JP2020037671A - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

To provide a liquid crystal composition that satisfies at least one characteristic selected from such characteristics as a high upper limit temperature, a low lower limit temperature, a low viscosity, an appropriate optical anisotropy, a great negative dielectric anisotropy, a high specific resistivity, a high stability against light, a high stability against heat, or has a proper balance between at least two characteristics; and an AM element containing the composition.SOLUTION: A liquid crystal composition contains at least one compound selected from a compound having a monovalent group as a first additive, and may contain a specific compound having a great negative dielectric anisotropy as a first component, a specific compound having a high upper limit temperature or a low viscosity as a second component, or a specific compound having a polymerizable group as a second additive.SELECTED DRAWING: None

Description

  The present invention relates to a liquid crystal composition, a liquid crystal display device containing the composition, and the like. In particular, the present invention relates to a liquid crystal composition having a negative dielectric anisotropy and a liquid crystal display device containing the composition and having a mode such as IPS, VA, FFS, or FPA. The present invention also relates to a polymer-supported alignment type 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). The classification based on the element driving method is PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex and the like, and AM is classified into TFT (thin film transistor), MIM (metal insulator metal) and the like. The classification of TFT is amorphous silicon and polycrystal silicon. The latter is classified into a high-temperature type and a low-temperature type according to the manufacturing process. The classification based on the light source is a 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 commercially available AM devices. The temperature range of the nematic phase is related to the temperature range in which the device can be used. The preferred upper limit temperature of the nematic phase is about 70 ° C. or higher, and the preferred lower limit temperature of the nematic phase is about −10 ° C. or lower. The viscosity of the composition is related to the response time of the device. A short response time is preferable for displaying a moving image on the element. Shorter response times are desirable even at 1 millisecond. Therefore, a small viscosity in the composition is preferred. Small viscosities at low temperatures are more preferred.

  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 operation 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 a general-purpose liquid crystal display device, 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 alignment 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.

  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. In a polymer sustained alignment (PSA) type AM device, a composition having a positive or negative dielectric anisotropy is used.

  Further, these liquid crystal display elements are required to have excellent display quality with no or suppressed display defects such as image sticking and display unevenness. In order to achieve this, various additives have been added to the liquid crystal composition to improve the reliability of the entire LCD panel.

JP 2017-105762 A

  An object of the present invention is to provide a liquid crystal composition containing a compound having an effect of suppressing display defects such as line afterimages and an antistatic effect. Other issues are high upper temperature of nematic phase, lower lower temperature of nematic phase, small viscosity, appropriate optical anisotropy, negatively large dielectric anisotropy, large specific resistance, high stability to light, It is to provide a liquid crystal composition that satisfies at least one of the properties such as high stability. Another object is to provide a liquid crystal composition having a suitable balance between at least two of these properties. Another object is to provide a liquid crystal display device containing such a composition. Another object is to provide a liquid crystal display element with excellent display quality, which has no or reduced display defects such as image sticking and display unevenness by using 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.

式（Ｓ）において、Ｒ^ａは、水素、Ｏ・、ＯＨ、炭素数１から２０のアルキル、炭素数３から２０の脂環式炭化水素基、または炭素数６から２０の芳香族炭化水素基であり、これらの基において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＮＨ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−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、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、ハロゲン、ＯＨ、ＮＨＲ^１ｂ、またはＮＲ^１ｃＲ^１ｄで置き換えられてもよく；
ここで、Ｒ^１ｂ、Ｒ^１ｃ、およびＲ^１ｄは、炭素数１から１０のアルキルである。 The present inventor has studied various liquid crystal compounds and various chemical substances, and found that the above problem can be solved by using a specific compound, thereby completing the present invention. That is, the present invention provides a liquid crystal having at least one compound selected from compounds having a monovalent group represented by the formula (S) as a first additive, having a nematic phase and a negative dielectric anisotropy. Provided is a composition, and a liquid crystal display device using the composition.

In the formula (S), ^Ra is hydrogen, O., OH, alkyl having 1 to 20 carbons, alicyclic hydrocarbon group having 3 to 20 carbons, or aromatic hydrocarbon group having 6 to 20 carbons. and, in these groups, at least one _-CH 2 is - is, -O -, - NH -, - CO -, - COO-, or may be replaced by -OCO-, at least one -CH ₂ —CH ₂ — may be replaced by —CH ＝ CH— or —C≡C—, and in these groups, at least one hydrogen is an alkyl having 1 to 10 carbons, an alkoxy having 1 to 10 carbons. , Halogen, OH, NHR ^1b , or NR ^1c R ^1d ;
Here, R ^1b , R ^1c and R ^1d are alkyl having 1 to 10 carbons.

  An advantage of the present invention is to provide a liquid crystal composition containing a compound having an effect of suppressing display defects such as line afterimage and an antistatic effect. Another advantage is that the upper limit temperature of the nematic phase, the lower limit temperature of the nematic phase, small viscosity, appropriate optical anisotropy, negatively large dielectric anisotropy, large specific resistance, high stability to light, high heat resistance It is to provide a liquid crystal composition that satisfies at least one of the properties such as high stability. Another advantage is to provide a liquid crystal composition having a suitable balance between at least two of these properties. Another advantage is to provide a liquid crystal display device containing such a composition. Another advantage is to provide a liquid crystal display element with excellent display quality, which has no or reduced display defects such as burn-in and display unevenness. An object of the present invention 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. A `` liquid crystalline compound '' is a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and having no liquid crystal phase, but for the purpose of adjusting properties such as temperature range, viscosity and dielectric anisotropy of the nematic phase. It is a general term for compounds to be mixed in the composition. This compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecule (liquid crystal molecule) is rod-like. "Polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. Liquid crystal compounds having alkenyl are not classified as polymerizable compounds in that sense.

  The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as 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 ratio 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 “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, the value increases to a positive value, and the composition has a negative dielectric anisotropy. For an object, it means that its value increases negatively. "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 at a temperature close to the upper limit temperature after prolonged use. It means 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 above compound (1z) will be described as an example. In the formula (1z), the symbols of 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 crossing one side of the ring β indicates that any hydrogen on the ring β may be replaced with 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. This rule is also applied when the symbol Ra is used for a plurality of compounds. This rule is also applied when a plurality of Ras are used for one compound.

  At least one compound selected from the compounds represented by the formula (1z) may be abbreviated as “compound (1z)”. “Compound (1z)” means one compound represented by the formula (1z), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas. The expression “at least one compound selected from the compounds 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。なお、好ましいテトラヒドロピラン−２，５−ジイルは、上限温度を上げるために右向き（Ｒ）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 preferred tetrahydropyran-2,5-diyl is rightward (R) to increase the maximum temperature. The same applies to a bonding group such as carbonyloxy (—COO— or —OCO—).

