JP2020002230A - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

To provide a liquid crystal composition capable of achieving vertical alignment of liquid crystal molecules by an action of a polymer, and a liquid crystal display element comprising the composition.SOLUTION: A liquid crystal composition is a nematic liquid crystal composition containing a specific liquid crystalline compound having positively large dielectric anisotropy as a first component and a polar compound having a polymerizable group as a first additive. The composition may contain a specific liquid crystalline compound having a high maximum temperature or small viscosity as a second component, a specific liquid crystalline compound having positive dielectric anisotropy as a third component, a specific liquid crystalline compound having negative dielectric anisotropy as a fourth component, and a polymerizable compound as a second additive. The liquid crystal display element comprises the above composition.SELECTED DRAWING: None

Description

  The present invention relates to a liquid crystal composition having a positive dielectric anisotropy, a liquid crystal display device containing the composition, and the like. In particular, the present invention relates to a liquid crystal composition containing a polar compound having a polymerizable group (or a polymer thereof) and capable of achieving vertical alignment of liquid crystal molecules by the action of the compound, and a liquid crystal display device.

  In a liquid crystal display device, classification based on the operation mode of liquid crystal molecules includes PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), and IPS. (In-plane switching), VA (vertical alignment), FFS (fringe field switching), and FPA (field-induced photo-reactive alignment). Classifications based on the element driving method are PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex and the like, and AM is classified into TFT (thin film transistor), MIM (metal insulator metal) and the like. TFTs are classified into 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 reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both natural light and backlight.

  The liquid crystal display device contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the characteristics of this composition, an AM device having good characteristics can be obtained. The relationships between these properties are summarized in Table 1 below. The characteristics of the composition will be further described based on a commercially available AM device. 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 more, and the preferred lower limit temperature of the nematic phase is about −10 ° C. or less. The viscosity of the composition is related to the response time of the device. A short response time is preferable for displaying a moving image on the element. Shorter response times are desirable even at 1 ms. Therefore, a small viscosity in the composition is preferred. Small viscosities at low temperatures are more preferred. The elastic constant of the composition is related to the contrast of the device. In order to increase the contrast in the device, a large elastic constant of 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, large or small optical anisotropy, that is, appropriate optical anisotropy is required. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate value of the product depends on the type of operating mode. This value ranges from about 0.30 μm to about 0.40 μm for the VA mode device, and from about 0.20 μm to about 0.30 μm for the IPS mode or FFS mode device. In these cases, a composition having a large optical anisotropy is preferable for a device having a small cell gap. The large dielectric anisotropy in the composition contributes to a low threshold voltage, small power consumption and a large contrast ratio in the device. Therefore, a large dielectric anisotropy is preferable. A large specific resistance in the composition contributes to a large voltage holding ratio 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 preferred. The stability of the composition to ultraviolet light and heat is related to the lifetime of the device. When this stability is high, the lifetime of the device is long. Such characteristics are preferable for an AM device used for a liquid crystal monitor, a liquid crystal television and the like.

  In general-purpose liquid crystal display devices, vertical alignment of liquid crystal molecules is achieved by a specific polyimide alignment film. In a polymer sustained alignment (PSA) type liquid crystal display device, a polymer is combined with an alignment film. First, a composition to which a small amount of a polymerizable compound is added is injected into a device. Next, the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of the device. The polymerizable compound polymerizes to form a polymer network 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 image sticking is improved. Such effects of the polymer can be expected for devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and 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 to which a small amount of a polymerizable compound and a small amount of a polar compound are added is injected into a device. Here, the polar compound is adsorbed and arranged on the substrate surface of the element. The liquid crystal molecules are aligned according to this arrangement. Next, the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of the device. Here, the polymerizable compound is polymerized to stabilize the alignment of the liquid crystal molecules. In this composition, since the alignment of the liquid crystal molecules can be controlled by the polymer and the polar compound, the response time of the device is shortened and the image sticking is improved. Further, in the case of an element having no alignment film, a step of forming an alignment film is unnecessary. Since there is no alignment film, the electric resistance of the device does not decrease due to the interaction between the alignment film and the composition. Such an effect by the combination of the polymer and the polar compound can be expected for a device having a mode such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

  In an AM device having a TN mode, a composition having a positive dielectric anisotropy is used. In an AM device having a VA mode, a composition having a negative dielectric anisotropy is used. In an AM device having the IPS mode or the FFS mode, a composition having a positive or negative dielectric anisotropy is used. A composition having a positive or negative dielectric anisotropy is used in a polymer supported alignment type AM device. In a device having no alignment film, a composition having a positive or negative dielectric anisotropy is used. Compositions having a positive dielectric anisotropy are disclosed in the following Patent Documents 1 to 4. In the present invention, a polar compound having a polymerizable group (or a polymer thereof) is combined with a liquid crystal compound, and this composition is used for a liquid crystal display element having no alignment film.

JP-T-2013-541028 JP-T-2013-543526A JP 2014-513150 A International Publication No. 2014-94959

  An object of the present invention is to provide a liquid crystal composition containing a polar compound having a polymerizable group (or a polymer thereof), wherein the polar compound has high compatibility with the liquid crystal compound at a low temperature. Having. Another object is to provide a liquid crystal composition capable of achieving vertical alignment of liquid crystal molecules by the action of a polymer generated from the polar compound. Other issues are high upper temperature of nematic phase, lower lower temperature of nematic phase, small viscosity, appropriate optical anisotropy, positively large dielectric anisotropy, large specific resistance, high stability to ultraviolet light, heat An object of the present invention is to provide a liquid crystal composition that satisfies at least one of characteristics such as high stability and a large elastic constant. Another object is to provide a liquid crystal composition having a suitable balance between at least two of these properties. Another problem is a liquid crystal display device containing such a composition. Another object is to provide an AM device having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long life.

ここで、Ｒ^１などの記号の定義は、後述の項１を参照のこと。 The present invention provides at least one compound selected from the compounds represented by the formula (1) as the first component, and at least one compound selected from the polar compounds represented by the formula (2) as the first additive And a liquid crystal display device containing the composition.

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

  An advantage of the present invention is to provide a liquid crystal composition containing a polar compound having a polymerizable group (or a polymer thereof), wherein the polar compound has high compatibility with the liquid crystal compound at a low temperature. Having. Another advantage is to provide a liquid crystal composition capable of achieving vertical alignment of liquid crystal molecules by the action of a polymer generated from the polar compound. Another advantage is the high upper temperature limit of the nematic phase, the lower minimum temperature of the nematic phase, small viscosity, appropriate optical anisotropy, positively large dielectric anisotropy, large specific resistance, high stability to ultraviolet rays, heat resistance An object of the present invention is to provide a liquid crystal composition that satisfies at least one of characteristics such as high stability and a large elastic constant. Another advantage is to provide a liquid crystal composition having a suitable balance between at least two of these properties. Another advantage is a liquid crystal display device containing such a composition. Another advantage is to provide an AM device having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a 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. "Liquid crystal compound" is a compound having a liquid crystal phase such as a nematic phase or a smectic phase or a compound having no liquid crystal phase, but having a composition for the purpose of adjusting properties such as temperature range, viscosity and dielectric anisotropy of the nematic phase. It is a generic term for compounds that are mixed with products. This compound has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecule (liquid crystal molecule) is rod-like. "Polymerizable compound" is a compound added to form 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 an optically active compound and a polymerizable compound are added to the liquid crystal composition as needed. The ratio of the liquid crystal compound is represented by a mass percentage (% by mass) based on the mass of the liquid crystal composition containing no additive, even when the additive is added. The proportion of the additive is represented by a mass percentage (% by mass) based on the mass of the liquid crystal composition containing no additive. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total mass of the liquid crystal compound. The proportions of the polymerization initiator and the polymerization inhibitor are exceptionally expressed based on the mass of the polymerizable compound.

  The “maximum temperature of the nematic phase” may be abbreviated as “maximum temperature”. The “minimum temperature of the nematic phase” may be abbreviated as “minimum temperature”. The expression “increase the dielectric anisotropy” means that when the composition has a positive dielectric anisotropy, it means that the value increases to a positive value, and the composition has a negative dielectric anisotropy. For a thing, it means that its value increases negatively. "High specific resistance" means that the composition has a large specific resistance in an initial stage and has a large specific resistance after prolonged use. "High voltage holding ratio" means that the device has a large voltage holding ratio not only at room temperature but also near the upper limit temperature in the initial stage, and a large voltage not only at room temperature but also near the upper limit temperature after long-term use. Having a retention rate. The characteristics of the composition and the device may be examined by a time-dependent change test.

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 compound (1z) will be described as an example. In the formula (1z), the symbols α and β surrounded by a hexagon correspond to the rings α and β, respectively, and represent a ring such as a six-membered ring or a condensed ring. When the subscript 'x' is 2, two rings α exist. 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 two. This rule also applies to other symbols, such as the linking 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 substituted substituents. 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) exist on the ring β. Also in this case, the rule "may be the same or different" is applied. This rule is also applied when the symbol Ra is used for a plurality of compounds.

  In formula (1z), for example, an expression such as “Ra and Rb are alkyl, alkoxy, or alkenyl” means that Ra and Rb are independently selected from the group of alkyl, alkoxy, and alkenyl. Means Here, the group represented by Ra and the group represented by Rb may be the same or different.

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

The expression "at least one 'A'" means that the number of 'A' is arbitrary. The expression "at least one 'A' may be replaced by 'B'" means that when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is two. In more than one case, their positions can be selected without restriction. Sometimes expression is used _- "it may be replaced by -O- least one -CH 2". In this _case, -CH ₂ -CH ₂ -CH ₂ - it is, -CH ₂ nonadjacent - may be converted _-O-CH 2 -O- to by is replaced by -O-. However, adjacent -CH ₂ - is not replaced by -O-. This replacement is -O-O-CH ₂ - is because (peroxide) is produced.

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 include cyclic alkyl. Linear alkyls are preferred over branched alkyls. The same applies to terminal groups such as alkoxy and alkenyl. Regarding the configuration of 1,4-cyclohexylene, trans is preferable to cis for increasing the maximum temperature. Since 2-fluoro-1,4-phenylene is bilaterally asymmetric, there are leftward (L) and rightward (R) directions.

The same applies to divalent groups such as tetrahydropyran-2,5-diyl. The same applies to a bonding group such as carbonyloxy (—COO— or —OCO—).

  The present invention includes the following items.

式（１）および式（２）において、環Ａおよび環Ｂは、１，４−シクロヘキシレン、１，４−フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレン、ピリミジン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはテトラヒドロピラン−２，５−ジイルであり；環Ｃおよび環Ｄ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−１，５−ジイル、ナフタレン−２，６−ジイル、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、またはピリジン−２，５−ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１０のアルキル、炭素数２から１０のアルケニル、炭素数１から１０のアルコキシ、または炭素数２から１０のアルケニルオキシで置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｚ^１およびＺ^２は、単結合、エチレン、ビニレン、メチレンオキシ、カルボニルオキシ、またはジフルオロメチレンオキシであり；Ｚ^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−ＣＨ₂−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ₂ＣＨ₂−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、１、２、３、または４であり；ｂは、０、１、２、または３であり、そしてａおよびｂの和は４以下であり；ｃは、０、１、２、または３であり；Ｘ^１およびＸ^２は、水素またはフッ素であり；Ｙ^１は、フッ素、塩素、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルオキシであり；Ｓｐ¹およびＳｐ²は、単結合または炭素数１から１５のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ₂−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ₂ＣＨ₂−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；Ｍ¹、Ｍ²、Ｍ³、およびＭ⁴は、水素、フッ素、塩素、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；Ｒ^１は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルであり；Ｒ^２は、水素、炭素数１から１０のアルキル、炭素数１から１０のアルコキシ、または炭素数１から１０のアルコキシアルキルであり、これらの基において、少なくとも１つの−ＣＨ₂ＣＨ₂−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｒ^３は、式（２−ａ）、式（２−ｂ）、および式（２−ｃ）で表される基から選択された基であり；

式（２−ａ）、式（２−ｂ）、および式（２−ｃ）において、Ｓｐ^３およびＳｐ^４は、単結合または炭素数１から１５のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ₂−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ₂ＣＨ₂−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｒ^４は、水素、炭素数１から１０のアルキル、炭素数１から１０のアルコキシ、または炭素数１から１０のアルコキシアルキルであり；Ｓ^１およびＳ^２は、＞Ｃ＜であり；Ｘ^３は、−ＯＨ、−ＮＨ₂、−Ｎ（Ｒ^５）₂、−ＣＯＯＨ、−ＳＨ、または−Ｓｉ（Ｒ^５）₃であり、ここで、Ｒ^５は、水素または炭素数１から１０のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ₂−は、−Ｏ−で置き換えられてもよく、少なくとも１つの−ＣＨ₂ＣＨ₂−は、−ＣＨ＝ＣＨ−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 1. Liquid crystal containing at least one compound selected from compounds represented by formula (1) as a first component and at least one compound selected from polar compounds represented by formula (2) as a first additive Composition.

