JPWO2019188920A1 - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

Satisfy at least one property in properties such as high upper limit temperature, lower lower limit temperature, low viscosity, suitable optical anisotropy, large permittivity anisotropy, large resistivity, high stability, large elastic constant. Alternatively, a liquid crystal composition having an appropriate balance with respect to at least two properties, and an AM element containing this composition are provided. A specific compound having a polymerizable group as the first additive, a specific compound having a negatively large dielectric anisotropy as the first component, and a specific compound having a high upper limit temperature or a small viscosity as the second component. , Or a liquid crystal composition which may contain a specific compound having a polymerizable group as a second additive.

Description

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

In liquid crystal display elements, the classification based on the operation mode of liquid crystal molecules is PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS. (In-plane switching), VA (vertical alignment), FFS (fringe field switching), FPA (field-induced photo-reactive alignment) and other modes. The classifications based on the drive method of the element are PM (passive matrix) and AM (active matrix). PM is classified into static and multiplex, 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 relationships in these properties are summarized in Table 1 below. The properties of the composition will be further described based on commercially available AM devices. The temperature range of the nematic phase is related to the temperature range in which the device can be used. The preferred upper limit temperature of the nematic phase is about 70 ° C. or higher, and the preferred lower limit temperature of the nematic phase is about −10 ° C. or lower. The viscosity of the composition is related to the response time of the device. A short response time is preferred for displaying moving images on the device. A shorter response time of even 1 millisecond is desirable. Therefore, a small viscosity in the composition is preferred. Small viscosities at low temperatures are even more preferred. The elastic constant of the composition is related to the contrast of the device. In order to increase the contrast ratio in the device, a large elastic constant in the composition is more preferable.

The optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large optical anisotropy or a small optical anisotropy, that is, an appropriate optical anisotropy is required. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate 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, an FFS mode or an FPA mode, a composition having positive or negative dielectric anisotropy is used. In the polymer support orientation type 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.

International Publication No. 2015-004954 Japanese Unexamined Patent Publication No. 2003-307720 Japanese Unexamined Patent Publication No. 2004-131704 European Patent Application Publication No. 1889894

The subjects of the present invention are a high upper limit temperature of the nematic phase, a lower lower limit temperature of the nematic phase, a small viscosity, an appropriate optical anisotropy, a negatively large dielectric anisotropy, a large specific resistance, a high stability against ultraviolet rays, and heat. It is to provide a liquid crystal composition that satisfies at least one of the properties such as high stability against 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 object is to provide a liquid crystal display device containing such a composition. Another challenge is to provide an AM device with characteristics such as short response time, high voltage retention, low threshold voltage, high contrast ratio, long lifetime.
Conventional polymerizable compounds have not been able to provide a liquid crystal composition that satisfies high stability against ultraviolet rays.

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；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；

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；
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の整数である。The present invention relates to a liquid crystal composition containing at least one compound selected from the polymerizable compound represented by the formula (1) as a first additive and having a nematic phase, and a liquid crystal display device containing this composition.

In formula (1), ring A ¹ and ring A ³ are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidine-2. -Il, or pyridin-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 is fluorine. Alternatively, it may be replaced with an alkyl having 1 to 12 carbon atoms replaced with chlorine; ring A ² is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1, 2-Diyl, Naphthalene-1,3-Diyl, Naphthalene-1,4-Diyl, Naphthalene-1,5-Diyl, Naphthalene-1,6-Diyl, Naphthalene-1,7-Diyl, Naphthalene-1,8- Diyl, Naphthalene-2,3-Diyl, Naphthalene-2,6-Diyl, Naphthalene-2,7-Diyl, Tetrahydropyran-2,5-Diyl, 1,3-Dioxane-2,5-Diyl, Pyrimidine-2 , 5-Diyl, or Pyridine-2,5-Diyl, in which at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, or at least 1 hydrogen. One hydrogen may be replaced with an alkyl having 1 to 12 carbon atoms replaced with fluorine or chlorine; P ¹ , P ² and P ³ are polymerizable groups and at least ^{P 1} , P ² and P ³ One is a polymerizable group represented by the formula (P-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 )-, 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 It is an alkylene having 1 to 10 carbon atoms, in which at least one −CH ₂ − may be replaced by −O−, −COO−, −OCO−, or −OCOO−, and at least one −. CH _2- CH _2- may be replaced with −CH = CH − or −C≡C−, and in these groups at least one hydrogen may be replaced with fluorine or chlorine; 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.
In formula (P-1), M ¹ is an alkyl having 1 to 5 carbon atoms; n is an integer of 1 to 5.