  The present invention includes the following items.

式（Ｓ）において、Ｒ^ａは、水素、Ｏ・、ＯＨ、炭素数１から２０のアルキル、炭素数３から２０の脂環式炭化水素基、または炭素数６から２０の芳香族炭化水素基であり、これらの基において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＮＨ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−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、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、ハロゲン、ＯＨ、ＮＨＲ^１ｂ、またはＮＲ^１ｃＲ^１ｄで置き換えられてもよく；
ここで、Ｒ^１ｂ、Ｒ^１ｃ、およびＲ^１ｄは、炭素数１から１０のアルキルである。 Item 1. A liquid crystal composition comprising at least one compound selected from compounds having a monovalent group represented by the formula (S) as a first additive, and having a nematic phase and negative dielectric anisotropy.

In the formula (S), ^Ra is hydrogen, O., OH, alkyl having 1 to 20 carbons, alicyclic hydrocarbon group having 3 to 20 carbons, or aromatic hydrocarbon group having 6 to 20 carbons. and, in these groups, at least one _-CH 2 is - is, -O -, - NH -, - CO -, - COO-, or may be replaced by -OCO-, at least one -CH ₂ —CH ₂ — may be replaced by —CH ＝ CH— or —C≡C—, and in these groups, at least one hydrogen is an alkyl having 1 to 10 carbons, an alkoxy having 1 to 10 carbons. , Halogen, OH, NHR ^1b , or NR ^1c R ^1d ;
Here, R ^1b , R ^1c and R ^1d are alkyl having 1 to 10 carbons.

式（１）において、Ｒ^ｂは、水素、フッ素、炭素数１から２０のアルキル、炭素数３から２０の脂環式炭化水素基、または炭素数６から２０の芳香族炭化水素基であり、これらの基において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＮＨ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−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、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、ハロゲン、ＯＨ、ＮＨＲ^１ｂ、またはＮＲ^１ｃＲ^１ｄで置き換えられてもよく；Ｒ^１ｂ、Ｒ^１ｃ、およびＲ^１ｄは、炭素数１から１０のアルキルであり；Ｍは、単結合、炭素数１から２０の四価の脂肪族炭化水素基、または炭素数６から２０の四価の芳香族炭化水素基であり、これらの基において、少なくとも１つの−ＣＨ_２−は、−Ｏ−または−Ｓ−で置き換えられてもよく、１つまたは２つの−ＣＨ＝ＣＨ−は−ＣＨ＝Ｎ−で置き換えられてもよく、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^ａおよびＺ^ｂは、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、炭素数１から２０のアルキレン、または炭素数２から２０のアルケニレンであり、これらの基において、少なくとも１つの水素は、フッ素、塩素、ＯＨで置き換えられてもよく；Ｑ^ａは、式（Ｓ）で表される一価基であり；ｎは、１、２、３、または４であり；ｍは、４−ｎであり；ただし、Ｍが単結合の場合、ｎおよびｍは１であり；

式（Ｓ）において、Ｒ^ａは、水素、Ｏ・、ＯＨ、炭素数１から２０のアルキル、炭素数３から２０の脂環式炭化水素基、または炭素数６から２０の芳香族炭化水素基であり、これらの基において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＮＨ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−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、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、ハロゲン、ＯＨ、ＮＨＲ^１ｂ、またはＮＲ^１ｃＲ^１ｄで置き換えられてもよく；
ここで、Ｒ^１ｂ、Ｒ^１ｃ、およびＲ^１ｄは、炭素数１から１０のアルキルである。 Item 2. Item 1. The liquid crystal composition according to item 1, comprising at least one compound selected from the compounds represented by formula (1) as the first additive.

In the formula (1), R ^b is hydrogen, fluorine, alkyl having 1 to 20 carbons, an alicyclic hydrocarbon group having 3 to 20 carbons, or an aromatic hydrocarbon group having 6 to 20 carbons, in these groups, at least one of _-CH 2 -, -O -, - NH -, - CO -, - COO-, or may be replaced by -OCO-, at least one _-CH 2 -CH ₂ -May be replaced by -CH = CH- or -C≡C-, in which at least one hydrogen is an alkyl having 1 to 10 carbons, an alkoxy having 1 to 10 carbons, a halogen, R ^1b , R ^1c , and R ^1d may be substituted with OH, NHR ^1b , or NR ^1c R ^1d ; R ^1b , R ^1c , and R ^1d are alkyl having 1 to 10 carbons; M is a single bond, 1 to 20 carbons Tetravalent fat A family hydrocarbon group or a tetravalent aromatic hydrocarbon group having 6 to 20 carbon atoms, in these groups, at least one -CH 2 _- may be replaced by -O- or -S- , one or two -CH = CH- may be replaced by -CH = N-, at least one hydrogen may be replaced by fluorine or chlorine; ^{Z a} and ^{Z b} is a single bond, -O-, -COO-, -OCO-, alkylene having 1 to 20 carbons or alkenylene having 2 to 20 carbons, in which at least one hydrogen is replaced by fluorine, chlorine, OH Q ^a is a monovalent group represented by the formula (S); n is 1, 2, 3, or 4; m is 4-n; In the case of a bond, n and m are 1;

In the formula (S), ^Ra is hydrogen, O., OH, alkyl having 1 to 20 carbons, alicyclic hydrocarbon group having 3 to 20 carbons, or aromatic hydrocarbon group having 6 to 20 carbons. and, in these groups, at least one _-CH 2 is - is, -O -, - NH -, - CO -, - COO-, or may be replaced by -OCO-, at least one -CH ₂ —CH ₂ — may be replaced by —CH ＝ CH— or —C≡C—, and in these groups, at least one hydrogen is an alkyl having 1 to 10 carbons, an alkoxy having 1 to 10 carbons. , Halogen, OH, NHR ^1b , or NR ^1c R ^1d ;
Here, R ^1b , R ^1c and R ^1d are alkyl having 1 to 10 carbons.