In the formulas (1) and (2), ring A and ring B are 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, and pyrimidine -2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; ring C and ring D are 1,4-cyclohexylene, 1,4-cyclohexyl Senylene, 1,4-phenylene, naphthalene-1,5-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6- Diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, Wherein at least one hydrogen is replaced by fluorine, chlorine, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 10 carbons, or alkenyloxy having 2 to 10 carbons And in these groups, at least one hydrogen may be replaced by fluorine or chlorine; Z ¹ and Z ² are a single bond, ethylene, vinylene, methyleneoxy, carbonyloxy or difluoromethyleneoxy Yes; Z ³ is a single bond or an alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, —CO—, —COO—, —OCO—, or — may be replaced by -OCOO-, at least one -CH ₂ CH ₂ - is, -CH = CH- or -C≡ And in these groups at least one hydrogen may be replaced by fluorine or chlorine; a is 1, 2, 3, or 4; b is 0, 1, 2, or 3, and the sum of a and b is 4 or less; c is 0, 1, 2 or be a 3,; ^{X 1} and ^{X 2} is hydrogen or fluorine; ^{Y 1} is Fluorine, chlorine, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen is fluorine or 2 carbon atoms replaced by chlorine 12 alkenyloxy; Sp ¹ and Sp ² is alkylene of 15 a single bond or 1 carbon atoms, the alkylene Oite, at least one of -CH ₂ -, -O -, - CO -, - COO -, - OCO-, or may be replaced by -OCOO-, at least one -CH ₂ CH ₂ - is —CH ＝ CH— or —C≡C—, in which at least one hydrogen may be replaced by fluorine or chlorine; M ¹ , M ² , M ³ , and M ⁴ is hydrogen, fluorine, chlorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine; R ¹ is 1 to 12 carbons alkyl, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons,; R ² is hydrogen, alkyl having 1 to 10 carbons, alkoxy having 10 carbon number of 1 or from 1 carbon atoms, 0 is an alkoxyalkyl, in these groups, at least one -CH ₂ CH ₂ - may be replaced by -CH = CH- or -C≡C-, and in the groups, at least one hydrogen May be replaced by fluorine or chlorine; R ³ is a group selected from the groups represented by formula (2-a), formula (2-b), and formula (2-c);

In the formulas (2-a), (2-b), and (2-c), Sp ³ and Sp ⁴ are each a single bond or an alkylene having 1 to 15 carbon atoms. -CH ₂ - is, -O -, - CO -, - COO -, - OCO-, or may be replaced by -OCOO-, at least one -CH ₂ CH ₂ - is, -CH = CH- or -C≡C-, in which at least one hydrogen may be replaced by fluorine or chlorine; R ⁴ is hydrogen, alkyl of 1 to 10 carbons, 1 carbon of 1 S ¹ and S ² are> C <; X ³ is —OH, —NH ₂ , —N (R ⁵ ) ₂ , — COOH, -SH, or Si ^(R 5) _3, wherein, ^{R 5} is hydrogen or alkyl having 1 to 10 carbon atoms, in the alkyl, at least one -CH ₂ - may be replaced by -O- , At least one —CH ₂ CH ₂ — may be replaced by —CH ＝ CH—, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine.

式（１−１）から式（１−１４）において、Ｒ^１は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルであり；Ｘ^１、Ｘ^２、Ｘ^４、Ｘ^５、Ｘ^６、Ｘ^７、Ｘ^８、Ｘ^９、Ｘ^１０、Ｘ^１１、Ｘ^１２、Ｘ^１３、Ｘ^１４およびＸ^１５は、水素またはフッ素であり；Ｙ^１は、フッ素、塩素、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルオキシである。 Item 2. Item 2. The liquid crystal composition according to item 1, comprising at least one compound selected from the compounds represented by formulas (1-1) to (1-14) as a first component.

In the formulas (1-1) to (1-14), R ¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons; X ¹ , X ^{1 2} , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ and X ¹⁵ are hydrogen or fluorine; Y ¹ is fluorine , Chlorine, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen is fluorine Or alkenyloxy having 2 to 12 carbon atoms replaced with chlorine.

式（２−１）から式（２−１８）において、Ｙ²、Ｙ³、Ｙ⁴、Ｙ⁵、Ｙ⁶およびＹ^７は、水素、フッ素、メチル、またはエチルであり；Ｚ^４およびＺ^５は、単結合または−ＣＨ₂ＣＨ₂−であり；Ｒ^４は、水素、炭素数１から１０のアルキル、炭素数１から１０のアルコキシ、または炭素数１から１０のアルコキシアルキルであり；Ｓ^１は、＞Ｃ＜であり；Ｓｐ¹、Ｓｐ^２、Ｓｐ^３、およびＳｐ^４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−ＣＨ₂−は、−Ｏ−で置き換えられてもよい。 Item 3. Item 3. The liquid crystal composition according to item 1 or 2, comprising at least one compound selected from the polar compounds represented by formulas (2-1) to (2-18) as a first additive.

In Formulas (2-1) to (2-18), Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and Y ⁷ are hydrogen, fluorine, methyl, or ethyl; and Z ⁴ and Z ⁵ It represents a single bond or -CH ₂ CH ₂ - and are; ^{R 4} is hydrogen, alkyl of 1 to 10 carbon atoms, alkoxyalkyl of alkoxy of 1 to 10 carbon atoms, or a carbon number of 1 to 10; ^{S 1} Is> C <; Sp ¹ , Sp ² , Sp ³ , and Sp ⁴ are a single bond or an alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is —O— May be replaced by

Item 4. Item 4. The liquid crystal composition according to any one of Items 1 to 3, wherein a ratio of the first component is in a range of 5% by mass to 55% by mass.

Item 5. Item 5. The liquid crystal composition according to any one of Items 1 to 4, wherein the proportion of the first additive is in the range of 0.05% by mass to 10% by mass.

式（３）において、Ｒ^６およびＲ^７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、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルであり；環Ｅおよび環Ｆは、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^６は、単結合、エチレン、ビニレン、メチレンオキシ、またはカルボニルオキシであり；ｄは、１、２、または３である。 Item 6. Item 6. The liquid crystal composition according to any one of items 1 to 5, comprising at least one compound selected from the compounds represented by formula (3) as the second component.

In the formula (3), R ⁶ and R ⁷ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen replaced with fluorine or chlorine. Ring E and ring F are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4 -Phenylene; Z ⁶ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; d is 1, 2, or 3.

式（３−１）から式（３−１３）において、Ｒ^６およびＲ^７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、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 7. Item 7. The liquid crystal composition according to any one of items 1 to 6, comprising at least one compound selected from the compounds represented by formulas (3-1) to (3-13) as a second component.

In the formulas (3-1) to (3-13), R ⁶ and R ⁷ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one of Hydrogen is alkenyl having 2 to 12 carbons in which hydrogen is replaced by fluorine or chlorine.

Item 8. Item 8. The liquid crystal composition according to item 6 or 7, 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、Ｒ^８は炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルであり；環Ｇは、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，３−ジフルオロ−１，４−フェニレン、２，６−ジフルオロ−１，４−フェニレン、ピリミジン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはテトラヒドロピラン−２，５−ジイルであり；Ｚ^７は、単結合、エチレン、ビニレン、またはカルボニルオキシであり；Ｘ^１６およびＸ^１７は、水素またはフッ素であり；Ｙ^８は、フッ素、塩素、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルオキシであり；ｅは、１、２、３、または４である。 Item 9. Item 10. The liquid crystal composition according to any one of items 1 to 8, comprising at least one compound selected from the compounds represented by formula (4) as a third component.

In the formula (4), R ⁸ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons; ring G is 1,4-cyclohexylene, 1,4 -Phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane Y is -2,5-diyl or tetrahydropyran-2,5-diyl; Z ⁷ is a single bond, ethylene, vinylene, or carbonyloxy; X ¹⁶ and X ¹⁷ are hydrogen or fluorine; ⁸ is fluorine, chlorine, at least one hydrogen alkyl having 1 carbon is replaced by fluorine or chlorine 12, at least one hydrogen fluorine or chlorine location Be replaced is alkoxy having 1 to 12 carbon atoms or at least one hydrogen having 2 to 12 carbons are replaced by fluorine or chlorine alkenyloxy,; e is 1, 2, 3, or 4.

式（４−１）から式（４−１６）において、Ｒ^８は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルである。 Item 10. Item 10. The liquid crystal composition according to any one of items 1 to 9, comprising at least one compound selected from the compounds represented by formulas (4-1) to (4-16) as a third component.

In the formulas (4-1) to (4-16), R ⁸ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons.

Item 11. Item 11. The liquid crystal composition according to item 9 or 10, wherein the proportion of the third component is in the range of 5% by mass to 50% by mass.

式（５）において、Ｒ^９およびＲ^１０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、または炭素数２から１２のアルケニルオキシであり；環Ｉおよび環Ｋ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Ｊ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^８およびＺ^９は、単結合、エチレン、ビニレン、メチレンオキシ、またはカルボニルオキシであり；ｆは、０、１、２、または３であり、ｇは、０または１であり、そしてｆとｇとの和は３以下である。 Item 12. Item 12. The liquid crystal composition according to any one of items 1 to 11, comprising at least one compound selected from the compounds represented by formula (5) as a fourth component.

In the formula (5), R ⁹ and R ¹⁰ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons. Ring I and ring K are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, wherein at least one hydrogen is replaced by fluorine or chlorine 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen is fluorine or Ring J is 2,3-difluoro-1,4-phenylene, 2-chloro B-3-Fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman -2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7- Diyl, or 1,1,6,7-tetrafluoroindan-2,5-diyl; Z ⁸ and Z ⁹ are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; 1, 2, or 3, g is 0 or 1, and the sum of f and g is 3 or less.

式（５−１）から式（５−３５）において、Ｒ^９およびＲ^１０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、または炭素数２から１２のアルケニルオキシである。 Item 13. Item 13. The liquid crystal composition according to any one of items 1 to 12, comprising at least one compound selected from the compounds represented by formulas (5-1) to (5-35) as a fourth component.

In the formulas (5-1) to (5-35), R ⁹ and R ¹⁰ represent hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon Alkenyloxy of the formulas 2 to 12;

Item 14. Item 14. The liquid crystal composition according to item 12 or 13, wherein the proportion of the fourth component is in the range of 3% by mass to 40% by mass.

式（６）において、環Ｌおよび環Ｕ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Ｔ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^１０およびＺ^１１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、そして少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ_３）−、または−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｐ^１、Ｐ^２、およびＰ^３は、項１に記載の式（２−ａ）、（２−ｂ）、および（２−ｃ）で表される基を含まない重合性基であり；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、そして少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；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以上である。 Item 15. Item 15. The liquid crystal composition according to any one of items 1 to 14, comprising at least one compound selected from the polymerizable compounds represented by the formula (6) as a second additive.

In the formula (6), ring L and ring U are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl Or pyridin-2-yl, wherein at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is fluorine or chlorine. May be replaced by alkyl having 1 to 12 carbons which is replaced by: T 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 atom is fluorine, chlorine, a carbon atom having 1 to 4 carbon atoms. 12 alkyl, 1 to 12 carbon alkoxy, or 1 to 12 carbon alkyl in which at least one hydrogen is replaced by fluorine or chlorine; Z ¹⁰ and Z ¹¹ may be a single bond or a carbon alkylene from C 1 10, in the alkylene, at least one of _-CH 2 -, -O -, - CO -, - COO-, or In may be replaced, and at least one _-CH 2 CH ₂ is -OCO- - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, or _{-C (CH 3) = C (} CH 3) - may be replaced by, in these groups, at least one hydrogen may be replaced by fluorine or ^chlorine; P 1, ^{P 2,} and ^{P 3} Is a polymerizable group that does not contain the groups represented by formulas (2-a), (2-b), and (2-c) described in item 1; Sp ⁵ , Sp ⁶ , and Sp ⁷ are A single bond or an alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — may be replaced with —O—, —COO—, —OCO—, or —OCOO— and at least one _-CH 2 CH - it may be replaced by -CH = CH- or -C≡C-, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; h is 0, 1 or 2 I, j, and k are 0, 1, 2, 3, or 4, and the sum of i, j, and k is 1 or more.