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

The usage of terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "composition" and "element", respectively. "Liquid crystal display element" is a general term for a liquid crystal display panel and a liquid crystal display module. 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. Parts per million (ppm) may be used. 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, the expression "Ra and Rb are alkyl, alkoxy, or alkenyl" means that Ra and Rb are independently selected from the group of alkyl, alkoxy, and alkenyl. To do. That is, the group represented by Ra and the group represented by Rb may be the same or different.

At least one compound selected from the compounds represented by 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-).

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；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；

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；
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の整数である。The present invention includes the following items.
Item 1. A liquid crystal composition containing at least one compound selected from the polymerizable compounds represented by the formula (1) as a first additive and having a nematic phase.

In formula (1), ring A ¹ and ring A ³ are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidine-2. -Il, or pyridin-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 is fluorine. Alternatively, it may be replaced with an alkyl having 1 to 12 carbon atoms replaced with chlorine; ring A ² is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1, 2-Diyl, Naphthalene-1,3-Diyl, Naphthalene-1,4-Diyl, Naphthalene-1,5-Diyl, Naphthalene-1,6-Diyl, Naphthalene-1,7-Diyl, Naphthalene-1,8- Diyl, Naphthalene-2,3-Diyl, Naphthalene-2,6-Diyl, Naphthalene-2,7-Diyl, Tetrahydropyran-2,5-Diyl, 1,3-Dioxane-2,5-Diyl, Pyrimidine-2 , 5-Diyl, or Pyridine-2,5-Diyl, in which at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, or at least 1 hydrogen. One hydrogen may be replaced with an alkyl having 1 to 12 carbon atoms replaced with fluorine or chlorine; P ¹ , P ² and P ³ are polymerizable groups and at least ^{P 1} , P ² and P ³ One is a polymerizable group represented by the formula (P-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 )-, 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 It is an alkylene having 1 to 10 carbon atoms, in which at least one −CH ₂ − may be replaced by −O−, −COO−, −OCO−, or −OCOO−, and at least one −. CH _2- CH _2- may be replaced with −CH = CH − or −C≡C−, and in these groups at least one hydrogen may be replaced with fluorine or chlorine; 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.
In formula (P-1), M ¹ is an alkyl having 1 to 5 carbon atoms; n is an integer of 1 to 5.

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-1) to formula (P-6), P ¹ , P ² , and P 1. Item 2. The liquid crystal composition according to Item 1, wherein at least one of P ^{3 is a polymerizable group represented by the formula (P-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；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；

ここで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い。
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 first additive.

In formulas (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, and 2 to 12 carbon atoms. be alkenyloxy or at least one hydrogen from a carbon number of 1 which is replaced by fluorine or chlorine 12 ^alkyl,; P 5, ^{P 6,} and ^{P 7} has the formula from the formula (P-1) (P- 4 ) Is a group selected from the polymerizable groups represented by), and ^{at least one of P 5} , P ^{6 and P 7} is a polymerizable group represented by the formula (P-1);

Here, M ¹ is an alkyl having 1 to 5 carbon atoms; M ² , M ³ and M ⁴ are hydrogen, fluorine, an alkyl having 1 to 5 carbon atoms, or at least one hydrogen is replaced with fluorine or chlorine. The resulting alkyl with 1 to 5 carbons; n is an integer from 1 to 5; Sp ¹ , Sp ² , and Sp ³ are single-bonded or alkylenes with 1 to 10 carbon atoms in this alkylene. , At least one −CH ₂ − may be replaced by −O −, −COO−, −OCO−, or −OCOO−, and at least one −CH ₂ −CH ₂₋ is −CH = CH−. Alternatively, it may be replaced by −C≡C−, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine.

Item 4. Item 6. The liquid crystal composition according to any one of Items 1 to 3, wherein the ratio of the first additive is in the range of 0.03% 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；そしてｅとｆとの和は３以下である。Item 5. Item 6. The liquid crystal composition according to any one of Items 1 to 4, which contains at least one compound selected from the compounds represented by the formula (2) as the first component.

In formula (2), 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, alkenyloxy having 2 to 12 carbon atoms, or at least. One hydrogen is an alkyl having 1 to 12 carbon atoms with fluorine or chlorine replaced; rings D and F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5- Diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2 in which at least one hydrogen is replaced with fluorine or chlorine, 6-diyl, chroman-2,6-diyl, or chroman-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine; ring 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 in There 7- diyl or 1,1,6,7- tetrafluoro indane-2,5-diyl,; ^{Z 3} and ^{Z 4} is a single bond, ethylene, methyleneoxy or carbonyloxy,; e is It 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.

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 6. Item 2. The liquid crystal composition according to any one of Items 1 to 5, which contains at least one compound selected from the group of compounds represented by the formulas (2-1) to (2-35) as the first component. 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. An alkenyloxy of 2 to 12, or an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine.