式（１−１）から式（１−５）において、Ｚ^ｃは、単結合、炭素数１から５のアルキレンまたは炭素数２から５のアルケニレンであり、これらの基において、少なくとも１つの水素は、ＯＨで置き換えられてもよく；Ｒ^ｃは、水素、炭素数１から２０のアルキル、炭素数３から２０の脂環式炭化水素基、または炭素数６から２０の芳香族炭化水素基であり、これらの基において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−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、ＯＨ、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６から２０の芳香族炭化水素基で置き換えられてもよく；ｓは、１から２０の整数であり；Ｑ^ｂは、式（Ｓ−１）で表される一価基であり；

式（Ｓ−１）において、Ｒ^ｄは、水素、Ｏ・、ＯＨ、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、または炭素数１から１０のアルコキシであり、これらの基において、少なくとも１つの水素は、ハロゲン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 compounds represented by formulas (1-1) to (1-5) as a first additive.

In the formulas (1-1) to (1-5), Z ^c is a single bond, an alkylene having 1 to 5 carbons or an alkenylene having 2 to 5 carbons. In these groups, at least one hydrogen is , OH; R ^c is hydrogen, alkyl having 1 to 20 carbons, alicyclic hydrocarbon having 3 to 20 carbons, or aromatic hydrocarbon having 6 to 20 carbons. , In these groups, at least one —CH ₂ — may be replaced by —O—, —CO—, —COO—, or —OCO—, and at least one —CH ₂ —CH ₂ — —CH ＝ CH— or —C≡C—, in which at least one hydrogen is OH, alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, or carbon having 1 to 10 carbons. 6 to 2 Is s, be of 1 to 20 integer; may be replaced by an aromatic hydrocarbon group Q ^b is a monovalent group represented by the formula (S-1);

In the formula (S-1), R ^d is hydrogen, O., OH, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkoxy having 1 to 10 carbons. , At least one hydrogen may be replaced by halogen.

Item 4. Item 4. The liquid crystal composition according to any one of Items 1 to 3, wherein a ratio of the first additive is in a range of 0.001% by mass to 2% by mass.

式（２）において、Ｒ^２ａおよびＲ^２ｂは、水素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルであり；環Ａおよび環Ｃ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Ｂ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^２ａおよびＺ^２ｂ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；ａは、０、１、２、または３であり、ｂは０または１であり；そしてａとｂとの和は３以下である。 Item 5. Item 5. The liquid crystal composition according to any one of items 1 to 4, comprising at least one compound selected from the compounds represented by formula (2) as a first component.

In the formula (2), R ^2a and R ^2b represent hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or at least Ring A and ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-, wherein one hydrogen is alkyl having 1 to 12 carbons replaced by fluorine or chlorine; Diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2 in which at least one hydrogen is replaced by fluorine or chlorine, 6-diyl, chroman-2,6-diyl, or a compound in which at least one hydrogen has been replaced by fluorine or chlorine. Ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl- 1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7 -Diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl or 1,1,6,7-tetrafluoroindan-2,5-diyl ; ^{Z 2a} and ^{Z 2b} is a single bond, ethylene, vinylene, methyleneoxy or carbonyloxy,; a is 0, 1, 2 or 3,, b is 0 or 1; and a and b The sum of 3 or less.

式（２−１）から式（２−３５）において、Ｒ^２ａおよびＲ^２ｂは、水素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルである。 Item 6. Item 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 formulas (2-1) to (2-35) as a first component.

In the formulas (2-1) to (2-35), R ^2a and R ^2b represent hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon number. It is an alkenyloxy having 2 to 12 carbons or an alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.

Item 7. Item 7. The liquid crystal composition according to item 5 or 6, wherein the proportion of the first component is in the range of 10% by mass to 90% by mass.

式（３）において、Ｒ^３ａおよびＲ^３ｂ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Ｄおよび環Ｅ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^３ａは、単結合、エチレン、ビニレン、メチレンオキシ、またはカルボニルオキシであり；ｃは、１、２、または３である。 Item 8. Item 8. The liquid crystal composition according to any one of items 1 to 7, comprising at least one compound selected from the compounds represented by formula (3) as the second component.

In the formula (3), R ^3a and R ^3b 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 D and ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4 -Phenylene; Z ^3a is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; c is 1, 2, or 3.

式（３−１）から式（３−１３）において、Ｒ^３ａおよびＲ^３ｂ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 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 formulas (3-1) to (3-13) as a second component.

In the formulas (3-1) to (3-13), R ^3a and R ^3b represent 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 10. Item 10. The liquid crystal composition according to item 8 or 9, wherein the proportion of the second component is in the range of 10% by mass to 90% by mass.

式（４）において、環Ｆおよび環Ｉ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Ｇ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^４ａおよびＺ^４ｂは、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ_３）−、または−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｐ^４ａ、Ｐ^４ｂ、およびＰ^４ｃは、重合性基であり；Ｓｐ^４ａ、Ｓｐ^４ｂ、およびＳｐ^４ｃは、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ｄは、０、１、または２であり；ｅ、ｆ、およびｇは、０、１、２、３、または４であり；そしてｅ、ｆ、およびｇの和は、１以上である。 Item 11. Item 11. The liquid crystal composition according to any one of items 1 to 10, comprising at least one compound selected from the polymerizable compounds represented by the formula (4) as the second additive.

In the formula (4), ring F and ring I 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. Ring G may be substituted with 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, 1 carbon atom or less. 12 alkyl, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen has been replaced by fluorine or chlorine; Z ^4a and Z ^4b 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, 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 ^{4a, P 4b} and ^{P 4c,} Is a polymerizable group; Sp ^4a , Sp ^4b , and Sp ^4c are a single bond or an alkylene having 1 to 10 carbon atoms, in which at least one -CH ₂ -is -O-,- COO—, —OCO—, or —OCOO—, and at least one of —CH ₂ —CH ₂ — may be replaced by —CH ＝ CH— or —C 、 C— Group Wherein at least one hydrogen may be replaced by fluorine or chlorine; d is 0, 1, or 2; e, f, and g are 0, 1, 2, 3, or 4 Yes; and the sum of e, f, and g is 1 or more.

式（Ｐ−１）から式（Ｐ−５）において、Ｍ^１、Ｍ^２、およびＭ^３は、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルである。 Item 12. Item 11. The liquid crystal composition according to item 11, wherein in formula (4), P ^4a , P ^4b , and P ^4c are groups selected from the polymerizable groups represented by formulas (P-1) to (P-5). object.

In Formulas (P-1) to (P-5), M ¹ , M ² , and M ³ represent hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen replaced with fluorine or chlorine. Alkyl having 1 to 5 carbon atoms.