式（Ｐ−１）から式（Ｐ−５）において、Ｍ^５、Ｍ^６、Ｍ^７、Ｍ^８、Ｍ^９、Ｍ^１０、Ｍ^１１、Ｍ^１２、およびＭ^１３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 16. Item 16. The liquid crystal according to item 15, wherein in the formula (6), P ¹ , P ² , and P ³ are groups selected from the polymerizable groups represented by the formulas (P-1) to (P-5). Composition.

In the formulas (P-1) to (P-5), M ⁵ , M ⁶ , M ⁷ , M ⁸ , M ⁹ , M ¹⁰ , M ¹¹ , M ¹² , and M ¹³ represent hydrogen, fluorine, and carbon number. Alkyl of 1 to 5 or alkyl of 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine.

式（６−１）から式（６−２９）において、Ｐ^１、Ｐ^２、およびＰ^３は、式（Ｐ−１）から式（Ｐ−３）で表される重合性基から選択された基であり、

ここで、Ｍ^５、Ｍ^６、Ｍ^７、Ｍ^８、Ｍ^９、Ｍ^１０、Ｍ^１１、およびＭ^１２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、そして少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。 Item 17. Item 17. The liquid crystal according to any one of items 1 to 16, comprising at least one compound selected from polymerizable compounds represented by formulas (6-1) to (6-29) as a second additive. Composition.

In the formulas (6-1) to (6-29), P ¹ , P ² , and P ³ are selected from the polymerizable groups represented by the formulas (P-1) to (P-3). Group,

Here, M ⁵ , M ⁶ , M ⁷ , M ⁸ , M ⁹ , M ¹⁰ , M ¹¹ , and M ¹² are hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is fluorine or chlorine. Sp ⁵ , Sp ⁶ , and Sp ⁷ are a single bond or an alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is an alkylene having 1 to 5 carbon atoms. , —O—, —COO—, —OCO—, or —OCOO—, and at least one —CH ₂ CH ₂ — is replaced by —CH ＝ CH— or —C≡C—. And in these groups at least one hydrogen may be replaced by fluorine or chlorine.

Item 18. Item 18. The liquid crystal composition according to any one of items 15 to 17, wherein a ratio of the second additive is in a range of 0.03% by mass to 10% by mass.

Item 19. Item 18. A liquid crystal display device containing the liquid crystal composition according to any one of items 1 to 18.

Item 20. Item 20. The liquid crystal display element according to item 19, wherein the operation mode of the liquid crystal display element is an IPS mode, a TN mode, an FFS mode, or an FPA mode, and the driving method of the liquid crystal display element is an active matrix method.

Item 21. Item 15. A polymer supported alignment type liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 14, wherein the first additive contained in the liquid crystal composition is polymerized.

Item 22. Item 19. A polymer supported alignment type liquid crystal display device comprising the liquid crystal composition according to any one of Items 15 to 18, wherein the first additive and the second additive contained in the liquid crystal composition are polymerized. .

Item 23. Item 15. A liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 14, wherein the first additive contained in the liquid crystal composition is polymerized and has no alignment film.

Item 24. Item 18. A liquid crystal display device having no alignment film, comprising the liquid crystal composition according to any one of items 15 to 18, wherein the first additive and the second additive contained in the liquid crystal composition are polymerized.

Item 25. Item 19. Use of the liquid crystal composition according to any one of items 1 to 18 in a liquid crystal display device.

Item 26. Item 19. Use of the liquid crystal composition according to any one of items 1 to 18 in a polymer supported alignment type liquid crystal display device.

Item 27. Item 19. Use of the liquid crystal composition according to any one of items 1 to 18 in a liquid crystal display device having no alignment film.

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

  The present invention also includes the following items. (C) The above composition containing at least two compounds selected from the polar compounds represented by the above formula (2). (D) The above composition further containing a polar compound different from the polar compound represented by the above formula (2). (E) an optically active compound, an antioxidant, an ultraviolet absorber, a quencher, a dye, a defoaming agent, a polymerizable compound different from the polymerizable compound represented by the above formula (6), a polymerization initiator, and polymerization inhibition A composition as described above comprising one, two or at least three of the additives, such as agents, polar compounds. (F) An AM device containing the above composition. (G) A device containing the above composition and having a mode of TN, ECB, OCB, IPS, FFS, VA, or FPA. (H) A transmission type device containing the above composition. (I) Use of the above composition as a composition having a nematic phase. (J) Use of a composition prepared by adding an optically active compound to the above composition as an optically active composition.

  The composition of the present invention will be described in the following order. First, the composition of the composition will be described. Second, the main characteristics of the component compounds and the main effects of the compounds on the composition will be described. Third, combinations of component compounds in the composition, desirable ratios, and the basis thereof will be described. Fourth, a preferred embodiment 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 component compounds 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. The composition may contain additives. Additives include optically active compounds, antioxidants, ultraviolet 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 a liquid crystal compound. Composition A further contains, in addition to the liquid crystal compound selected from compound (1), compound (3), compound (4), and compound (5), other liquid crystal compounds, additives, and the like. Is also good. “Other liquid crystal compounds” are liquid crystal compounds different from compound (1), compound (3), compound (4), and compound (5). Such compounds are mixed into the composition for the purpose of further adjusting the properties.

  Composition B consists essentially of only a liquid crystal compound selected from compound (1), compound (3), compound (4), and compound (5). "Substantially" means that the composition B may contain additives, but does not contain other liquid crystal compounds. Composition B has a smaller number of component compounds than composition A. From the viewpoint of reducing costs, composition B is more preferable than composition A. Composition A is more preferable than composition B from the viewpoint that the properties can be further adjusted by mixing other liquid crystal compounds.

  Second, main characteristics of the component compounds and main effects of the compounds on the composition and the device will be described. Table 2 summarizes the main characteristics of the component compounds. 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 component compounds, and the symbol 0 (zero) means smaller than S (small).

  The main effects of the component compounds on the properties of the composition when the component compounds are mixed into the composition are as follows. Compound (1) increases the dielectric anisotropy. Compound (3) increases the maximum temperature or decreases the viscosity. Compound (4) increases the dielectric anisotropy and lowers the minimum temperature. Compound (5) increases the dielectric constant in the minor axis direction. Compound (5) is added for the purpose of adjusting the elastic constant of the composition and adjusting the voltage-transmittance curve of the device.

  The compound (2) is adsorbed on the substrate surface by the action of the polar group, and controls the alignment of the liquid crystal molecules. In order to obtain the desired effect, it is essential that the compound (2) has high compatibility with the liquid crystal compound. The compound (2) has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and has a rod-like molecular structure, which is most suitable for this purpose. The compound (6) is added for the purpose of making it more compatible with a polymer-supported alignment type device. Compound (2) or compound (6) gives a polymer by polymerization. This polymer stabilizes the orientation of liquid crystal molecules, thereby shortening the response time of the device and improving image burn-in. From the viewpoint of the alignment of liquid crystal molecules, the polymer of the compound (2) is effective. The polymer of the compound (6) is effective from the viewpoint of long-term stability. The combination of compound (2) and compound (6) is more effective. A synergistic effect can be expected with this combination. In this combination, better long-term stability than compound (2) alone can be expected.

  Third, combinations of component compounds in the composition, desirable ratios, and the basis thereof will be described. Preferred combinations of the component compounds are Compound (1) + Compound (2), Compound (1) + Compound (2) + Compound (3), Compound (1) + Compound (2) + Compound (4), Compound (1) ) + Compound (2) + compound (5), compound (1) + compound (2) + compound (6), compound (1) + compound (2) + compound (3) + compound (4), compound (1 ) + Compound (2) + compound (3) + compound (5), compound (1) + compound (2) + compound (3) + compound (6), compound (1) + compound (2) + compound (4) ) + Compound (5), compound (1) + compound (2) + compound (4) + compound (6), compound (1) + compound (2) + compound (5) + compound (6), compound (1 ) + Compound (2) + compound (3) + compound (4) + compound (5), compound (1) + compound (2) + compound 3) + Compound (4) + Compound (6), or compound (1) + Compound (2) + Compound (3) + Compound (4) + Compound (5) + Compound (6). More preferred combinations are compound (1) + compound (2) + compound (3), compound (1) + compound (2) + compound (3) + compound (4), compound (1) + compound (2) + Compound (3) + compound (6) or compound (1) + compound (2) + compound (3) + compound (4) + compound (6).

  The desirable ratio of the compound (1) is about 5% by mass or more for increasing the dielectric anisotropy, and about 55% by mass or less for decreasing the minimum temperature or decreasing the viscosity. A more desirable ratio is in the range of about 5% to about 45% by weight. A particularly desirable ratio is in the range of about 10% to about 35% by weight.

  The desirable ratio of the compound (2) is about 0.05% by mass or more for aligning liquid crystal molecules, and about 10% by mass or less for preventing display failure of the device. A more desirable ratio is in the range of about 0.1% to about 7% by weight. A particularly desirable ratio is in the range from about 0.5% to about 5% by weight.

  The desirable ratio of the compound (3) is about 10% by mass or more for increasing the maximum temperature or decreasing the viscosity, and about 90% by mass or less for increasing the dielectric anisotropy. A more desirable ratio is in the range of about 15% to about 85% by weight. A particularly desirable ratio is in the range from about 20% to about 80% by weight.

  A desirable ratio of the compound (4) is about 5% by mass or more for increasing the dielectric anisotropy, and about 50% by mass or less for lowering the minimum temperature. A more desirable ratio is in the range of about 5% to about 40% by weight. A particularly desirable ratio is in the range from about 5% to about 30% by weight.

  The desirable ratio of the compound (5) is about 3% by mass or more for increasing the dielectric constant in the minor axis direction, and about 40% by mass or less for decreasing the minimum temperature. A more desirable ratio is in the range of about 5% to about 35% by weight. A particularly desirable ratio is in the range of about 10% to about 35% by weight.

  The desirable ratio of the compound (6) is about 0.03% by mass or more in order to improve the long-term stability of the alignment, and is about 10% by mass or less in order to prevent display failure of the device. A more desirable ratio is in the range of about 0.1% to about 2% by weight. A particularly desirable ratio is in the range from about 0.2% to about 1.0% by weight.

  Fourth, a preferred embodiment of the component compounds will be described. First, the four liquid crystal compounds will be described together. Next, the first additive (a polar compound having a polymerizable group) and the second additive (a polymerizable compound) will be described in this order.

(A) Liquid crystal compound In the formulas (1), (3), (4), and (5), R ¹ represents alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or carbon It is an alkenyl of the formulas 2 to 12. Desirable R ¹ is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat. R ⁶ and R ⁷ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Alkenyl. Desirable R ⁶ or R ⁷ is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat, and alkenyl having 2 to 12 carbons for decreasing the minimum temperature or decreasing the viscosity. .

R ⁸ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons. Desirable R ⁸ is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat. R ⁹ and R ¹⁰ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons. Desirable R ⁹ or R ¹⁰ is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat, and alkoxy having 1 to 12 carbons for increasing the dielectric anisotropy.

  Preferred alkyls are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. More preferred alkyl is methyl, ethyl, propyl, butyl, or pentyl for decreasing the viscosity.

  Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. More preferred alkoxy is methoxy or ethoxy for decreasing the viscosity.

  Preferred alkenyls are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More preferred alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for decreasing the viscosity. The preferred configuration of -CH = CH- in these alkenyls depends on the position of the double bond. From the viewpoint of decreasing the viscosity, etc., trans is preferable in alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl. Cis is preferred in alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl.

  Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. More preferred alkenyloxy for decreasing the viscosity is allyloxy or 3-butenyloxy.