Item 7. Item 5. The liquid crystal composition according to Item 5 or 6, wherein the proportion of the first component 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 8. Item 6. The liquid crystal composition according to any one of Items 1 to 7, which contains at least one compound selected from the compounds represented by the formula (3) as the second component.

In formula (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 carbons in which at least one hydrogen is replaced with fluorine or chlorine. Alkyl of numbers 1 to 12, or 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 single bond, ethylene, or carbonyloxy; g is 1, 2, or 3 is there.

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 9. Item 6. The liquid crystal composition according to any one of Items 1 to 8, which contains at least one compound selected from the compounds represented by the formulas (3-1) to (3-13) as the second component.

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 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 10. Item 8. The liquid crystal composition according to Item 8 or 9, wherein the proportion of the second component 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；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；

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、そしてｉ、ｊ、およびｋの和は、１以上であり；
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 11. Item 6. The liquid crystal composition according to any one of Items 1 to 10, which contains at least one compound selected from the polymerizable compounds represented by the formula (4) as the second additive.

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; 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, pyrimidin-2,5- Diyl, or pyridine-2,5-diyl, in these rings at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least one hydrogen. It may be replaced with an alkyl having 1 to 12 carbon atoms replaced with fluorine or chlorine; Z ⁶ and Z ⁷ are single-bonded or alkylenes having 1 to 10 carbon atoms, in which at least one -CH ₂ − may be replaced by −O −, −CO−, −COO−, or −OCO−, and at least one −CH ₂ −CH ₂₋ is −CH = CH−, −C (CH _3). ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )-, and in these groups at least one hydrogen is fluorine or chlorine. May be replaced with; P ⁹ , P ¹⁰ , and P ¹¹ are groups selected from the polymerizable groups represented by formulas (P-7) to (P-11);

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 is present. , Fluorine or chlorine; h is 0, 1, or 2; i, j, and k are 0, 1, 2, 3, or 4, and i, j, and The sum of k is greater than or equal to 1;
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、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；

ここで、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のアルキルであり；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い。Item 12. Item 2. The liquid crystal composition according to any one of Items 1 to 11, which contains at least one compound selected from the compounds represented by the formulas (4-1) to (4-29) as the second additive. ..

In formulas (4-1) to (4-29), P ¹² , P ¹³ , and P ¹⁴ are polymerizables selected from the groups represented by formulas (P-7) to (P-9). Is the basis;

Here, M ⁵ , M ⁶ , and M ⁷ 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; Sp. ⁵ , Sp ⁶ and Sp ⁷ are single-bonded or alkylenes having 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.

Item 13. Item 2. The liquid crystal composition according to Item 11 or 12, wherein the proportion of the second additive is in the range of 0.03% by mass to 10% by mass.

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

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

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

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

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

The present invention also includes the following sections. (A) As a third additive, at least one of additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound. The above composition further containing. (B) AM device containing the above composition. (C) A polymer-supported orientation (PSA) type AM device containing the above composition. (D) A polymer-supported orientation (PSA) type AM device containing the above composition and in which the polymerizable compound in the composition is polymerized. (E) A device containing the above composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA. (F) A transmissive device containing the above composition. (G) Use of the above composition as a composition having a nematic phase. (H) Use of an optically active composition obtained by adding an optically active compound to the above composition.

The composition of the present invention will be described in the following order. First, the composition of the composition will be described. Secondly, the main properties of the component compound and the main effect of this compound on the composition and the device will be described. Thirdly, the combination of the component compounds in the composition, the preferable ratio, 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, quenchers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. This composition is classified into composition A and composition B from the viewpoint of 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. Composition B has a smaller number of components than composition A. The composition B is preferable to the composition A from the viewpoint of reducing the cost. Composition A is preferable to composition B from the viewpoint that the properties can be further adjusted by mixing other liquid crystal compounds.

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

Thirdly, the combination of the components in the composition, the preferable ratio of the component compounds, and the rationale thereof will be described. A preferred combination of ingredients in the composition is compound (1) + compound (2), compound (1) + compound (2) + compound (3), or compound (1) + compound (2) + compound (3) + Compound (4). A more preferred combination is compound (1) + compound (2) + compound (3).

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 0.8% by mass. A particularly preferable ratio is in the range of about 0.3% by mass to about 0.5% 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 80% by mass. A particularly preferable ratio is in the range of about 30% by mass to about 70% 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 20% by mass to about 80% by mass. A particularly preferable ratio is in the range of about 30% by mass to about 70% by mass.

Polymerizable compounds such as compound (4) 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 0.8% by mass. A particularly preferable ratio is in the range of about 0.3% by mass to about 0.5% by mass.