式（４−１）から式（４−２９）において、Ｓｐ^４ａ、Ｓｐ^４ｂ、およびＳｐ^４ｃは、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｐ^４ｄ、Ｐ^４ｅ、およびＰ^４ｆは、式（Ｐ−１）から式（Ｐ−３）で表される基から選択された重合性基であり；

式（Ｐ−１）から式（Ｐ−３）において、Ｍ^１、Ｍ^２、およびＭ^３は、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルである。 Item 13. Item 13. The liquid crystal according to any one of items 1 to 12, comprising at least one compound selected from polymerizable compounds represented by formulas (4-1) to (4-29) as a second additive. Composition.

In the formulas (4-1) to (4-29), Sp ^4a , Sp ^4b , and Sp ^4c are a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — May be replaced by —O—, —COO—, —OCO—, or —OCOO—, and at least one of —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; P ^4d , P ^4e , and P ^4f are represented by the formulas (P-1) to (P-3) A polymerizable group selected from the groups represented by

In the formulas (P-1) to (P-3), M ¹ , M ² , and M ³ represent hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen replaced with fluorine or chlorine. Alkyl having 1 to 5 carbon atoms.

Item 14. Item 14. The liquid crystal composition according to any one of Items 11 to 13, wherein a ratio of the second additive is in a range of 0.03% by mass to 10% by mass.

Item 15. Item 15. A liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 14.

Item 16. Item 16. The liquid crystal display element according to item 15, wherein an operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and a driving method of the liquid crystal display element is an active matrix method.

Item 17. Item 15. A polymer-supported alignment type liquid crystal display device comprising the liquid crystal composition according to any one of items 11 to 14, wherein a polymerizable compound in the liquid crystal composition is polymerized.

Item 18. Item 15. Use of the liquid crystal composition according to any one of items 1 to 14 in a liquid crystal display device.

Item 19. Item 15. Use of the liquid crystal composition according to any one of Items 11 to 14 in a polymer-supported alignment type liquid crystal display device.

  The present invention also includes the following items. (A) one compound selected from additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, and a polymerization inhibitor, two compounds, or A composition as described above comprising three or more compounds. (B) An AM device containing the above composition. (C) The above composition further containing a polymerizable compound, and a polymer supported alignment (PSA) type AM device containing this composition. (D) A polymer-supported alignment (PSA) type AM device containing the above composition, wherein the polymerizable compound in the composition is polymerized. (E) A device containing the above composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA. (F) A transmission device containing the above composition. (G) Use of the above composition as a composition having a nematic phase. (H) Use as an optically active composition by adding an optically active compound to the above composition.

  The composition of the present invention will be described in the following order. First, the constitution of the component compounds in 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, the combination of the components in the composition, the preferable ratio of the components, 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. The composition A may further contain other liquid crystal compounds, additives, and the like, in addition to the liquid crystal compounds selected from the compound (2) and the compound (3). "Other liquid crystal compounds" are liquid crystal compounds different from compound (2) and compound (3). Such compounds are mixed into the composition for the purpose of further adjusting the properties.

  Composition B consists essentially of a liquid crystal compound selected from compound (2) and compound (3). “Substantially” means that the composition B may contain additives, but does not contain other liquid crystal compounds. Composition B has a smaller number of components 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 based on the effects of the present invention. In the symbols in Table 2, L means large or high, M means medium, and S means small or low. The symbols L, M, and S are classifications based on qualitative comparison between component compounds, and 0 (zero) means smaller than S.

  The main effects of the component compounds are as follows. The first additive functions as a display failure suppressing agent such as burn-in and display unevenness. Since the compound (1) is added in a small amount, it does not affect properties such as the maximum temperature, optical anisotropy, and dielectric anisotropy in many cases. Compound (2) increases the dielectric anisotropy and lowers the minimum temperature. Compound (3) decreases the viscosity or increases the maximum temperature. Since compound (4) is polymerizable, it gives a polymer by polymerization. This polymer stabilizes the alignment of the liquid crystal molecules, thereby shortening the response time of the device.

The display quality may be significantly reduced due to the long-term use of the liquid crystal display device. One of the factors that can be considered is that, due to long-time driving, a slight concentration of charged particles inherent in the liquid crystal composition, or some sort of difference between an element member other than the liquid crystal composition and the liquid crystal composition. For this reason, potential is accumulated and display defects such as image sticking and display unevenness occur.

  The first additive of the present invention is at least one compound selected from compounds having a monovalent group represented by the formula (S). By adding this compound, the resistance of the liquid crystal display element can be extremely reduced without significantly lowering the specific resistance value of the liquid crystal composition. The amino group site of this compound is attracted to an adsorption site (for example, a carbonyl group on the surface of the alignment film) of a peripheral material of the LCD panel, thereby forming an adsorption layer. The resistance value of this layer is low, so that uneven distribution of charged particles and accumulation of potential are suppressed, and display defects such as burn-in and display unevenness are suppressed. It acts as a so-called local antistatic agent.

  Third, a combination of components in the composition, a preferable ratio of the component compounds, and the basis thereof will be described. Preferred combinations of components in the composition are: first additive + compound (2), first additive + compound (3), first additive + compound (2) + compound (3), first additive + compound (2) + second additive, first additive + compound (3) + second additive, or first additive + compound (2) + compound (3) + second additive. A more preferred combination is the first additive + compound (2) + compound (3) or the first additive + compound (2) + compound (3) + second additive.

  A desirable ratio of the first additive is about 0.001% by mass or more, and about 2% by mass or less to lower the minimum temperature. A more desirable ratio is in the range of about 0.010% to about 1.000% by weight. A particularly desirable ratio is in the range from about 0.020% to about 0.150% by weight.

  The desirable ratio of the compound (2) is about 10% by mass or more for increasing the dielectric anisotropy and about 90% by mass or less for lowering the minimum temperature. A more desirable ratio is in the range of about 20% to about 80% by weight. A particularly desirable ratio is in the range from about 30% to about 70% 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 20% to about 80% by weight. A particularly desirable ratio is in the range from about 30% to about 70% by weight.

  The second additive is added to the composition for the purpose of making the device compatible with the polymer-supported orientation type device. A preferable ratio of the second additive is about 0.03% 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 2% by weight. A particularly desirable ratio is in the range of about 0.2% to about 1.0% by weight.