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

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

  Ring A and ring B are 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylenepyrimidine-2,5-diyl in which at least one hydrogen is replaced by fluorine or chlorine, 1,3-dioxane -2,5-diyl or tetrahydropyran-2,5-diyl. Desirable ring A or ring B is 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,6-difluoro-1,4-phenylene for increasing optical anisotropy. Ring E and ring F are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. Desirable ring E or ring F is 1,4-cyclohexylene for decreasing the viscosity, and 1,4-phenylene for increasing the optical anisotropy. Ring G is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene , Pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl. Desirable ring G is 1,4-phenylene or 2-fluoro-1,4-phenylene for increasing optical anisotropy.

  Ring I and ring K are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, and 1 or more in which at least one hydrogen is replaced by fluorine or chlorine. , 4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl, chroman-2,6-diyl wherein at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen is fluorine or chlorine Is chroman-2,6-diyl replaced by Preferred examples of "1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine" include 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, or 2-chloro -3-fluoro-1,4-phenylene. Desirable ring I or ring K is 1,4-cyclohexylene for decreasing the viscosity, tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and 1,4-phenylene.

好ましい環Ｊは、誘電率異方性を上げるために２，３−ジフルオロ−１，４−フェニレンである。 Ring J 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-tetrafluorofluoren-2,7-diyl (FLF4), 4,6- Difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2), or 1,1,6,7-tetrafluoroindan-2,5-diyl (InF4) It is.

Preferred ring J is 2,3-difluoro-1,4-phenylene for increasing the dielectric anisotropy.

Z ¹ and Z ² are a single bond, ethylene, vinylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy. Desirable Z ¹ or Z ² is a single bond for decreasing the viscosity. Z ⁶ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Desirable Z ⁶ is a single bond for decreasing the viscosity. Z ⁷ is a single bond, ethylene, vinylene, or carbonyloxy. Desirable Z ⁷ is a single bond for decreasing the viscosity. Z ⁸ and Z ⁹ are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Desirable Z ⁸ or Z ⁹ is a single bond for decreasing the viscosity, and methyleneoxy for increasing the dielectric anisotropy.

X ¹ , X ² , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ , X ¹⁶ , and X ¹⁷ are It is hydrogen or fluorine. X ¹ , X ² , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ , X ¹⁶ or X ¹⁷ are preferable. And fluorine for increasing the dielectric anisotropy.

Y ¹ and Y ⁸ are fluorine, chlorine, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, and alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Or alkenyloxy having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine. Desirable Y ¹ or Y ⁸ is fluorine for decreasing the minimum temperature. A preferred example of an alkyl in which at least one hydrogen is replaced by fluorine or chlorine is trifluoromethyl. A preferred example of alkoxy wherein at least one hydrogen is replaced by fluorine or chlorine is trifluoromethoxy. A preferred example of alkenyloxy in which at least one hydrogen has been replaced by fluorine or chlorine is trifluorovinyloxy.

  a is 1, 2, 3, or 4, b is 0, 1, 2, or 3, and the sum of a and b is 4 or less. Desirable a is 2 or 3 for increasing dielectric anisotropy. Desirable b is 0 or 1 for decreasing the minimum temperature. d is 1, 2, or 3. Desirable d is 1 for decreasing the viscosity, and 2 for decreasing the minimum temperature. e is 1, 2, 3, or 4. Desirable e is 2 or 3 for increasing dielectric anisotropy. f is 0, 1, 2, or 3, g is 0 or 1, and the sum of f and g is 3 or less. Desirable f is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature. Desirable g is 0 for decreasing the viscosity, and 1 for decreasing the minimum temperature.

(B) First additive The compound (2) is preferably stable to ultraviolet light and heat. When the compound (2) is added to the composition, the compound preferably does not lower the voltage holding ratio of the device. Compound (2) preferably has low volatility. The preferred molar mass is at least 130 g / mol. A more preferred molar mass ranges from 150 g / mol to 700 g / mol. Preferred compound (2) has a polymerizable group such as acryloyloxy (—OCO—CH ＝ CH ₂ ) and methacryloyloxy (—OCO— (CH ₃ ) C ＝ CH ₂ ).

式（２−ａ）、式（２−ｂ）、および式（２−ｃ）において、Ｓｐ^３およびＳｐ^４は、単結合または炭素数１から１５のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。好ましいＳｐ^３およびＳｐ^４は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよい。Ｒ^４は、水素、炭素数１から１０のアルキル、炭素数１から１０のアルコキシ、または炭素数１から１０のアルコキシアルキルであり、好ましいＲ^４は水素、炭素数１から７のアルキル、炭素数１から７のアルコキシ、または炭素数１から７のアルコキシアルキルである。Ｓ^１およびＳ^２は、＞Ｃ＜であり、Ｘ^３は、−ＯＨ、−ＮＨ_２、−Ｎ（Ｒ^５）_２、−ＣＯＯＨ、−ＳＨ、または−Ｓｉ（Ｒ^５）_３であり、ここで、Ｒ^５は、水素または炭素数１から１０のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−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。液晶組成物への高い溶解度の観点から、Ｘ^１は−ＯＨまたは−ＮＨ_２であることが特に好ましい。−ＯＨは、高いアンカー力を有するので−Ｏ−、−ＣＯ−、または−ＣＯＯ−よりも好ましい。複数のヘテロ原子（窒素、酸素）を有する基は、特に好ましい。そのような極性基を有する化合物は、低い濃度であっても有効である。 R ² is hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, or alkoxyalkyl having 1 to 10 carbons. In these groups, at least one —CH ₂ CH ₂ — is It may be replaced by -CH = CH- or -C 置 き 換 え C-, in which at least one hydrogen may be replaced by fluorine or chlorine. Desirable R ² is hydrogen, alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, or alkoxyalkyl having 1 to 5 carbons. More preferred R ² is alkyl having 1 to 5 carbons. R ³ is a group selected from the groups represented by the formulas (2-a), (2-b), and (2-c), and preferred R ³ is a group represented by the formula (2-a) or the formula (2-a). (2-b).

In the formulas (2-a), (2-b), and (2-c), Sp ³ and Sp ⁴ are each a single bond or an alkylene having 1 to 15 carbon atoms. -CH ₂ - is, -O -, - CO -, - COO -, - OCO-, or may be replaced by -OCOO-, at least one _-CH 2 CH ₂ - is, -CH = CH- or It may be replaced by -C≡C-, in which at least one hydrogen may be replaced by fluorine or chlorine. Preferred Sp ³ and Sp ⁴ are a single bond or an alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, —CO—, —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 the groups, at least one hydrogen , May be replaced by fluorine. R ⁴ is hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons or alkoxyalkyl having 1 to 10 carbons, and preferable R ⁴ is hydrogen, alkyl having 1 to 7 carbons, carbon number It is an alkoxy having 1 to 7 or an alkoxyalkyl having 1 to 7 carbon atoms. S ¹ and S ² are> C <, and X ³ is —OH, —NH ₂ , —N (R ⁵ ) ₂ , —COOH, —SH, or —Si (R ⁵ ) ₃ , where Wherein R ⁵ is hydrogen or alkyl having 1 to 10 carbons, in which at least one —CH ₂ — may be replaced by —O— and at least one —CH ₂ CH ₂ — May be replaced by -CH = CH-, in which at least one hydrogen may be replaced by fluorine or chlorine. From the viewpoint of high solubility in the liquid crystal composition, it is particularly preferred ^{X 1} is -OH or -NH _2. -OH is preferable to -O-, -CO-, or -COO- because it has a high anchoring force. Groups having more than one heteroatom (nitrogen, oxygen) are particularly preferred. The compound having such a polar group is effective even at a low concentration.

  Ring C and ring D are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,5-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2, 6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, Or pyridine-2,5-diyl, wherein at least one hydrogen is fluorine, chlorine, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 10 carbons, Or alkenyloxy having 2 to 10 carbon atoms, and in these groups, at least one hydrogen is replaced by fluorine or chlorine. Good. Preferred ring C and ring D are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3- Dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl or 3-ethyl-1,4-phenylene, in which at least one hydrogen is fluorine, It may be replaced by alkyl having 1 to 7 carbons, alkenyl having 2 to 7 carbons, or alkoxy having 1 to 7 carbons. Particularly preferred ring C and ring D are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, naphthalene-2,6-diyl, or 3-ethyl-1,4-phenylene It is.

Z ³ is a single bond or an alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is —O—, —CO—, —COO—, —OCO—, or —OCOO— And at least one —CH ₂ CH ₂ — may be replaced by —CH ＝ CH— or —C≡C—, in which at least one hydrogen is fluorine or chlorine May be replaced by Preferred ^{Z 3} is a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - CH = CH -, - C≡C -, - COO -, - OCO -, - CF 2 O -, - OCF ₂ —, —CH ₂ O—, —OCH ₂ —, or —CF ＝ CF—. More preferred Z ³ is a single bond or —CH ₂ CH ₂ —.

Sp ¹ and Sp ² are a single bond or alkylene having 1 to 15 carbon atoms, in which at least one —CH ₂ — is —O—, —CO—, —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 the groups, at least one of hydrogen, It may be replaced by fluorine or chlorine. Preferred Sp ¹ and Sp ² are a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — may be replaced by —O— and at least one —CH ₂ CH ₂ — may be replaced by —CH ＝ CH—. Further preferred Sp ¹ and Sp ² are a single bond or alkylene having 1 to 5 carbon atoms, in which at least one —CH ₂ — may be replaced by —O—.

M ¹ , M ² , M ³ , and M ⁴ are hydrogen, fluorine, chlorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced with fluorine or chlorine. . Desirable M ¹ , M ² , M ³ or M ⁴ is hydrogen or alkyl having 1 to 3 carbons.

  c is 0, 1, 2, or 3. Preferred c is 1 or 2.

In Formulas (2-1) to (2-18), Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , and Y ⁷ are hydrogen, fluorine, methyl, or ethyl.

(C) Second additive In formula (6), ring L and ring U are 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 having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least One hydrogen may be replaced by alkyl having 1 to 12 carbons replaced by fluorine or chlorine. Preferred ring L or ring U is phenyl.

  Ring T 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 fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is replaced by fluorine or chlorine. From the obtained 1 carbon atoms may be replaced by alkyl of 12. Preferred ring T is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ¹⁰ and Z ¹¹ are a single bond or an alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, —CO—, —COO—, or —OCO—. may be replaced, and at least one _-CH 2 CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, or -C (CH ₃ ) = C (CH ₃ ) —, in which at least one hydrogen may be replaced by fluorine or chlorine. Preferred ^{Z 10} or ^{Z 11} is a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or -OCO-. More preferred Z ¹⁰ or Z ¹¹ is a single bond.

In the formula (6), P ¹ , P ² and P ³ each represent a polymerizable group having no group represented by the formulas (2-a), (2-b) and (2-c) It is. The polymerizable group ^is no -OH, -OR _0, -NH 2, a polar group such as -NHR ⁰ or -N ^{(R 0)} _2,. Here, R ⁰ is alkyl having 1 to 12 carbons. Desirable P ¹ , P ² or P ³ is a group selected from the polymerizable groups represented by the formulas (P-1) to (P-5). More preferred P ¹ , P ² , or P ³ is a group represented by the formula (P-1), the formula (P-2), or the formula (P-3). Particularly preferred P ¹ , P ² or P ³ is a group represented by the formula (P-1) or the formula (P-2). Most preferred P ¹ , P ² , or P ³ is a group represented by the formula (P-1). A preferred group represented by the formula (P-1) is acryloyloxy (—OCO—CH ＝ CH ₂ ) or methacryloyloxy (—OCO—C (CH ₃ ) ＝ CH ₂ ). The wavy lines in the formulas (P-1) to (P-5) indicate binding sites.

In the formulas (P-1) to (P-5), M ⁵ , M ⁶ , M ⁷ , M ⁸ , M ⁹ , M ¹⁰ , M ¹¹ , M ¹² , and M ¹³ represent hydrogen, fluorine, and carbon number. Alkyl of 1 to 5 or alkyl of 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Preferred M ⁵ , M ⁶ , M ⁷ , M ⁸ , M ⁹ , M ¹⁰ , M ¹¹ , M ¹² or M ¹³ are hydrogen or methyl for increasing reactivity. More preferred M ⁵ , M ¹⁰ , or M ¹³ is hydrogen or methyl, and more preferred M ⁶ , M ⁷ , M ⁸ , M ⁹ , M ¹¹ , or M ¹² is hydrogen.