Fourth, preferable forms of the component compounds will be described. First, the two liquid crystal compounds will be described together, and then the two additives will be described.
(A) Liquid liquid compounds In the formulas (2) and (3), R ¹ and R ² are 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. It is an alkenyloxy of 2 to 12, 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 and an alkoxy having 1 to 12 carbon atoms to increase dielectric anisotropy. R ³ and R ⁴ are alkyls with 1 to 12 carbon atoms, alkoxys with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, and alkyls with 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 methyl, ethyl, propyl, butyl, or pentyl to reduce viscosity.

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

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

Preferred 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 ring D or ring F is 1,4-cyclohexylene to reduce the viscosity or to raise the upper temperature limit, and 1,4-phenylene to increase the optical anisotropy.

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. 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 to reduce the viscosity or to raise the upper temperature limit, and 1,4-phenylene to increase the optical anisotropy.

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

Divalent groups such as methyleneoxy are asymmetrical. In methyleneoxy, −CH ₂ O− is preferred over _{−OCH 2 −.} In carbonyloxy, -COO- is preferred over -OCO-.

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. Preferred e is 1 for lowering the viscosity and 2 for raising the upper limit temperature. 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 for raising the upper temperature limit.

(B) an additive formula (1) and formula (4), ring ^{A 1} and ring ^{A 3} is cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3 -Dioxane-2-yl, pyrimidin-2-yl, or pyridin-2-yl, in which at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbon atoms, 1 to 12 carbon atoms Alkoxy, or at least one hydrogen, may be replaced with fluorine or an alkyl having 1 to 12 carbon atoms in which chlorine is 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.

Rings I and K are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl, or pyridin-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. It may be replaced with 1 to 12 alkyl. 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.

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.

P ⁹ , P ¹⁰ , and P ¹¹ are groups selected from the polymerizable groups represented by the formulas (P-7) to (P-11). The wavy lines of the formulas (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, 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. Preferred M ⁵ , M ⁶ or M ⁷ is hydrogen or methyl to increase reactivity. The more preferred M ⁵ is hydrogen or methyl, and the more preferred M ⁶ or M ⁷ is hydrogen.

Z ¹ , Z ² , 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 it may be replaced by -OCO-, at least one _-CH 2 -CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) - , Or —C (CH ₃ ) = C (CH ₃ ) −, and in these groups, at least one hydrogen may be replaced with fluorine or chlorine. Preferred Z ¹ , Z ² , Z ⁶ or Z ⁷ are single bonds, -CH _2- CH _{2- , -CH 2} O-, -OCH _2- , -COO-, or -OCO-. More preferred Z ¹ , Z ² , Z ⁶ or Z ⁷ are single bonds.

Sp ¹ , Sp ² , Sp ³ , 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 -OCOO- may be replaced, and at least one -CH ₂ -CH _2- may be replaced with -CH = CH- or -C≡C-, these At least one hydrogen may be replaced with fluorine or chlorine. Preferred Sp ¹ , Sp ² , Sp ³ , 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 ¹ , Sp ² , Sp ³ , Sp ⁵ , Sp ⁶ , or Sp ⁷ 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. 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 (1-29) according to Item 3. In these compounds, at least one of the first additives is compound (1-1), compound (1-2), compound (1-24), compound (1-25), compound (1-26), compound. It is preferably (1-27) or compound (1-29). At least two of the first additives are compound (1-1) and compound (1-2), compound (1-1) and compound (1-18), compound (1-2) and compound (1-24). , Compound (1-2) and compound (1-25), compound (1-2) and compound (1-26), compound (1-25) and compound (1-26), or compound (1-18). And a combination of compound (1-24) is preferred.

Preferred compounds (2) are compounds (2-1) to compounds (2-35) according to Item 6. In these compounds, at least one of the first components is compound (2-1), compound (2-3), compound (2-6), compound (2-8), compound (2-10), compound ( 2-13), compound (2-14), or compound (2-18) is preferred. At least two of the first components 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 It is preferably a combination of (2-10), compound (2-6) and compound (2-18), or compound (2-10) and compound (2-14).

Preferred compounds (3) are compounds (3-1) to compounds (3-13) according to Item 9. In these compounds, at least one of the second components is compound (3-1), compound (3-3), compound (3-5), compound (3-6), compound (3-7), or compound. (3-9) is preferable. At least two of the second components are compound (3-1) and compound (3-3), compound (3-1) and compound (3-5), or compound (3-1) and compound (3-6). Is preferable.

Preferred compounds (4) are compounds (4-1) to compounds (4-29) according to Item 12. In these compounds, at least one of the second additives is compound (4-1), compound (4-2), compound (4-24), compound (4-25), compound (4-26), or It is preferably compound (4-27). At least two of the second additives are compound (4-1) and compound (4-2), compound (4-1) and compound (4-18), compound (4-2) and compound (4-24). , Compound (4-2) and compound (4-25), compound (4-2) and compound (4-26), compound (4-25) and compound (4-26), or compound (4-18). And a combination of compound (4-24) is preferred.

