = C (CH ₃ ) −, or −C (CH _3). ) = C (CH ₃ )-may be replaced, and in these groups at least one hydrogen may be replaced with fluorine or chlorine;
Sp ⁵ , Sp ⁶ , and Sp ⁷ are single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH ₂ − is -O-, -COO-, -OCO-, or. It may be replaced by −OCOO −, at least one −CH ₂ −CH ₂ − may be replaced by −CH = CH− or −C≡C−, and in these groups, at least one hydrogen , May be replaced with fluorine or chlorine;
h is 0, 1, or 2;
i, j, and k are 0, 1, 2, 3, or 4, and the sum of i, j, and k is greater than or equal to 1.
P ⁹ , P ¹⁰ , and P ¹¹ are groups selected from the polymerizable groups represented by the formulas (P-7) to (P-11);

In formulas (P-7) to (P-11), M ⁵ , M ⁶ , and M ⁷ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen replaced with fluorine or chlorine. It is an alkyl having 1 to 5 carbon atoms. The liquid crystal composition according to any one of claims 1 to 13, which contains at least one compound selected from the compounds represented by the formulas (4-1) to (4-29) as the additive Z. ..

In equations (4-1) to (4-29),
Sp ⁵ , Sp ⁶ , and Sp ⁷ are single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH ₂ − is -O-, -COO-, -OCO-, Alternatively, it may be replaced by −OCOO −, and at least one −CH ₂ −CH ₂ − may be replaced by −CH = CH − or −C≡C−, and at least one hydrogen in these groups. May be replaced with fluorine or chlorine;
P ¹² , P ¹³ and P ¹⁴ are polymerizable groups selected from the groups represented by the formulas (P-7) to (P-9);

In formulas (P-7) to (P-9), M ⁵ , M ⁶ , and M ⁷ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen replaced with fluorine or chlorine. It is an alkyl having 1 to 5 carbon atoms. The liquid crystal composition according to claim 13 or 14, wherein the proportion of the additive Z is in the range of 0.03% by mass to 10% by mass. A liquid crystal display device containing the liquid crystal composition according to any one of claims 1 to 15. The liquid crystal display element according to claim 16, wherein the operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and the drive method of the liquid crystal display element is an active matrix method. A polymer-supported oriented liquid crystal display element containing the liquid crystal composition according to any one of claims 1 to 15 or having a polymerizable compound in the liquid crystal composition polymerized. Use of the liquid crystal composition according to any one of claims 1 to 15 in a liquid crystal display element. Use of the liquid crystal composition according to any one of claims 1 to 15 in a polymer-supported oriented liquid crystal display device.