In the formula (6), Sp ⁵ , Sp ⁶ and Sp ⁷ are a single bond or an alkylene having 1 to 10 carbon atoms. In the alkylene, at least one of _-CH 2 -, -O -, - COO -, - OCO-, or may be replaced by -OCOO-, and at least one _-CH 2 CH ₂ - is, -CH = CH- or -C≡C-, in which at least one hydrogen may be replaced by fluorine or chlorine. Preferred Sp ⁵ , Sp ⁶ , or Sp ⁷ is a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CO—CH ＝ CH—, or -CH = CH-CO-. Further preferred Sp ⁵ , Sp ⁶ , or Sp ⁷ is a single bond.

  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 1 or more. Preferred i, j, and k are 1 or 2.

  Fifth, preferred component compounds are shown. Desirable compounds (1) are the compounds (1-1) to (1-14) described in item 2. In these compounds, at least one of the first components is a compound (1-3), a compound (1-4), a compound (1-7), a compound (1-9), a compound (1-10), or a compound (1-12) is preferable. At least two of the first components are compound (1-3) and compound (1-4), compound (1-3) and compound (1-7), compound (1-3) and compound (1-10), The compound (1-7) and the compound (1-10), or the combination of the compound (1-9) and the compound (1-10) are preferable.

Preferred compound (2) is compound (2-1) to compound (2-18) described in item 3. In these compounds, it is preferable that at least one of the first additives is a compound (2-1) to a compound (2-9). It is preferable that at least two of the first additives are a combination of the compound (2-1) and the compound (2-9).

  Desirable compounds (3) are the compounds (3-1) to (3-13) described in item 7. In these compounds, at least one of the second components is a compound (3-1), a compound (3-3), a compound (3-5), a compound (3-6), a compound (3-8), or a compound (3-13) is preferable. At least two of the second components are compound (3-1) and compound (3-3), compound (3-1) and compound (3-5), compound (3-1) and compound (3-8), Alternatively, a combination of the compound (3-3) and the compound (3-5) is preferable.

  Desirable compounds (4) are the compounds (4-1) to (4-16) described in item 10. In these compounds, at least one of the third components is compound (4-4), compound (4-8), compound (4-9), compound (4-11), compound (4-12), compound (4-12). 4-13) or compound (4-16). At least two of the third components are compound (4-9) and compound (4-12), compound (4-11) and compound (4-12), compound (4-12) and compound (4-13), Alternatively, a combination of the compound (4-12) and the compound (4-16) is preferable.

  Preferred compounds (5) are the compounds (5-1) to (5-35) described in item 13. In these compounds, at least one of the fourth components is a compound (5-1), a compound (5-3), a compound (5-6), a compound (5-8), a compound (5-10), a compound (5-10). 5-14) or compound (5-17). At least two of the first components are compound (5-1) and compound (5-8), compound (5-1) and compound (5-14), compound (5-3) and compound (5-8), Compound (5-3) and compound (5-14), compound (5-3) and compound (5-17), compound (5-6) and compound (5-8), compound (5-6) and compound A combination of (5-10), compound (5-6) and compound (5-17), compound (5-10) and compound (5-17) is preferable.

  Preferred compound (6) is the compound (6-1) to the compound (6-29) described in item 17. More preferred compound (6) includes compound (6-1), compound (6-2), compound (6-3), compound (6-4), compound (6-5), compound (6-6), Compound (6-7), compound (6-18), compound (6-20), compound (6-23), compound (6-24), compound (6-25), and compound (6-26) is there. Particularly preferred compound (6) is compound (6-2), compound (6-3), compound (6-4), and compound (6-18).

  Sixth, additives other than the first and second additives that may be added to the composition will be described. Such additives include optically active compounds, antioxidants, ultraviolet 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 a compound are the compound (7-1) to the compound (7-5). A desirable ratio of the optically active compound is about 5% by mass or less. A more desirable ratio is in the range of about 0.01% to about 2% by weight.

An antioxidant is used to prevent a decrease in specific resistance due to heating in the atmosphere, or to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after using the device for a long time. Added to the product. Preferred examples of the antioxidant include compound (8-1) to compound (8-3).

  Since the compound (8-2) has low volatility, it is effective to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after using the device for a long time. A desirable ratio of the antioxidant is about 50 ppm or more to obtain the effect, and about 600 ppm or less so as not to lower the upper limit temperature or increase the lower limit temperature. A more desirable ratio is in the range of about 100 ppm to about 300 ppm.

  Preferred examples of the ultraviolet absorber include a benzophenone derivative, a benzoate derivative, and a triazole derivative. Light stabilizers such as sterically hindered amines are also preferred. Preferred examples of the light stabilizer include compound (9-1) to compound (9-16). A preferable ratio in these absorbents and stabilizers is about 50 ppm or more for obtaining the effect, and about 10,000 ppm or less so as not to lower the upper limit temperature or increase the lower limit temperature. A more desirable ratio is in the range of about 100 ppm to about 10,000 ppm.

  The quencher is a compound that receives the light energy absorbed by the liquid crystal compound and converts it into heat energy, thereby preventing the decomposition of the liquid crystal compound. Preferred examples of the quencher include compound (10-1) to compound (10-7). The preferable ratio in these quenchers is about 50 ppm or more for obtaining the effect, and about 20,000 ppm or less for not raising the minimum temperature. A more desirable ratio is in the range of about 100 ppm to about 10,000 ppm.

  A dichroic dye such as an azo dye or an anthraquinone dye is added to the composition in order to make the device compatible with a device of a GH (guest host) mode. A preferred proportion of the dye ranges from about 0.01% to about 10% by weight. To prevent foaming, antifoaming agents such as dimethyl silicone oil, methyl phenyl silicone oil and the like are added to the composition. A desirable ratio of the defoaming agent is about 1 ppm or more for obtaining the effect, and about 1000 ppm or less for preventing display defects. A more desirable ratio is in the range of about 1 ppm to about 500 ppm.

  A polymerizable compound is used for adapting to a polymer supported alignment (PSA) type device. Compound (2) and compound (6) are suitable for this purpose. Along with compound (2) and compound (6), a polymerizable compound different from compound (2) and compound (6) may be added to the composition. Preferred examples of such a polymerizable compound include compounds such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), and vinyl ketone. Further preferred examples are acrylates or methacrylates. A desirable ratio of the compound (2) and the compound (6) is about 10% by mass or more based on the total mass of the polymerizable compound. A more desirable ratio is about 50% by mass or more. A particularly desirable ratio is about 80% by mass or more. A particularly desirable ratio is also 100% by mass. The reactivity of the polymerizable compound or the liquid crystal is changed by changing the type of the compound (2) and the compound (6), or by combining the compound (2) and the compound (6) with another polymerizable compound in an appropriate ratio. The pretilt angle of the molecule can be adjusted. By optimizing the pretilt angle, a short response time of the device can be achieved. Since the alignment of the liquid crystal molecules is stabilized, a large contrast ratio and a long lifetime can be achieved.

  This polymerizable compound is polymerized by irradiation with ultraviolet light. The polymerization may be carried out in the presence of a suitable initiator such as a photopolymerization initiator. The appropriate conditions for the polymerization, the appropriate type of initiator, and the appropriate amounts are known to those skilled in the art and are described in the literature. For example, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF) which is a photopolymerization initiator is suitable for radical polymerization. A preferred ratio of the photopolymerization initiator is in a range from about 0.1% to about 5% by weight based on the total weight of the polymerizable compound. A more desirable ratio is in the range of about 1% to about 3% by weight.

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

The polar compound is an organic compound having polarity. Here, a compound having an ionic bond is not included. Atoms such as oxygen, sulfur, and nitrogen are more electronegative and tend to have a partial negative charge. Carbon and hydrogen tend to be neutral or have a partial positive charge. Polarity results from the non-uniform distribution of partial charges between different types of atoms in a compound. For example, polar compounds have _{-OH, -COOH, -SH, -NH 2} ,> NH, at least one of the> N-moiety like.

  Seventh, a method for synthesizing component compounds will be described. These compounds can be synthesized by known methods. The synthesis method is exemplified. Compound (1-4) and compound (1-10) are synthesized by the method described in JP-A-10-251186. The method for synthesizing compound (2) is described in the Examples section. Compound (3-1) is synthesized by the method described in JP-A-59-176221. Compound (4-4) and compound (4-8) are synthesized by the method described in JP-A-2-233626. Compound (5-1) and compound (5-8) are synthesized by the method described in JP-T-2-503441. Compound (6-18) is synthesized by the method described in JP-A-7-101900. Compound (8-1) can be obtained from Aldrich (Sigma-Aldrich Corporation). Compound (8-2) and the like are synthesized by the method described in US Pat. No. 3,660,505.

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

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

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

  An example of a method for manufacturing a polymer-supported orientation type device is as follows. An element having two substrates called an array substrate and a color filter substrate is prepared. This substrate has an alignment film. At least one of the substrates has an electrode layer. A liquid crystal composition is prepared by mixing a liquid crystal compound. A polymerizable compound is added to the composition. If necessary, additives may be further added. This composition is injected into the device. Light irradiation is performed with a voltage applied to this element. Ultraviolet light is preferred. The polymerizable compound is polymerized by light irradiation. The polymerization produces a composition containing the polymer. The polymer-supported orientation-type device is manufactured by such a procedure.

  In this procedure, when a voltage is applied, the liquid crystal molecules are aligned by the action of the alignment film and the electric field. The molecules of the polymerizable compound are also oriented according to this orientation. In this state, the polymerizable compound is polymerized by ultraviolet rays, so that a polymer maintaining this orientation is generated. The effect of the polymer shortens the response time of the device. Since image sticking is a malfunction of liquid crystal molecules, sticking is also improved by the effect of this polymer. It should be noted that the polymerizable compound in the composition may be preliminarily polymerized, and the composition may be disposed between the substrates of the liquid crystal display device.

  When a polar compound having a polymerizable group such as the compound (2) is used, an alignment film is not required on the substrate of the device. Devices without alignment films are manufactured from substrates without alignment films according to the procedure described in the two preceding paragraphs.

  In this procedure, compound (2) is arranged on the substrate because the polar group interacts with the substrate surface. The liquid crystal molecules are aligned according to this arrangement. When a voltage is applied, the alignment of liquid crystal molecules is further promoted. In this state, the polymerizable group is polymerized by ultraviolet rays, so that a polymer maintaining this orientation is produced. The effect of the polymer additionally stabilizes the orientation of the liquid crystal molecules and shortens the response time of the device. Since image sticking is a malfunction of liquid crystal molecules, sticking is also improved by the effect of this polymer.

  The present invention will be described in more detail by way of examples. The invention is not limited by these examples. The present invention includes a mixture of the composition (M1) and the composition (M2). The 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 characteristics of the compound, the composition and the device were measured by the following methods.

NMR analysis: For measurement, DRX-500 manufactured by Bruker Biospin was used. ^{In the 1} H-NMR measurement, the sample was dissolved in a deuterated solvent such as CDCl _3, and the measurement was performed at room temperature under the conditions of 500 MHz and 16 accumulations. Tetramethylsilane was used as an internal standard. ^In the measurement of ¹⁹ F-NMR, CFCl ₃ was used as an internal standard, and the measurement was performed 24 times. 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 Chromatography Analysis: A GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for measurement. The carrier gas is helium (2 mL / min). The sample vaporization chamber was set at 280 ° C, and the detector (FID) was set at 300 ° C. For separation of the component compounds, a capillary column DB-1 manufactured by Agilent Technologies Inc. (length: 30 m, inner diameter: 0.32 mm, film thickness: 0.25 μm; stationary liquid phase: dimethylpolysiloxane; nonpolar) was used. The column was kept at 200 ° C. for 2 minutes and then heated to 280 ° C. at a rate of 5 ° C./min. A sample was prepared in an acetone solution (0.1% by mass), and 1 μL of the solution was injected into a sample vaporization chamber. The recorder is a Chromatopac Model C-R5A manufactured by Shimadzu Corporation or its equivalent. The resulting gas chromatogram showed the peak retention time and peak area corresponding to the component compounds.

  A solvent such as chloroform or hexane may be used to dilute the sample. The following capillary column may be used to separate the component compounds. Agilent Technologies Inc. HP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm), Restek Corporation Rtx-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm), BP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by SGE International Pty. Ltd. For the purpose of preventing compound peaks from overlapping, 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.