Sixth, additives that may be added to the composition will be described. Such additives include optically active compounds, antioxidants, UV absorbers, quenchers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules to give a twist angle. Examples of such compounds are compound (5-1) to compound (5-5). 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 (6-1) to compounds (6-3) and the like.

Since the compound (6-2) 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 the UV absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as sterically hindered amines are also preferred. Preferred examples of the light stabilizer are compounds (7-1) to compounds (7-16) and the like. The preferable ratio of these absorbents and stabilizers is about 50 ppm or more in order to obtain the effect, and is 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 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 (8-1) to compounds (8-7) and the like. The preferred proportion of these quenchers is about 50 ppm or more to obtain the effect and about 20000 ppm or less to lower 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) and compound (4) are suitable for this purpose. A polymerizable compound different from these compounds may be added to the composition together with the compound (1) and the compound (4). Preferred examples of other 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 and methacrylates.
By changing the type of compound (1) or compound (4), or by combining compound (1) or compound (4) with a polymerizable compound different from compound (1) or compound (4) in an appropriate ratio. Therefore, the reactivity of the polymerizable compound and the pretilt angle of the liquid crystal molecules can be adjusted. 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.

Polymerizable compounds such as compound (1) and compound (4) are polymerized by UV irradiation. Polymerization may be carried out in the presence of a suitable polymerization 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 a polymerizable compound such as compound (1) or compound (4), a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine and the like.

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. Examples of synthesis of compound (1) are described in the Examples section. Compound (2-1) is synthesized by the method described in JP-A-2000-053602. Compound (3-1) is synthesized by the method described in JP-A-59-176221. Compound (4-19) is synthesized by the method described in JP-A-7-101900. Antioxidants are commercially available. Compound (6-1) is available from Sigma-Aldrich Corporation. Compound (6-2) and the like are synthesized by the method described in US Pat. No. 3,660,505.

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

Finally, the use of the composition will be described. Most compositions have a lower limit temperature of about −10 ° C. or lower, an upper limit temperature of about 70 ° C. or higher, and an optical anisotropy in the range of about 0.07 to about 0.20. Compositions having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the proportions of the constituent compounds or by mixing other liquid crystal compounds. Furthermore, a composition having an optical anisotropy in the range of about 0.10 to about 0.30 may be prepared by 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 device having an IPS mode or an FFS mode, the orientation of the liquid crystal molecules may be parallel to or perpendicular to the glass substrate when no voltage is applied. These elements may be reflective, transmissive or transflective. Use for transmissive devices is preferred. It can also be used for non-crystalline silicon-TFT elements or polycrystalline silicon-TFT elements. It can also be used for an NCAP (nematic curvilinear aligned phase) type device produced by microencapsulating this composition and a PD (polymer dispersed) type device in which a three-dimensional network polymer is formed in the composition.

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 assembled. 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.

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

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

Gas chromatograph analysis: A GC-14B type gas chromatograph manufactured by Shimadzu Corporation was used for the measurement. The carrier gas is helium (2 mL / min). The sample vaporization chamber was set to 280 ° C. and the detector (FID) was set to 300 ° C. A capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm; fixed liquid phase was dimethylpolysiloxane; non-polar) manufactured by Agilent Technologies Inc. was used for separation of the component compounds. The column was held at 200 ° C. for 2 minutes and then warmed to 280 ° C. at a rate of 5 ° C./min. The sample was prepared in an acetone solution (0.1% by 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 detected by gas chromatography (FID). The area ratio of the peak in the gas chromatogram corresponds to the ratio (mass ratio) of the liquid crystal compound. When the capillary column described above is used, the correction coefficient of each liquid crystal compound may be regarded as 1. Therefore, the proportion (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) precipitates at this ratio at 25 ° C, 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) deliberated and enacted by the Japan Electronics and Information Technology Industries Association (hereinafter referred to as JEITA), or modified. It was a method. A thin film transistor (TFT) was not attached to the TN element used for the measurement.

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

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

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

(4) Viscosity (rotational viscosity; γ1; measured at 25 ° C.; mPa · s): The 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 carried out using light having a wavelength of 589 nm and using an Abbe refractometer with a polarizing plate attached to the eyepiece. After rubbing the surface of the main prism in one direction, the sample was dropped onto the main prism. The refractive index n‖ was measured when the direction of polarization was parallel to the direction of rubbing. The refractive index n⊥ was measured when the direction of polarization was perpendicular to the direction of rubbing. The value of optical anisotropy was calculated from the equation of Δn = n ‖ −n ⊥.