式（Ｓ）において、Ｒ^ａは、水素、Ｏ・、ＯＨ、炭素数１から２０のアルキル、炭素数３から２０の脂環式炭化水素基、または炭素数６から２０の芳香族炭化水素基であり、これらの基において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＮＨ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−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、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、ハロゲン、ＯＨ、ＮＨＲ^１ｂ、またはＮＲ^１ｃＲ^１ｄで置き換えられてもよい。Ｒ^１ｂ、Ｒ^１ｃ、およびＲ^１ｄは、炭素数１から１０のアルキルである。好ましいＲ^ａは、メチルである。好ましいＲ^１ｂ、Ｒ^１ｃ、またはＲ^１ｄは、炭素数１から５のアルキルである。 Fourth, a preferred embodiment of the component compounds will be described. In the formula (1), R ^b is hydrogen, fluorine, alkyl having 1 to 20 carbons, an alicyclic hydrocarbon group having 3 to 20 carbons, or an aromatic hydrocarbon group having 6 to 20 carbons, in these groups, at least one of _-CH 2 -, -O -, - NH -, - CO -, - COO-, or may be replaced by -OCO-, at least one _-CH 2 -CH ₂ -May be replaced by -CH = CH- or -C≡C-, in which at least one hydrogen is an alkyl having 1 to 10 carbons, an alkoxy having 1 to 10 carbons, a halogen, It may be replaced by OH, NHR ^1b , or NR ^1c R ^1d . R ^1b , R ^1c and R ^1d are alkyl having 1 to 10 carbons. Desirable ^Rb is hydrogen, alkyl having 1 to 20 carbons, alicyclic hydrocarbon group having 6 to 15 carbons, or aromatic hydrocarbon group having 6 to 15 carbons. Desirable R ^1b , R ^1c or R ^1d is alkyl having 1 to 5 carbons. M is a single bond, a C 1-20 tetravalent aliphatic hydrocarbon group, or a C 6-20 tetravalent aromatic hydrocarbon group, and in these groups, at least one —CH ₂ -May be replaced by -O- or -S-, one or two -CH = CH- may be replaced by -CH = N-, and at least one hydrogen is fluorine or chlorine. It may be replaced. Desirable M is a tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a tetravalent aromatic hydrocarbon group having 6 to 10 carbon atoms. Z ^a and ^{Z b} is a single bond, -O -, - COO -, - OCO-, alkenyl alkyl of from 1 to 20 carbon atoms, or from 2 to 20 carbon atoms, and in the groups, at least one hydrogen May be replaced by fluorine, chlorine, OH. Preferred ^{Z a} or ^{Z b} is a single bond, -COO -, - OCO-, or alkyl of 1 to 5 carbon atoms. Q ^a is a monovalent group represented by the formula (S). n is 1, 2, 3, or 4, and m is 4-n. Preferred n is 2 or 4.

In the formula (S), ^Ra is hydrogen, O., OH, alkyl having 1 to 20 carbons, alicyclic hydrocarbon group having 3 to 20 carbons, or aromatic hydrocarbon group having 6 to 20 carbons. and, in these groups, at least one _-CH 2 is - is, -O -, - NH -, - CO -, - COO-, or may be replaced by -OCO-, at least one -CH ₂ —CH ₂ — may be replaced by —CH ＝ CH— or —C≡C—, and in these groups, at least one hydrogen is an alkyl having 1 to 10 carbons, an alkoxy having 1 to 10 carbons. , Halogen, OH, NHR ^1b , or NR ^1c R ^1d . R ^1b , R ^1c and R ^1d are alkyl having 1 to 10 carbons. Preferred ^Ra is methyl. Desirable R ^1b , R ^1c or R ^1d is alkyl having 1 to 5 carbons.

ここで、Ｒ^ｄは、水素、Ｏ・、ＯＨ、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、または炭素数１から１０のアルコキシであり、これらの基において、少なくとも１つの水素は、ハロゲンで置き換えられてもよい。好ましいＲ^ｄはメチルである。
In the formulas (1-1) to (1-5), Z ^c is a single bond, an alkylene having 1 to 5 carbons, or an alkenylene having 2 to 5 carbons. May be replaced by OH. Preferred ^Zc is a single bond, methylene, or ethylene. R ^c is hydrogen, alkyl having 1 to 20 carbons, an alicyclic hydrocarbon group having 3 to 20 carbons, or an aromatic hydrocarbon group having 6 to 20 carbons, and in these groups, at least one -CH ₂ - is, -O -, - CO -, - COO-, or it may be replaced by -OCO-, at least one _-CH 2 -CH ₂ - is, -CH = CH- or -C≡ In these groups, at least one hydrogen may be OH, alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, or aromatic hydrocarbon having 6 to 20 carbons. May be replaced by Desirable R ^c is an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms in which at least one hydrogen is replaced by OH. s is an integer from 1 to 20. Preferred s is an integer from 1 to 8. Q ^b is a monovalent group represented by the formula (S-1).

Here, R ^d is hydrogen, O., OH, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkoxy having 1 to 10 carbons. In these groups, at least one hydrogen May be replaced by halogen. Preferred R ^d is methyl.

Hereinafter, typical specific examples of the first additive will be described, but the present invention is not limited thereto.

In the formulas (2) and (3), R ^2a and R ^2b represent hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, Alkenyloxy or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Desirable R ^2a or R ^2b is alkyl having 1 to 12 carbons for increasing stability, and alkoxy having 1 to 12 carbons for increasing dielectric anisotropy. R ^3a and R ^3b 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 ^3a or R ^3b is alkenyl having 2 to 12 carbons for decreasing the viscosity, and alkyl having 1 to 12 carbons for increasing the stability.

  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. Trans is preferable in alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity. Cis is preferred in alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl.

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

または

であり、好ましくは

である。 Ring A and ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1 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. Preferred ring A or ring C is 1,4-cyclohexylene for decreasing the viscosity, tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and ring A or C for increasing the optical anisotropy. 1,4-phenylene. Tetrahydropyran-2,5-diyl is

Or

And preferably

It is.

好ましい環Ｂは、粘度を下げるために２，３−ジフルオロ−１，４−フェニレンであり、光学異方性を下げるために２−クロロ−３−フルオロ−１，４−フェニレンであり、誘電率異方性を上げるために７，８−ジフルオロクロマン−２，６−ジイルである。 Ring B 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.

Desirable ring B is 2,3-difluoro-1,4-phenylene for decreasing the viscosity, 2-chloro-3-fluoro-1,4-phenylene for decreasing the optical anisotropy, and a dielectric constant. 7,8-difluorochroman-2,6-diyl for increasing anisotropy.

  Ring D and ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. Desirable ring D or ring E is 1,4-cyclohexylene for decreasing the viscosity or increasing the maximum temperature, and 1,4-phenylene for decreasing the minimum temperature.

Z ^2a and Z ^2b are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Desirable Z ^2a or Z ^2b is a single bond for decreasing the viscosity, ethylene for decreasing the minimum temperature, and methyleneoxy for increasing the dielectric anisotropy. Z ^3a is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Desirable Z ³ is a single bond for decreasing the viscosity.