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

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

The following mother liquid crystals were used. The ratios of the component compounds are shown by mass%.

  Measurement method: The characteristics were measured by the following methods. Most of these methods are described in the JEITA standard (JEITA ED-2521B) established by the Japan Electronics and Information Technology Industries Association (JEITA), or modified methods thereof. Met. No thin film transistor (TFT) was attached to the TN device used for the measurement.

(1) Maximum temperature of nematic phase (NI; ° C.): A sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature when a part of the sample changed from a nematic phase to an isotropic liquid was measured. The maximum temperature of the nematic phase may be abbreviated as “maximum 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, when the sample remained in a nematic phase at −20 ° C. and changed to a crystalline or smectic phase at −30 ° C., _TC was described as <−20 ° C. The minimum temperature of the nematic phase may be abbreviated as “minimum temperature”.

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

(4) Viscosity (rotational viscosity; γ1; measured at 25 ° C .; mPa · s): Measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). Followed. A sample was placed in a TN device having a twist angle of 0 ° and a distance (cell gap) between two glass substrates of 5 μm. A voltage was applied to this device stepwise in the range of 16V to 19.5V at 0.5V intervals. After no application for 0.2 seconds, application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). A peak current and a peak time of a transient current generated by this application were measured. These measurements and M.P. The rotational viscosity value was obtained from the calculation formula (8) on page 40 of Imai et al. The dielectric anisotropy required for this calculation was measured by the method described in Measurement (6).

(5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25 ° C.): The measurement was performed using an Abbe refractometer having a polarizing plate attached to an eyepiece using light having a wavelength of 589 nm. After rubbing the surface of the main prism in one direction, a sample was dropped on the main prism. The refractive index n‖ was measured when the direction of polarized light was parallel to the direction of rubbing. The refractive index n⊥ was measured when the direction of polarized light was perpendicular to the direction of rubbing. The value of the optical anisotropy was calculated from the equation: Δn = n∥−n⊥.

(6) Dielectric anisotropy (Δε; measured at 25 ° C.): A sample was placed in a TN device in which a distance (cell gap) between two glass substrates was 9 μm and a twist angle was 80 degrees. A sine wave (10 V, 1 kHz) was applied to the device, and a dielectric constant (ε‖) in a major axis direction of the liquid crystal molecule was measured after 2 seconds. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε （) of the liquid crystal molecules in the minor axis direction was measured. The value of the dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.

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

(8) Voltage holding ratio (initial VHR; measured at 60 ° C .;%): A sample was sealed in a VA device on a glass substrate having no alignment film. The distance (cell gap) between the two glass substrates was 3.5 μm. The device was sealed with an adhesive that cured with ultraviolet light after the sample was injected. The VA element was charged by applying a pulse voltage (1 V, 60 microseconds). The decaying voltage was measured for 1667 milliseconds using a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined. The area B was the area when there was no attenuation. The voltage holding ratio was expressed as a percentage of the area A to the area B.

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

(10) Voltage holding ratio (heating VHR; measured at 60 ° C .;%): After heating the VA element into which the sample was injected, the voltage holding ratio was measured, and the stability to heat was evaluated. For the measurement, a VA element on a glass substrate having no alignment film was used, and the distance (cell gap) between the two glass substrates was 3.5 μm. A sample was injected into the device, and heated in a thermostat at 140 ° C. for 1 hour. Then, the measurement of the heating VHR was performed under the same measurement conditions as the initial VHR. A composition having a large heated VHR has a large stability to heat. The heating VHR is preferably at least 90%, more preferably at least 95%.

(12) Response time (τ; measured at 25 ° C .; ms): An LCD5100 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 at 5 kHz. A sample was put in an FFS element in which an interval (cell gap) between two glass substrates was 3.5 μm and no alignment film was provided. The device was sealed with an ultraviolet-curable adhesive. The device was irradiated with ultraviolet rays of 78 mW / cm ² (405 nm) for 359 seconds (28 J) while applying a voltage of 30 V. For ultraviolet irradiation, a multi-metal lamp for ultraviolet curing, M04-L41, manufactured by Eye Graphics Co., Ltd. was used. A rectangular wave (120 Hz) was applied to this device. At this time, the device was irradiated with light from a vertical direction, and the amount of light transmitted through the device was measured. The maximum light amount was considered to be 100% transmittance, and the minimum light amount was considered to be 0% transmittance. The maximum voltage of the rectangular wave was set so that the transmittance was 90%. The minimum voltage of the rectangular wave was set to 2.5 V at which the transmittance was 0%. The response time was represented by the time required for the transmittance to change from 90% to 10% (fall time; millisecond).

(13) Elastic constant (K; measured at 25 ° C .; pN): An HP4284A LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd. was used for the measurement. A sample was placed in a horizontal alignment element in which a distance (cell gap) between two glass substrates was 20 μm. A charge of 0 to 20 volts was applied to the device, and the capacitance and applied voltage were measured. The measured values of the capacitance (C) and the applied voltage (V) were fitted using the equations (2.98) and (2.101) on page 75 of “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun). Then, the values of K11 and K33 were obtained from the equation (2.99). Next, K22 was calculated using the values of K11 and K33 obtained previously in equation (3.18) on page 171. The elastic constant K was represented by the average value of K11, K22, and K33 thus determined.

(14) Specific resistance (ρ; measured at 25 ° C .; Ωcm): 1.0 mL of a sample was placed in a container equipped with electrodes. A DC voltage (10 V) was applied to the container, and a DC current after 10 seconds was measured. The specific resistance was calculated from the following equation. (Specific resistance) = {(voltage) × (electrical capacity of container)} / {(direct current) × (dielectric constant of vacuum)}.

(15) Pretilt Angle A spectroscopic ellipsometer M-2000U (manufactured by JA Woollam Co., Inc.) was used for measuring the pretilt angle.

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

[Synthesis Example 1]
Synthesis of Compound (PC-1)

First Step Compound (T-1) (40 g), triethylamine (33.7 ml) and dimethylformamide (DMF) (3000 ml) were charged into a reactor and cooled to 0 ° C. Compound (T-2) (23.19 g) was added thereto, and the mixture was stirred for 12 hours while returning to room temperature. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate = 1: 1) to obtain compound (T-3) (2.69 g; 5%).

Step 2 Compound (T-3) (5.0 g), compound (T-4) (4.19 g), DMAP (1.15 g), and dichloromethane (55.0 ml) were placed in a reactor and brought to 0 ° C. Cool. A solution of DCC (5.8 g) in dichloromethane (30.0 ml) was slowly added dropwise thereto, and the mixture was stirred for 12 hours while returning to room temperature. After filtering off the insoluble matter, the reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate = 9: 1) to obtain compound (T-5) (5.03 g; 58%). THP represents a tetrahydropyranyl group.

Step 3 Compound (T-5) (5.03 g), pyridinium p-toluenesulfonate (PPTS) (1.45 g), THF (25.0 ml), and methanol (25.0 ml) were charged into a reactor, Stirred at 50 ° C. for 4 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 2: 1). Further purification was performed by recrystallization from heptane to obtain compound (PC-1) (2.73 g; 67%).

The NMR analysis value of the obtained compound (PC-1) is as follows.
¹ H-NMR: chemical shift δ (ppm; CDCl ₃ ): 6.23 (s, 1H), 6.07 (s, 1H), 5.80 (d, J = 1.1 Hz, 1H), 5. 53 (t, J = 1.6 Hz, 1H), 4.79-4.65 (m, 2H), 4.32 (d, J = 6.8 Hz, 2H), 2.30 (t, J = 6 .6 Hz, 1H), 2.09-2.00 (m, 4H), 1.93 (s, 3H), 1.85-1.76 (m, 4H), 1.43-1.31 (m , 4H), 1.19-1.07 (m, 6H).
Transition temperature: C 119 (Polymerization initiation temperature: 123 ° C)

  (2-18) can be synthesized from compound (2-1) while referring to the method described in Synthesis Examples.

  Examples of the composition are shown below. The component compounds were represented by symbols based on the definitions in Table 3 below. In Table 3, the configuration for 1,4-cyclohexylene is trans. The number in parentheses after the symbolized compound indicates the chemical formula to which the compound belongs. The symbol (-) means other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is a percentage by mass (% by mass) based on the mass of the liquid crystal composition containing no additive. Finally, the characteristic values of the composition were summarized.

Example 1 of device Raw Materials A liquid crystal composition to which a first additive (polar compound) and a second additive (polymerizable compound) were added was injected into an element having no alignment film. After applying ultraviolet light while applying a voltage, the vertical alignment of liquid crystal molecules in this device was examined. Whether or not the liquid crystal molecules were sufficiently aligned was determined by a light leakage test. This is because no light leakage is observed when the vertical alignment is achieved. First, the raw materials will be described. The raw materials were appropriately selected from compositions (M1) to (M13), polar compounds (PC-1) to (PC-12), and polymerizable compounds (RM-1) to (RM-8). The composition was as follows:

Composition (M1)
5-HXB (F, F) -F (1-1) 3%
3-HHXB (F, F) -F (1-2) 6%
3-BB (F, F) XB (F, F) -F (1-4) 6%
3-BB (2F, 3F) XB (F, F) -F (1-4) 4%
3-HHB (F, F) XB (F, F) -F (1-5) 4%
3-HBB (2F, 3F) XB (F, F) -F (1-7) 5%
5-BB (F) B (F, F) XB (F) B (F, F) -F (1-14) 2%
3-HH-V (3-1) 22%
3-HH-V1 (3-1) 10%
5-HB-O2 (3-2) 5%
3-HHEH-3 (3-4) 3%
3-HBB-2 (3-6) 7%
5-B (F) BB-3 (3-7) 3%
3-HB-CL (4-1) 3%
3-HHB-OCF3 (4-3) 3%
3-HGB (F, F) -F (4-6) 3%
3-HB (F) B (F, F) -F (4-9) 5%
3-HHBB (F, F) -F (4-14) 6%
NI = 77.2 ° C .; Tc <−20 ° C .; Δn = 0.101; Δε = 5.8; Vth = 1.88 V; η = 13.7 mPa · s;

Composition (M2)
5-HXB (F, F) -F (1-1) 6%
3-HHXB (F, F) -F (1-2) 6%
2-BB (F) B (F, F) XB (F) -F (1-10) 3%
3-BB (F) B (F, F) XB (F) -F (1-10) 3%
4-BB (F) B (F, F) XB (F) -F (1-10) 4%
2-HH-5 (3-1) 8%
3-HH-V (3-1) 10%
3-HH-V1 (3-1) 7%
4-HH-V (3-1) 10%
4-HH-V1 (3-1) 8%
5-HB-O2 (3-2) 7%
4-HHEH-3 (3-4) 3%
V2-BB (F) B-1 (3-8) 3%
5-HB-CL (4-1) 5%
V-HB (F) B (F, F) -F (4-9) 5%
3-HHB (F) B (F, F) -F (4-15) 7%
1O1-HBBH-3 (-) 5%
NI = 78.5 ° C .; Tc <−20 ° C .; Δn = 0.095; Δε = 3.4; Vth = 1.50 V; η = 8.4 mPa · s; γ 1 = 54.2 mPa · s.

Composition (M3)
3-HHXB (F, F) -F (1-2) 7%
3-BB (F, F) XB (F, F) -F (1-4) 10%
5-HHB (F, F) XB (F, F) -F (1-5) 6%
3-HBB (2F, 3F) XB (F, F) -F (1-7) 5%
2-HH-3 (3-1) 8%
3-HH-V (3-1) 20%
3-HH-V1 (3-1) 7%
4-HH-V (3-1) 6%
5-HB-O2 (3-2) 5%
V2-B2BB-1 (3-9) 3%
3-HHEBH-3 (3-11) 5%
3-HHEBH-5 (3-11) 5%
3-HHEB (F, F) -F (4-5) 5%
5-HBEB (F, F) -F (4-10) 5%
2-HHB (F) B (F, F) -F (4-15) 3%
NI = 90.3 ° C .; Tc <−20 ° C .; Δn = 0.0088; Δε = 5.4; Vth = 1.69V; η = 13.7 mPa · s; γ 1 = 60.6 mPa · s.