(6) Permittivity anisotropy (Δε; measured at 25 ° C.): The value of permittivity anisotropy was calculated from the equation Δε = ε‖−ε⊥. The permittivity (ε‖ and ε⊥) was measured as follows.
1) Measurement of permittivity (ε‖): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a well-washed glass substrate. After rotating the glass substrate with a spinner, it was heated at 150 ° C. for 1 hour. 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 (VHR-1; measured at 25 ° C.;%): The TN element used for the measurement had a polyimide alignment film, and the distance (cell gap) between the two glass substrates was 5 μm. .. This device was sealed with an adhesive that cures with ultraviolet light after the sample was placed. A pulse voltage (60 microseconds at 5 V) was applied to the TN element to charge it. The decaying voltage was measured with a high-speed voltmeter for 16.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit period was determined. Area B was the area when there was no attenuation. The voltage holding ratio is expressed as a percentage of the area A with respect to the area B.

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

(10) Voltage retention rate (VHR-3; measured at 25 ° C.;%): After irradiation with ultraviolet rays, the voltage retention rate was measured to evaluate the stability against ultraviolet rays. The TN device used for the measurement had a polyimide alignment film, and the cell gap was 5 μm. A sample was injected into this device and irradiated with light for 30 minutes. The light source was an ultra-high pressure mercury lamp USH-500D (manufactured by Ushio, Inc.), and the distance between the element and the light source was 20 cm. In the measurement of VHR-3, the voltage attenuated for 166.7 milliseconds was measured. Compositions with large VHR-3 have great stability to UV light. VHR-3 is preferably 90% or more, more preferably 95% or more.

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

(12) Response time (τ; measured at 25 ° C.; ms): An LCD5200 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 500 Hz.
The distance between the two glass substrates (cell gap) was 3.2 μm, and the sample was placed in a PSA element in normally black mode. ^{This element was irradiated with ultraviolet rays of 76 mW / cm 2} while applying a voltage of 15 V, and the pretilt angle was set to 0.9 ± 0.2 °. A metal halide lamp (US4-X0401FKTN) manufactured by Eye Graphic Co., Ltd. was used for irradiation with ultraviolet rays. Next, ultraviolet rays of 3.8 mW / cm ² were irradiated for 60 minutes without applying a voltage. A black light (F40T10) manufactured by Eye Graphic Co., Ltd. was used for irradiation with ultraviolet rays. A square wave (30 Hz, 7.5 V, 1 second) was applied to this device. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. It was considered that the transmittance was 100% when the amount of light was maximum, and the transmittance was 0% when the amount of light was minimum. The response time was expressed as the time required for the transmittance to change from 90% to 10% (fall time; fall time; millisecond).

(13) 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 "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), equations (2.98) and (2.11) on page 75. Then, the value of the elastic constant was obtained from the equation (2.10).

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

[Synthesis Example 1]
Synthesis of polymerizable compound (1-2-1)

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, and the compound (1-2-1) (4.13 g, yield) was purified. 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.

The compounds in the examples are represented by symbols based on the definitions in Table 3 below. In Table 3, the molecular configuration for 1,4-cyclohexylene is trance. The number in parentheses after the symbol corresponds to the compound number. The symbol (-) means other liquid crystal compounds. The proportion (percentage) of the liquid crystal compound is a mass percentage (mass%) based on the mass of the liquid crystal composition. Finally, the characteristic values of the composition are summarized.

[Composition Example 1]
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 <-20 ° C; Δn = 0.105; Δε = -2.7; Vth = 2.43V; η = 16.2 mPa · s.

測定方法（１０）に記載した方法で、電圧保持率を測定した。
ＮＩ＝７８．４℃；ＶＨＲ−３＝９０．８％．[Example 1]
A polymerizable compound (1-2-1) was added to the composition of Composition Example 1 at a ratio of 0.3% by mass.

The voltage holding ratio was measured by the method described in the measuring method (10).
NI = 78.4 ° C; VHR-3 = 90.8%.

測定方法（１０）に記載した方法で、電圧保持率を測定した。
ＮＩ＝７８．４℃；ＶＨＲ−３＝８１．０％．[Comparative Example 1]
The polymerizable compound A was added to the composition of Composition Example 1 at a ratio of 0.3% by mass.

The voltage holding ratio was measured by the method described in the measuring method (10).
NI = 78.4 ° C; VHR-3 = 81.0%.

Comparison of properties The composition of Example 1 contains a polymerizable compound (1-2-1) in a proportion of 0.3% by mass. The VHR-3 of this composition was 90.8%. In Comparative Example 1, a polymerizable compound A having a similar structure was used instead of the polymerizable compound (1-2-1). As a result, VHR-3 of the composition was 81.0%. As described above, the composition of Example 1 had a large VHR-3 as compared with the composition of Comparative Example 1. Therefore, it is concluded that the liquid crystal composition of the present invention has excellent properties.

Other composition examples are shown below.

[Composition Example 2]
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 Example 3]
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 Example 4]
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 Example 5]
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.