In methyleneoxy, _-CH 2 O-is -OCH ₂ - preferred over. In carbonyloxy, -COO- is more preferable than -OCO-.

  a is 0, 1, 2 or 3, b is 0 or 1, and the sum of a and b is 3 or less. Desirable a is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature. Desirable b is 0 for decreasing the viscosity, and 1 for decreasing the minimum temperature. c is 1, 2 or 3. Desirable c is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.

In the formula (4), P ^4a , P ^4b , and P ^4c are polymerizable groups. Desirable P ^4a , P ^4b or P ^4c is a polymerizable group selected from the groups represented by the formulas (P-1) to (P-5). More preferred P ^4a , P ^4b , or P ^4c is a group (P-1) or a group (P-2). Particularly preferred groups (P-1) is, -OCO-CH = CH ₂ or _{-OCO-C (CH} 3) a = CH _2. The wavy line from the group (P-1) to the group (P-5) indicates a binding site.

In the group (P-1) to the group (P-5), M ¹ , M ² , and M ³ represent hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen replaced with fluorine or chlorine. Alkyl having 1 to 5 carbon atoms. Preferred M ¹ , M ² , or M ³ is hydrogen or methyl for increasing reactivity. More preferred M ¹ is methyl, and more preferred M ² or M ³ is hydrogen.

In Formulas (4-1) to (4-29), P ^4d , P ^4e , and P ^4f are groups represented by Formulas (P-1) to (P-3). Desirable P ^4d , P ^4e , or P ^4f is a group (P-1) or a group (P-2). Further preferred compounds of formula (P-1) is, -OCO-CH = CH ₂ or _{-OCO-C (CH} 3) a = CH _2. The wavy lines in the formulas (P-1) to (P-3) indicate binding sites.

In the formula (4), Sp ^4a , Sp ^4b , and Sp ^4c are a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO—. , -OCO-, or it may be replaced by -OCOO-, at least one _-CH 2 -CH ₂ - may be replaced by -CH = CH- or -C≡C-, and in the groups , At least one hydrogen may be replaced by fluorine or chlorine. Preferred Sp ^4a , Sp ^4b , or Sp ^4c 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 ^4a , Sp ^4b , or Sp ^4c is a single bond.

  Ring F and Ring I are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl, or pyridine-2-yl. And in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or carbon having at least one hydrogen replaced by fluorine or chlorine. It may be replaced by 1 to 12 alkyl. Preferred ring F or ring I is phenyl. Ring G 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 G is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ^4a and Z ^4b are a single bond or an alkylene having 1 to 10 carbons, wherein at least one —CH ₂ — is —O—, —CO—, —COO—, or —OCO—. may be replaced, 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 ^4a or Z ^4b is a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, or —OCO—. More preferred Z ^4a or Z ^4b is a single bond.

  d is 0, 1, or 2. Desirable d is 0 or 1. e, f, and g are 0, 1, 2, 3, or 4, and the sum of e, f, and g is 1 or more. Preferred e, f, or g is 1 or 2.

  Fifth, preferred component compounds are shown. Preferred compounds (1) are the compounds (1-1) to (1-5) described in item 3. Of these compounds, compound (1-1) or compound (1-2) is preferred.

  Preferred compound (2) is the compound (2-1) to the compound (2-35) described in item 6. In these compounds, at least one of the first components is a compound (2-1), a compound (2-3), a compound (2-6), a compound (2-8), a compound (2-10), a compound ( 2-14) or compound (2-16). At least two of the first components are compound (2-1) and compound (2-8), compound (2-1) and compound (2-14), compound (2-3) and compound (2-8), Compound (2-3) and compound (2-14), compound (2-3) and compound (2-16), compound (2-6) and compound (2-8), compound (2-6) and compound A combination of (2-10), compound (2-6) and compound (2-16), compound (2-10) and compound (2-16) is preferable.

  Desirable compounds (3) are the compounds (3-1) to (3-13) described in item 9. 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 (3-9) is preferable. At least two of the second components are compound (3-1) and compound (3-3), compound (3-1) and compound (3-5), or compound (3-1) and compound (3-6) Is preferable.

  Preferred compounds (4) are the compounds (4-1) to (4-29) described in item 13. In these compounds, at least one of the second additives is compound (4-1), compound (4-2), compound (4-24), compound (4-25), compound (4-26), or Compound (4-27) is preferred. At least two of the second additives are compound (4-1) and compound (4-2), compound (4-1) and compound (4-18), compound (4-2) and compound (4-24) , Compound (4-2) and compound (4-25), compound (4-2) and compound (4-26), compound (4-25) and compound (4-26), or compound (4-18) And the compound (4-24).

  Sixth, 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 compound (5-1) to compound (5-5). 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.

In order 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 element for a long time, the compound (6-1) ) To (6-3), an antioxidant such as compound (6-3) may be further added to the composition.

  Since the compound (6-2) 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 (7-1) to compound (7-16). 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 maximum temperature or increase the minimum 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 liquid crystal compound from being decomposed. Preferred examples of the quencher include compound (8-1) to compound (8-7). A desirable 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 GH (guest host) mode device. The preferred proportion of dye ranges from about 0.01% to about 10% by weight. To prevent foaming, an antifoaming agent such as dimethyl silicone oil or methyl phenyl silicone oil is added to the composition. A desirable ratio of the antifoaming 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 in order to adapt to a device of a polymer supported alignment (PSA) type. Compound (4) is suitable for this purpose. A polymerizable compound different from compound (4) may be added to the composition together with compound (4). Preferred examples of such 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 derivatives of acrylate or methacrylate. A desirable ratio of the compound (4) is 10% by mass or more based on the total mass of the polymerizable compound. A more desirable ratio is 50% by mass or more. A particularly desirable ratio is 80% by mass or more. The most desirable ratio is 100% by mass.

  A polymerizable compound such as the compound (4) 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, the photoinitiators Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF) are suitable for radical polymerization. A preferred ratio of the photopolymerization initiator ranges 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 a polymerizable compound such as the compound (4), a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine and the like.

  Seventh, a method for synthesizing component compounds will be described. These compounds can be synthesized by known methods. The synthesis method is exemplified. Compound (1-A) is available from Tokyo Chemical Industry (TCI). Compound (2-1) is synthesized by the method described in JP-A-2000-053602. Compound (3-1) is synthesized by the method described in JP-A-59-176221. Compound (4-18) is synthesized by the method described in JP-A-7-101900. Antioxidants are commercially available. Compound (6-1) is available from Aldrich (Sigma-Aldrich Corporation). Compound (6-2) and the like are synthesized by the method described in US Pat. No. 3,660,505.