Composition (M4)
3-BB (F, F) XB (F, F) -F (1-4) 12%
3-HBBXB (F, F) -F (1-7) 3%
3-BB (F) B (F, F) XB (F) -F (1-10) 3%
3-BB (F) B (F, F) XB (F, F) -F (1-10) 3%
4-BB (F) B (F, F) XB (F, F) -F (1-10) 5%
5-BB (F) B (F, F) XB (F, F) -F (1-10) 4%
2-HH-3 (3-1) 6%
3-HH-5 (3-1) 6%
3-HH-V (3-1) 25%
3-HH-VFF (3-1) 6%
5-HB-O2 (3-2) 7%
V-HHB-1 (3-5) 6%
V-HBB-2 (3-6) 5%
3-HHBB (F, F) -F (4-14) 5%
4-HHBB (F, F) -F (4-14) 4%
NI = 78.3 ° C .; Tc <−20 ° C .; Δn = 0.107; Δε = 7.0; Vth = 1.55V; η = 11.6 mPa · s; γ1 = 55.6 mPa · s.

Composition (M5)
3-HHXB (F, F) -F (1-2) 6%
3-BB (F, F) XB (F, F) -F (1-4) 8%
3-BB (F) B (F, F) XB (F, F) -F (1-10) 3%
4-BB (F) B (F, F) XB (F, F) -F (1-10) 6%
5-BB (F) B (F, F) XB (F, F) -F (1-10) 5%
3-HH-V (3-1) 30%
3-HH-V1 (3-1) 5%
3-HHB-O1 (3-5) 2%
V-HHB-1 (3-5) 5%
2-BB (F) B-3 (3-8) 6%
3-HHBB (F, F) -F (4-14) 5%
4-HHBB (F, F) -F (4-14) 4%
F3-HH-V (-) 15%
NI = 82.0 ° C .; Tc <−20 ° C .; Δn = 0.104; Δε = 5.7; Vth = 1.43V; η = 11.8 mPa · s; γ1 = 62.1 mPa · s.

Composition (M6)
3-GB (F, F) XB (F, F) -F (1-3) 5%
3-HGB (F, F) XB (F, F) -F (1-6) 5%
2-dhBB (F, F) XB (F, F) -F (1-8) 4%
3-dhB (F, F) B (F, F) XB (F) B (F, F) -F (1-13) 3%
3-BB (2F, 5F) B-3 (3) 3%
2-HH-3 (3-1) 14%
2-HH-5 (3-1) 4%
3-HH-V (3-1) 26%
1V2-HH-3 (3-1) 5%
1V2-BB-1 (3-3) 3%
3-HB (F) HH-2 (3-10) 4%
5-HBB (F) B-2 (3-13) 6%
7-HB (F, F) -F (4-2) 3%
3-HGB (F, F) -F (4-6) 3%
5-GHB (F, F) -F (4-7) 4%
3-BB (F) B (F, F) -CF3 (4-13) 2%
3-HHBB (F, F) -F (4-14) 4%
3-GBB (F) B (F, F) -F (4-16) 2%
NI = 78.3 ° C .; Tc <−20 ° C .; Δn = 0.094; Δε = 5.9; Vth = 1.25 V; η = 12.8 mPa · s;

Composition (M7)
3-BB (F) B (F, F) XB (F, F) -F (1-10) 3%
4-BB (F) B (F, F) XB (F, F) -F (1-10) 5%
3-BB (F, F) XB (F) B (F, F) -F (1-12) 3%
5-BB (F) B (F, F) XB (F) B (F, F) -F (1-14) 4%
2-HH-5 (3-1) 8%
3-HH-V (3-1) 25%
3-HH-V1 (3-1) 7%
4-HH-V1 (3-1) 6%
5-HB-O2 (3-2) 5%
7-HB-1 (3-2) 5%
VFF-HHB-O1 (3-5) 8%
VFF-HHB-1 (3-5) 3%
3-HH2BB (F, F) -F (4) 3%
4-HH2BB (F, F) -F (4) 3%
3-HBB (F, F) -F (4-8) 5%
5-HBB (F, F) -F (4-8) 4%
3-BB (F) B (F, F) -F (4-12) 3%
NI = 80.0 ° C .; Tc <−20 ° C .; Δn = 0.101; Δε = 4.6; Vth = 1.71 V; η = 11.0 mPa · s; γ 1 = 47.2 mPa · s.

Composition (M8)
3-BB (F, F) XB (F, F) -F (1-4) 10%
3-GB (F) B (F, F) XB (F, F) -F (1-9) 6%
5-GB (F, F) XB (F) B (F, F) -F (1-11) 5%
5-HBBH-3 (3) 5%
3-HH-V (3-1) 30%
3-HH-V1 (3-1) 10%
1V2-HH-3 (3-1) 8%
3-HH-VFF (3-1) 8%
V2-BB-1 (3-3) 2%
5-HB (F) BH-3 (3-12) 5%
3-HHB (F, F) -F (4-4) 8%
3-GB (F) B (F, F) -F (4-11) 3%
NI = 76.6 ° C .; Tc <−20 ° C .; Δn = 0.0088; Δε = 5.5; Vth = 1.81 V; η = 12.1 mPa · s; γ 1 = 60.2 mPa · s.

Composition (M9)
3-HHB (F, F) XB (F, F) -F (1-5) 5%
5-HHB (F, F) XB (F, F) -F (1-5) 3%
3-HGB (F, F) XB (F, F) -F (1-6) 5%
3-GB (F) B (F, F) XB (F, F) -F (1-9) 5%
4-GB (F) B (F, F) XB (F, F) -F (1-9) 5%
2-HH-5 (3-1) 3%
3-HH-5 (3-1) 5%
3-HH-V (3-1) 24%
4-HH-V (3-1) 5%
1V2-HH-3 (3-1) 5%
3-HHEH-3 (3-4) 5%
5-B (F) BB-2 (3-7) 3%
5-B (F) BB-3 (3-7) 2%
5-HEB (F, F) -F (4) 3%
5-HB-CL (4-1) 5%
3-HHB-OCF3 (4-3) 4%
3-HHEB (F, F) -F (4-5) 4%
3-HBEB (F, F) -F (4-10) 3%
5-HBEB (F, F) -F (4-10) 3%
3-BB (F) B (F, F) -F (4-12) 3%
NI = 78.6 ° C .; Tc <−20 ° C .; Δn = 0.091; Δε = 6.8; Vth = 1.52V; η = 15.5 mPa · s;

Composition (M10)
3-HHXB (F, F) -F (1-2) 9%
3-BB (F, F) XB (F, F) -F (1-4) 5%
3-HH-V (3-1) 25%
3-HH-V1 (3-1) 10%
5-HB-O2 (3-2) 10%
7-HB-1 (3-2) 5%
V2-BB-1 (3-3) 3%
3-HHB-1 (3-5) 4%
1V-HBB-2 (3-6) 5%
5-HBB (F) B-2 (3-13) 6%
3-HBB (F, F) -F (4-8) 3%
3-BB (F) B (F, F) -F (4-12) 4%
3-BB (F) B (F, F) -CF3 (4-13) 4%
3-GBB (F) B (F, F) -F (4-16) 3%
4-GBB (F) B (F, F) -F (4-16) 4%
NI = 79.6 ° C .; Tc <−20 ° C .; Δn = 0.111; Δε = 4.7; Vth = 1.86V; η = 9.7 mPa · s; γ1 = 49.9 mPa · s.

Composition (M11)
3-BB (F, F) XB (F, F) -F (1-4) 14%
3-dhB (F, F) B (F, F) XB (F) B (F, F) -F (1-13) 7%
3-BB (2F, 5F) B-3 (3) 3%
2-HH-5 (3-1) 5%
3-HH-V (3-1) 30%
3-HH-V1 (3-1) 3%
3-HH-VFF (3-1) 10%
3-HHB-1 (3-5) 4%
3-HHB-3 (3-5) 5%
3-HHB-O1 (3-5) 3%
3-HHEBH-3 (3-11) 3%
3-HHEBH-4 (3-11) 4%
3-HHEBH-5 (3-11) 3%
7-HB (F, F) -F (4-2) 6%
NI = 82.7 ° C .; Tc <−20 ° C .; Δn = 0.085; Δε = 5.1; Vth = 1.70V; η = 8.0 mPa · s; γ1 = 53.9 mPa · s.

Composition (M12)
3-BB (F) B (F, F) XB (F, F) -F (1-10) 3%
4-BB (F) B (F, F) XB (F, F) -F (1-10) 5%
3-BB (F, F) XB (F) B (F, F) -F (1-12) 3%
5-BB (F) B (F, F) XB (F) B (F, F) -F (1-14) 4%
2-HH-5 (3-1) 8%
3-HH-V (3-1) 28%
4-HH-V1 (3-1) 7%
5-HB-O2 (3-2) 2%
7-HB-1 (3-2) 5%
VFF-HHB-O1 (3-5) 8%
VFF-HHB-1 (3-5) 3%
3-HH2BB (F, F) -F (4) 3%
4-HH2BB (F, F) -F (4) 3%
3-HBB (F, F) -F (4-8) 5%
5-HBB (F, F) -F (4-8) 4%
3-BB (F) B (F, F) -F (4-12) 3%
3-HBB (2F, 3F) -O2 (5-14) 2%
2-BB (2F, 3F) B-3 (5-19) 4%
NI = 81.9 ° C .; Tc <−20 ° C .; Δn = 0.09; Δε = 4.8; Vth = 1.75 V; η = 13.3 mPa · s; γ 1 = 57.4 mPa · s.

Composition (M13)
5-HHB (F, F) XB (F, F) -F (1-5) 3%
3-HGB (F, F) XB (F, F) -F (1-6) 4%
3-HBBXB (F, F) -F (1-7) 6%
3-GB (F) B (F, F) XB (F, F) -F (1-9) 5%
4-GB (F) B (F, F) XB (F, F) -F (1-9) 5%
3-HH-5 (3-1) 4%
3-HH-V (3-1) 21%
3-HH-V1 (3-1) 3%
4-HH-V (3-1) 4%
1V2-HH-3 (3-1) 6%
5-B (F) BB-2 (3-7) 3%
5-B (F) BB-3 (3-7) 2%
5-HEB (F, F) -F (4) 3%
5-HB-CL (4-1) 2%
3-HHB-OCF3 (4-3) 4%
3-HHEB (F, F) -F (4-5) 4%
3-HBEB (F, F) -F (4-10) 3%
5-HBEB (F, F) -F (4-10) 3%
3-BB (F) B (F, F) -F (4-12) 3%
3-HB (2F, 3F) -O2 (5-1) 3%
3-BB (2F, 3F) -O2 (5-6) 2%
3-HHB (2F, 3F) -O2 (5-8) 4%
F3-HH-V (-) 3%
NI = 78.1 ° C .; Tc <−20 ° C .; Δn = 0.100; Δε = 6.6; Vth = 1.50V; η = 16.2 mPa · s; γ1 = 61.8 mPa · s.

Polar compounds (PC-1) to (PC-12) are the first additives.

Polymerizable compounds (RM-1) to (RM-8) are the second additives.

2. Example 1 of vertical alignment of liquid crystal molecules
A polar compound (PC-1) as a first additive was added to the composition (M1) at a ratio of 5% by mass to prepare a liquid crystal composition. This liquid crystal composition was injected on a hot stage at 100 ° C. into an element having no alignment film and having a distance (cell gap) between two glass substrates of 4.0 μm. The polar compound (PC-1) was polymerized by irradiating ultraviolet rays (28 J) using an ultra-high pressure mercury lamp USH-250-BY (manufactured by Ushio Inc.) while applying a voltage to the device. This device was set in a polarizing microscope in which a polarizer and an analyzer were arranged orthogonally, and the device was irradiated with light from below to observe whether or not there was light leakage. When the liquid crystal molecules in the liquid crystal composition were sufficiently aligned and there was no light leakage, the vertical alignment was determined to be “good”. When light leakage was observed, the orientation was determined to be “poor”.

Examples 2 to 31
A device having no alignment film was manufactured using a liquid crystal composition prepared by adding a polar compound having a polymerizable group to the composition. The presence or absence of light leakage was observed in the same manner as in Example 1. The results are summarized in Table 4. In Example 27, a polymerizable compound (RM-1) was further added at a ratio of 0.5% by mass.

  As can be seen from Table 4, in Examples 1 to 13, the types of the composition and the polar compound were changed, but no light leakage was observed. This result indicates that the liquid crystal molecules in the liquid crystal composition are vertically aligned even if the device has no alignment film. In Example 14, the polymerizable compound (RM-1) was further added, but similar results were obtained.