[Composition Example 6]
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 Example 7]
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 Example 8]
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 Example 9]
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 Example 10]
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%
1O1-HBBH-5 (-) 4%
NI = 93.0 ° C; Tc <-30 ° C; Δn = 0.123; Δε = -4.0; Vth = 2.27V; η = 29.6 mPa · s.

[Composition Example 11]
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 Example 12]
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 Example 13]
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 Example 14]
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 Example 15]
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 Example 16]
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 Example 17]
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 Example 18]
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 Example 19]
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 Example 20]
3-HB (2F, 3F) -O2 (2-1) 12%
3-BB (2F, 3F) -O2 (2-6) 10%
5-BB (2F, 3F) -O2 (2-6) 4%
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 Example 21]
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 Example 22]
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 Example 23]
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 Example 24]
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 Example 25]
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 Example 26]
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 Example 27]
2O-B (2F) B (2F, 3F) -O2 (2-7) 5%
2O-B (2F) B (2F, 3F) -O4 (2-7) 7%
2-HHB (2F, 3F) -O2 (2-8) 2%
3-HHB (2F, 3F) -O2 (2-8) 7%
V-HBB (2F, 3F) -O2 (2-14) 8%
3-HBB (2F, 3F) -O2 (2-14) 9%
4-HBB (2F, 3F) -O2 (2-14) 4%
3-HB (2F) B (2F, 3F) -O2 (2-18) 9%
3-HH-V (3-1) 19%
2-HH-3 (3-1) 20%
3-HH-4 (3-1) 2%
1-BB-2 (3-3) 2%
1-BB-3 (3-3) 4%
3-HHB-1 (3-5) 2%
NI = 74.5 ° C; Tc <-20 ° C; Δn = 0.109; Δε = -3.1; Vth = 2.37 V.

[Examples 2 to 27]
The following polymerizable compounds (1-1-1) to (1-26-2) were added to the compositions of Composition Examples 2 to 27. Table 4 shows the combinations of the composition example and the polymerizable compound.

Table 4. Examples 2 to 27

The liquid crystal composition of the present invention has a high upper limit temperature, a lower lower limit temperature, a small viscosity, an appropriate optical anisotropy, a negatively large dielectric anisotropy, a large resistivity, a high stability against ultraviolet rays, and a high stability against heat. , Satisfy at least one property in properties such as large elastic constants, or have an appropriate balance with respect to at least two properties. 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, so that it can be used for a liquid crystal monitor, a liquid crystal television, or the like. ..

Claims (18)

A liquid crystal composition containing at least one compound selected from the polymerizable compounds represented by the formula (1) as a first additive and having a nematic phase.

In formula (1), ring A ¹ and ring A ³ are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidine-2. -Il, or pyridin-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 is fluorine. Alternatively, it may be replaced with an alkyl having 1 to 12 carbon atoms replaced with chlorine; ring A ² is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1, 2-Diyl, Naphthalene-1,3-Diyl, Naphthalene-1,4-Diyl, Naphthalene-1,5-Diyl, Naphthalene-1,6-Diyl, Naphthalene-1,7-Diyl, Naphthalene-1,8- Diyl, Naphthalene-2,3-Diyl, Naphthalene-2,6-Diyl, Naphthalene-2,7-Diyl, Tetrahydropyran-2,5-Diyl, 1,3-Dioxane-2,5-Diyl, Pyrimidine-2 , 5-Diyl, or Pyridine-2,5-Diyl, in which at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, or at least 1 hydrogen. One hydrogen may be replaced with an alkyl having 1 to 12 carbon atoms replaced with fluorine or chlorine; P ¹ , P ² and P ³ are polymerizable groups and at least ^{P 1} , P ² and P ³ One is a polymerizable group represented by the formula (P-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 )-, 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 It is an alkylene having 1 to 10 carbon atoms, in which at least one −CH ₂ − may be replaced by −O−, −COO−, −OCO−, or −OCOO−, and at least one −. CH _2- CH _2- may be replaced with −CH = CH − or −C≡C−, and in these groups at least one hydrogen may be replaced with fluorine or chlorine; 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.
In formula (P-1), M ¹ is an alkyl having 1 to 5 carbon atoms; n is an integer of 1 to 5. In formula (1), P ¹ , P ² and P ³ are groups selected from the polymerizable groups represented by formula (P-1) to formula (P-6), P ¹ , P ² and P. The liquid crystal composition according to claim 1, wherein at least one of ^{3 is a polymerizable group represented by the formula (P-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 first additive.