  Compounds for which synthesis methods were not described are described in Organic Syntheses (John Wiley & Sons, Inc), Organic Reactions (John Wiley & Sons, Inc), and Comprehensive Organic Synthesis. 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 together by heating.

  Finally, the use of the composition will be described. The composition primarily has a lower temperature limit of about -10 ° C or less, an upper temperature limit of about 70 ° C or more, and an optical anisotropy in the range of about 0.07 to about 0.20. A composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the ratio of the component compounds or by mixing other liquid crystal compounds. 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 or 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 TN, OCB, IPS mode or FFS mode is particularly preferable. In an AM device having an IPS mode or an FFS mode, when no voltage is applied, the arrangement of liquid crystal molecules may be parallel to or perpendicular to the glass substrate. These elements may be of a reflective, transmissive or transflective type. 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 device produced by microencapsulation and a PD (polymer dispersed) type device in which a three-dimensional network polymer is formed in the composition.

  The present invention will be described in more detail by way of examples. The invention is not limited by these examples. The present invention includes a mixture of the composition of Example 1 and the composition of Example 2. The 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 methods described below.

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 chromatographic analysis: For measurement, a GC-14B gas chromatograph manufactured by Shimadzu Corporation was used. 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. After maintaining the column at 200 ° C. for 2 minutes, the temperature was raised 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 obtained gas chromatogram showed the peak retention time and the peak area corresponding to the component compounds.

  As a solvent for diluting the sample, chloroform, hexane, or the like may be used. 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 the 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 or 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 the compound (15% by mass) with mother liquid crystals (85% by mass). The characteristic values of the compounds were calculated by extrapolation from the values obtained by the measurement. (Extrapolated value) = {(measured value of sample) −0.85 × (measured value of mother liquid crystal)} / 0.15. When the smectic phase (or crystal) precipitates at this ratio at 25 ° C., the ratio between the compound and the mother liquid crystal is changed in the order of 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 lower limit 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): For the measurement, a rotational viscosity measurement system LCM-2 manufactured by Toyo Corporation was used. A sample was injected into a VA device in which a distance (cell gap) between two glass substrates was 10 μm. A rectangular wave (55 V, 1 ms) was applied to this device. The peak current and the peak time of the transient current generated by this application were measured. Using these measured values and the dielectric anisotropy, the value of the rotational viscosity was obtained. The dielectric anisotropy was measured by the method described in Measurement (6).

(5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25 ° C.): Measurement was carried out 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.): The value of the dielectric anisotropy was calculated from the equation: Δ ＝= ‖∥−⊥. The dielectric constant (ε‖ and ε⊥) was measured as follows.
1) Measurement of dielectric constant (ε‖): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a well-cleaned glass substrate. After rotating the glass substrate with a spinner, it was heated at 150 ° C. for 1 hour. A sample was placed in a VA device in which the distance (cell gap) between two glass substrates was 4 μm, and the device was sealed with an adhesive that cured with ultraviolet light. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε‖) in the major axis direction of the liquid crystal molecules was measured.
2) Measurement of dielectric constant (ε⊥): A polyimide solution was applied to a well-cleaned glass substrate. After firing this glass substrate, a rubbing treatment was performed on the obtained alignment film. A sample was placed in a TN device in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. 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.

(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 is placed in a normally black mode VA device in which the distance between two glass substrates (cell gap) is 4 μm and the rubbing direction is antiparallel, and an adhesive that cures this device with ultraviolet light is used. And sealed. The voltage (60 Hz, rectangular wave) applied to this device was increased stepwise from 0 V to 20 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 created 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 10%.

(8) Voltage holding ratio (VHR-9; measured at 25 ° C .;%): The TN device used for the measurement had a polyimide alignment film, and the distance between two glass substrates (cell gap) was 5 μm. . The device was sealed with an adhesive that cured with ultraviolet light after the sample was placed. The TN device was charged by applying a pulse voltage (1 V, 60 microseconds). The decaying voltage was measured with a high-speed voltmeter for 16.67 milliseconds, 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 (VHR-10; measured at 60 ° C .;%): The voltage holding ratio was measured in the same procedure as described above except that the voltage holding ratio was measured at 60 ° C. instead of 25 ° C. The obtained value was represented by VHR-10.

(10) Voltage holding ratio (VHR-11; measured at 60 ° C .;%): After irradiation with ultraviolet rays, the voltage holding ratio was measured, and the stability to ultraviolet rays was evaluated. The TN device used for the measurement had a polyimide alignment film, and the cell gap was 5 μm. A sample was injected into the device, and irradiated with ultraviolet rays of 5 mW / cm ² for 167 minutes. The light source was a black light manufactured by Eye Graphics Co., Ltd., F40T10 / BL (peak wavelength: 369 nm), and the distance between the element and the light source was 5 mm. In the measurement of VHR-11, a decaying voltage was measured for 16.67 milliseconds. A composition having a large VHR-11 has a large stability to ultraviolet light.

(11) Voltage holding ratio (VHR-12; measured at 60 ° C .;%): After heating the TN device into which the sample was injected in a thermostat at 120 ° C. for 20 hours, the voltage holding ratio was measured, and the stability to heat was measured. Was evaluated. In the measurement of VHR-12, a decaying voltage was measured for 16.67 milliseconds. Compositions having a large VHR-12 have a large stability to heat.

(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 into a normally black mode VA device in which the distance between two glass substrates (cell gap) was 4 μm and the rubbing direction was antiparallel. The device was sealed with an adhesive that cured with ultraviolet light. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to the 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 response time was represented by the time required for the transmittance to change from 90% to 10% (fall time; millisecond).

(13) Specific resistance (ρ; measured at 25 ° C .; Ωcm): A sample (1.0 mL) was injected into a vessel 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)}.

(14) Resistance value of liquid crystal display element (ρ; measured at 60 ° C .; Ω): The DC voltage applied to the TN element into which the sample was injected was increased stepwise from 0 V to 10 V in steps of 0.1 V. At this time, the current value flowing through the element was measured, and a voltage value-current value straight line was created. According to Ohm's law, the reciprocal of the slope was defined as the resistance value of the element.

(15) Line Image Sticking Parameter (LISP;%): Line image sticking was generated by applying an electric stress to the liquid crystal display element. The luminance of the area with the line afterimage and the luminance of the remaining area were measured. The rate at which the luminance was reduced by the line afterimage was calculated, and the ratio was used to represent the size of the line afterimage.