  The liquid crystal composition of the present invention can be used for a liquid crystal monitor, a liquid crystal television and the like.

Claims (27)

Liquid crystal containing at least one compound selected from compounds represented by formula (1) as a first component and at least one compound selected from polar compounds represented by formula (2) as a first additive Composition.

In the formulas (1) and (2), ring A and ring B are 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, and pyrimidine -2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; ring C and ring D are 1,4-cyclohexylene, 1,4-cyclohexyl Senylene, 1,4-phenylene, naphthalene-1,5-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6- Diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, Wherein at least one hydrogen is replaced by fluorine, chlorine, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 10 carbons, or alkenyloxy having 2 to 10 carbons And in these groups, at least one hydrogen may be replaced by fluorine or chlorine; Z ¹ and Z ² are a single bond, ethylene, vinylene, methyleneoxy, carbonyloxy or difluoromethyleneoxy Yes; Z ³ is a single bond or an alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, —CO—, —COO—, —OCO—, or — may be replaced by -OCOO-, at least one -CH ₂ CH ₂ - is, -CH = CH- or -C≡ And in these groups at least one hydrogen may be replaced by fluorine or chlorine; a is 1, 2, 3, or 4; b is 0, 1, 2, or 3, and the sum of a and b is 4 or less; c is 0, 1, 2 or be a 3,; ^{X 1} and ^{X 2} is hydrogen or fluorine; ^{Y 1} is Fluorine, chlorine, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen is fluorine or 2 carbon atoms replaced by chlorine 12 alkenyloxy; Sp ¹ and Sp ² is alkylene of 15 a single bond or 1 carbon atoms, the alkylene Oite, at least one of -CH ₂ -, -O -, - CO -, - COO -, - OCO-, or may be replaced by -OCOO-, at least one -CH ₂ CH ₂ - is —CH ＝ CH— or —C≡C—, in which at least one hydrogen may be replaced by fluorine or chlorine; M ¹ , M ² , M ³ , and M ⁴ is hydrogen, fluorine, chlorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine; R ¹ is 1 to 12 carbons alkyl, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons,; R ² is hydrogen, alkyl having 1 to 10 carbons, alkoxy having 10 carbon number of 1 or from 1 carbon atoms, 0 is an alkoxyalkyl, in these groups, at least one -CH ₂ CH ₂ - may be replaced by -CH = CH- or -C≡C-, and in the groups, at least one hydrogen May be replaced by fluorine or chlorine; R ³ is a group selected from the groups represented by formula (2-a), formula (2-b), and formula (2-c);

In the formulas (2-a), (2-b), and (2-c), Sp ³ and Sp ⁴ are each a single bond or an alkylene having 1 to 15 carbon atoms. -CH ₂ - is, -O -, - CO -, - COO -, - OCO-, or may be replaced by -OCOO-, at least one -CH ₂ CH ₂ - is, -CH = CH- or -C≡C-, in which at least one hydrogen may be replaced by fluorine or chlorine; R ⁴ is hydrogen, alkyl of 1 to 10 carbons, 1 carbon of 1 S ¹ and S ² are> C <; X ³ is —OH, —NH ₂ , —N (R ⁵ ) ₂ , — COOH, -SH, or Si ^(R 5) _3, wherein, ^{R 5} is hydrogen or alkyl having 1 to 10 carbon atoms, in the alkyl, at least one -CH ₂ - may be replaced by -O- , At least one —CH ₂ CH ₂ — may be replaced by —CH ＝ CH—, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine. The liquid crystal composition according to claim 1, wherein the liquid crystal composition contains at least one compound selected from the compounds represented by Formulas (1-1) to (1-14) as a first component.

In the formulas (1-1) to (1-14), R ¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons; X ¹ , X ^{1 2} , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ and X ¹⁵ are hydrogen or fluorine; Y ¹ is fluorine , Chlorine, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen is fluorine Or alkenyloxy having 2 to 12 carbon atoms replaced with chlorine. The liquid crystal composition according to claim 1, comprising at least one compound selected from polar compounds represented by formulas (2-1) to (2-18) as a first additive.

In Formulas (2-1) to (2-18), Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and Y ⁷ are hydrogen, fluorine, methyl, or ethyl; and Z ⁴ and Z ⁵ It represents a single bond or -CH ₂ CH ₂ - and are; ^{R 4} is hydrogen, alkyl of 1 to 10 carbon atoms, alkoxyalkyl of alkoxy of 1 to 10 carbon atoms, or a carbon number of 1 to 10; ^{S 1} Is> C <; Sp ¹ , Sp ² , Sp ³ , and Sp ⁴ are a single bond or an alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is —O— May be replaced by   The liquid crystal composition according to claim 1, wherein a ratio of the first component is in a range of 5% by mass to 55% by mass.   The liquid crystal composition according to claim 1, wherein a ratio of the first additive is in a range of 0.05% by mass to 10% by mass. The liquid crystal composition according to any one of claims 1 to 5, further comprising at least one compound selected from the compounds represented by formula (3) as the second component.

In the formula (3), R ⁶ and R ⁷ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen replaced with fluorine or chlorine. Ring E and ring F are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4 -Phenylene; Z ⁶ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; d is 1, 2, or 3. The liquid crystal composition according to any one of claims 1 to 6, wherein the liquid crystal composition contains at least one compound selected from the compounds represented by Formulas (3-1) to (3-13) as a second component. .

In the formulas (3-1) to (3-13), R ⁶ and R ⁷ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one of Hydrogen is alkenyl having 2 to 12 carbons in which hydrogen is replaced by fluorine or chlorine.   The liquid crystal composition according to claim 6, wherein a ratio of the second component is in a range of 10% by mass to 90% by mass. The liquid crystal composition according to any one of claims 1 to 8, further comprising at least one compound selected from the compounds represented by formula (4) as the third component.

In the formula (4), R ⁸ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons; ring G is 1,4-cyclohexylene, 1,4 -Phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane Y is -2,5-diyl or tetrahydropyran-2,5-diyl; Z ⁷ is a single bond, ethylene, vinylene, or carbonyloxy; X ¹⁶ and X ¹⁷ are hydrogen or fluorine; ⁸ is fluorine, chlorine, at least one hydrogen alkyl having 1 carbon is replaced by fluorine or chlorine 12, at least one hydrogen fluorine or chlorine location Be replaced is alkoxy having 1 to 12 carbon atoms or at least one hydrogen having 2 to 12 carbons are replaced by fluorine or chlorine alkenyloxy,; e is 1, 2, 3, or 4. The liquid crystal composition according to any one of claims 1 to 9, further comprising at least one compound selected from the compounds represented by Formulas (4-1) to (4-16) as a third component. .

In the formulas (4-1) to (4-16), R ⁸ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons.   The liquid crystal composition according to claim 9, wherein the proportion of the third component is in a range from 5% by mass to 50% by mass. The liquid crystal composition according to any one of claims 1 to 11, further comprising at least one compound selected from the compounds represented by the formula (5) as a fourth component.

In the formula (5), R ⁹ and R ¹⁰ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons. Ring I and ring K are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, wherein at least one hydrogen is replaced by fluorine or chlorine 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen is fluorine or Ring J is 2,3-difluoro-1,4-phenylene, 2-chloro B-3-Fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman -2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7- Diyl, or 1,1,6,7-tetrafluoroindan-2,5-diyl; Z ⁸ and Z ⁹ are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; 1, 2, or 3, g is 0 or 1, and the sum of f and g is 3 or less. The liquid crystal composition according to any one of claims 1 to 12, comprising at least one compound selected from the compounds represented by Formulas (5-1) to (5-35) as a fourth component. .

In the formulas (5-1) to (5-35), R ⁹ and R ¹⁰ represent hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon Alkenyloxy of the formulas 2 to 12;   14. The liquid crystal composition according to claim 12, wherein a ratio of the fourth component is in a range of 3% by mass to 40% by mass. The liquid crystal composition according to any one of claims 1 to 14, further comprising at least one compound selected from the polymerizable compounds represented by the formula (6) as the second additive.

In the formula (6), ring L and ring U are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl Or pyridin-2-yl, wherein at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is fluorine or chlorine. May be replaced by alkyl having 1 to 12 carbons which is replaced by: T 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 atom is fluorine, chlorine, a carbon atom having 1 to 4 carbon atoms. 12 alkyl, 1 to 12 carbon alkoxy, or 1 to 12 carbon alkyl in which at least one hydrogen is replaced by fluorine or chlorine; Z ¹⁰ and Z ¹¹ may be a single bond or a carbon alkylene from C 1 10, in the alkylene, at least one of _-CH 2 -, -O -, - CO -, - COO-, or In may be replaced, and at least one _-CH 2 CH ₂ is -OCO- - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, or _{-C (CH 3) = C (} CH 3) - may be replaced by, in these groups, at least one hydrogen may be replaced by fluorine or ^chlorine; P 1, ^{P 2,} and ^{P 3} Is a polymerizable group that does not contain the groups represented by formulas (2-a), (2-b), and (2-c) according to claim 1; Sp ⁵ , Sp ⁶ , and Sp ⁷ is a single bond or alkylene having a carbon number of 1 to 10, in the alkylene, at least one of _-CH 2 -, -O -, - COO -, - OCO-, or -OCOO- may be replaced by and at least one _-CH 2 C H ₂ — may be replaced by —CH ＝ CH— or —C≡C— and in these groups at least one hydrogen may be replaced by fluorine or chlorine; h is 0, 1, Or 2; i, j, and k are 0, 1, 2, 3, or 4, and the sum of i, j, and k is 1 or more. The formula (6) according to claim 15, wherein P ¹ , P ² , and P ³ are groups selected from the polymerizable groups represented by the formulas (P-1) to (P-5). Liquid crystal composition.

In the formulas (P-1) to (P-5), M ⁵ , M ⁶ , M ⁷ , M ⁸ , M ⁹ , M ¹⁰ , M ¹¹ , M ¹² , and M ¹³ represent hydrogen, fluorine, and carbon number. Alkyl of 1 to 5 or alkyl of 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine. The method according to any one of claims 1 to 16, wherein the second additive contains at least one compound selected from polymerizable compounds represented by the formulas (6-1) to (6-29). Liquid crystal composition.

In the formulas (6-1) to (6-29), P ¹ , P ² , and P ³ are selected from the polymerizable groups represented by the formulas (P-1) to (P-3). Group,

Here, M ⁵ , M ⁶ , M ⁷ , M ⁸ , M ⁹ , M ¹⁰ , M ¹¹ , and M ¹² are hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is fluorine or chlorine. Sp ⁵ , Sp ⁶ , and Sp ⁷ are a single bond or an alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is an alkylene having 1 to 5 carbon atoms. , —O—, —COO—, —OCO—, or —OCOO—, and at least one —CH ₂ CH ₂ — is replaced by —CH ＝ CH— or —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 15 to 17, wherein a ratio of the second additive is in a range of 0.03% by mass to 10% by mass.   A liquid crystal display device comprising the liquid crystal composition according to claim 1.   20. The liquid crystal display device according to claim 19, wherein an operation mode of the liquid crystal display device is one of an IPS mode, a TN mode, an FFS mode, and an FPA mode, and a driving system of the liquid crystal display device is an active matrix system.   A liquid crystal display device of a polymer-supported alignment type, comprising the liquid crystal composition according to claim 1, wherein the first additive contained in the liquid crystal composition is polymerized.   A liquid crystal display of a polymer supported alignment type, comprising the liquid crystal composition according to any one of claims 15 to 18, wherein the first additive and the second additive contained in the liquid crystal composition are polymerized. element.   A liquid crystal display device comprising the liquid crystal composition according to any one of claims 1 to 14, wherein the first additive contained in the liquid crystal composition is polymerized and has no alignment film.   A liquid crystal display device having no alignment film, comprising the liquid crystal composition according to claim 15, wherein the first additive and the second additive contained in the liquid crystal composition are polymerized. .   Use of the liquid crystal composition according to any one of claims 1 to 18 in a liquid crystal display device.   Use of the liquid crystal composition according to any one of claims 1 to 18 in a polymer supported alignment type liquid crystal display device.   Use of the liquid crystal composition according to any one of claims 1 to 18 in a liquid crystal display device having no alignment film.