In formulas (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, and 2 to 12 carbon atoms. a alkenyloxy or at least one hydrogen is alkyl having 1 carbon is replaced by fluorine or chlorine ^12,, P 5, ^{P 6,} and ^{P 7} has the formula from the formula (P-1) (P- 4 ) Is a group selected from the polymerizable groups represented by); ^{at least one of P 5} , P ⁶ , and P ⁷ is a polymerizable group represented by the formula (P-1);

Here, M ¹ is an alkyl having 1 to 5 carbon atoms; M ² , M ³ and M ⁴ are hydrogen, fluorine, an alkyl having 1 to 5 carbon atoms, or at least one hydrogen is replaced with fluorine or chlorine. The resulting alkyl with 1 to 5 carbons; n is an integer from 1 to 5; Sp ¹ , Sp ² , and Sp ³ are single-bonded or alkylenes with 1 to 10 carbon atoms in this alkylene. , At least one −CH ₂ − may be replaced by −O −, −COO−, −OCO−, or −OCOO−, and at least one −CH ₂ −CH ₂₋ is −CH = CH−. Alternatively, it may be replaced by −C≡C−, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine.
The liquid crystal composition according to any one of claims 1 to 3, wherein the proportion of the first additive is in the range of 0.03% by mass to 10% by mass. The liquid crystal composition according to any one of claims 1 to 4, which contains at least one compound selected from the compounds represented by the formula (2) as the first component.

In formula (2), 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, alkenyloxy having 2 to 12 carbon atoms, or at least. One hydrogen is an alkyl having 1 to 12 carbon atoms with fluorine or chlorine replaced; rings D and F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5- Diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2 in which at least one hydrogen is replaced with fluorine or chlorine, 6-diyl, chroman-2,6-diyl, or chroman-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine; ring 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 in There 7- diyl or 1,1,6,7- tetrafluoro indane-2,5-diyl,; ^{Z 3} and ^{Z 4} is a single bond, ethylene, methyleneoxy or carbonyloxy,; e is It 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 liquid crystal according to any one of claims 1 to 5, which contains at least one compound selected from the group of compounds represented by formulas (2-1) to (2-35) as a first component. Composition.

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. An alkenyloxy of 2 to 12, or an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. The liquid crystal composition according to claim 5 or 6, wherein the proportion of the first component is in the range of 10% by mass to 90% by mass. The liquid crystal composition according to any one of claims 1 to 7, which contains at least one compound selected from the compounds represented by the formula (3) as the second component.

In formula (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 carbons in which at least one hydrogen is replaced with fluorine or chlorine. Alkyl of numbers 1 to 12, or 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 single bond, ethylene, or carbonyloxy; g is 1, 2, or 3 is there. The liquid crystal composition according to any one of claims 1 to 8, which contains at least one compound selected from the compounds represented by the formulas (3-1) to (3-13) as the second component. ..

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 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 8 or 9, wherein the proportion of the second component is in the range of 10% by mass to 90% by mass. The liquid crystal composition according to any one of claims 1 to 10, which contains at least one compound selected from the polymerizable compounds represented by the formula (4) as the second additive.

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; 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, pyrimidin-2,5- Diyl, or pyridine-2,5-diyl, in these rings at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least one hydrogen. It may be replaced with an alkyl having 1 to 12 carbon atoms replaced with fluorine or chlorine; Z ⁶ and Z ⁷ are single-bonded or alkylenes having 1 to 10 carbon atoms, in which at least one -CH ₂ − may be replaced by −O −, −CO−, −COO−, or −OCO−, and at least one −CH ₂ −CH ₂₋ is −CH = CH−, −C (CH _3). ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )-, and in these groups at least one hydrogen is fluorine or chlorine. May be replaced with; P ⁹ , P ¹⁰ , and P ¹¹ are groups selected from the polymerizable groups represented by formulas (P-7) to (P-11);

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 is present. , Fluorine or chlorine; h is 0, 1, or 2; i, j, and k are 0, 1, 2, 3, or 4, and i, j, and The sum of k is greater than or equal to 1;
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 11, which contains at least one compound selected from the compounds represented by the formulas (4-1) to (4-29) as the second additive. Stuff.

In formulas (4-1) to (4-29), P ¹² , P ¹³ , and P ¹⁴ are polymerizables selected from the groups represented by formulas (P-7) to (P-9). Is the basis;

Here, M ⁵ , M ⁶ , and M ⁷ 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; Sp. ⁵ , Sp ⁶ and Sp ⁷ are single-bonded or alkylenes having 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. The liquid crystal composition according to claim 11 or 12, wherein the proportion of the second additive 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 13. The liquid crystal display element according to claim 14, wherein the operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and the drive method of the liquid crystal display element is an active matrix method. A polymer-supported oriented liquid crystal display device containing the liquid crystal composition according to any one of claims 1 to 13 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 13 in a liquid crystal display element. Use of the liquid crystal composition according to any one of claims 1 to 13 in a polymer-supported oriented liquid crystal display device.