(15a) Measurement of luminance: An image of the element was photographed using an imaging color luminance meter (PM-1433F-0, manufactured by Radiant Zemax). This image was analyzed using software (Prometric 9.1, manufactured by Radiant Imaging) to calculate the luminance of each region of the element.

(15b) Setting of stress voltage: A sample was placed in a liquid crystal display device having a matrix structure (16 cells of 4 cells vertically × 4 cells horizontally), and the device was sealed with an adhesive which was cured by ultraviolet rays. A polarizing plate was arranged on each of the upper and lower surfaces of the device so that the polarization axes were orthogonal to each other. The device was irradiated with light and a voltage was applied. The luminance of the transmitted light at each voltage was measured. The voltage when the luminance became maximum was abbreviated as V255. The voltage when the luminance became 21.6% of V255 (that is, 127 gradations) was abbreviated as V127.

(15c) Stress condition: V255 and 0.5 V were applied to the device at 60 ° C. for 23 hours to display a checker pattern. Next, V127 was applied, the entire surface was turned on, and the luminance was measured.

(15d) Calculation of line afterimage: Of the 16 cells, 4 cells at the center (2 cells vertically × 2 cells horizontally) were used for the calculation. These 4 cells were divided into 25 areas (5 vertical cells × 5 horizontal cells). The average luminance of four regions (two vertical cells × two horizontal cells) at the four corners was abbreviated as luminance A. The region excluding the four corner regions from the 25 regions was cross-shaped. The minimum value of the luminance was abbreviated as luminance B in four regions except the central cross region from the cross-shaped region. The line afterimage was calculated from the following equation.
(Line afterimage) = (brightness A−brightness B) / brightness A × 100.

  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.

[Comparative Example 1]
3-HB (2F, 3F) -O2 (2-1) 4%
2-BB (2F, 3F) -O2 (2-6) 8%
3-BB (2F, 3F) -O2 (2-6) 8%
V2-BB (2F, 3F) -O2 (2-6) 2%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 10%
V-HHB (2F, 3F) -O4 (2-8) 4%
2-HHB (2F, 3F) -O2 (2-8) 2%
3-HHB (2F, 3F) -O2 (2-8) 4%
5-HHB (2F, 3F) -O2 (2-8) 3%
3-HH2B (2F, 3F) -O2 (2-9) 10%
3-HDhB (2F, 3F) -O2 (2-13) 10%
3-dhBB (2F, 3F) -O2 (2-16) 2%
3-HH-V (3-1) 20%
3-HHB-1 (3-5) 3%
3-HBB-2 (3-6) 6%
NI = 89.9 ° C .; Tc <−20 ° C .; Δn = 0.111; Δε = −4.1; Vth = 1.98V; LISP = 28.4%

Example 1 was a composition obtained by adding the compound (1-A) to the composition of Comparative Example 1.
[Example 1]
3-HB (2F, 3F) -O2 (2-1) 4%
2-BB (2F, 3F) -O2 (2-6) 8%
3-BB (2F, 3F) -O2 (2-6) 8%
V2-BB (2F, 3F) -O2 (2-6) 2%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 10%
V-HHB (2F, 3F) -O4 (2-8) 4%
2-HHB (2F, 3F) -O2 (2-8) 2%
3-HHB (2F, 3F) -O2 (2-8) 4%
5-HHB (2F, 3F) -O2 (2-8) 3%
3-HH2B (2F, 3F) -O2 (2-9) 10%
3-HDhB (2F, 3F) -O2 (2-13) 10%
3-dhBB (2F, 3F) -O2 (2-16) 2%
3-HH-V (3-1) 20%
3-HHB-1 (3-5) 3%
3-HBB-2 (3-6) 6%
Compound (1-A) was added to the composition at a rate of 0.100% by mass.
NI = 89.9 ° C .; Tc <−20 ° C .; Δn = 0.111; Δε = −4.1; Vth = 1.98V; LISP = 1.5%

A composition in which the compound (1-C) was added to the composition of Comparative Example 1 was used as Example 2.
[Example 2]
3-HB (2F, 3F) -O2 (2-1) 4%
2-BB (2F, 3F) -O2 (2-6) 8%
3-BB (2F, 3F) -O2 (2-6) 8%
V2-BB (2F, 3F) -O2 (2-6) 2%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 10%
V-HHB (2F, 3F) -O4 (2-8) 4%
2-HHB (2F, 3F) -O2 (2-8) 2%
3-HHB (2F, 3F) -O2 (2-8) 4%
5-HHB (2F, 3F) -O2 (2-8) 3%
3-HH2B (2F, 3F) -O2 (2-9) 10%
3-HDhB (2F, 3F) -O2 (2-13) 10%
3-dhBB (2F, 3F) -O2 (2-16) 2%
3-HH-V (3-1) 20%
3-HHB-1 (3-5) 3%
3-HBB-2 (3-6) 6%
Compound (1-C) was added to the composition at a rate of 0.100% by mass.
NI = 89.9 ° C .; Tc <−20 ° C .; Δn = 0.111; Δε = −4.1; Vth = 1.98V; LISP = 2.4%

  Further, in order to confirm the effects on image sticking and display unevenness, line afterimages were observed. The liquid crystal compositions of Comparative Example 1, Example 1, and Example 2 were placed in a liquid crystal display device, and line afterimages were observed. The line afterimage was observed in an initial state before stress application and in a state after stress application (Table 4).

  In the initial state, it can be seen that display defects such as image sticking and display unevenness have not occurred. After the application, in Comparative Example 1, line afterimages are clearly observed between the electrodes, and burn-in of the checker pattern is slightly observed. On the other hand, in Examples 1 and 2, no line afterimage occurs, and it can be seen that there is no change from the initial state.

Table 4. Afterimage observation result

[Example 3]
2-H1OB (2F, 3F) -O2 (2-3) 8%
3-H1OB (2F, 3F) -O2 (2-3) 9%
2-HHB (2F, 3F) -O2 (2-8) 3%
3-HHB (2F, 3F) -O2 (2-8) 4%
2-HBB (2F, 3F) -O2 (2-14) 5%
3-HBB (2F, 3F) -O2 (2-14) 11%
4-HBB (2F, 3F) -O2 (2-14) 5%
5-HBB (2F, 3F) -O2 (2-14) 10%
2-HH-3 (3-1) 20%
3-HH-4 (3-1) 4%
3-HB-O2 (3-2) 14%
3-HBB-2 (3-6) 7%
Compound (1-B) was added to the composition at a rate of 0.050% by mass.
NI = 77.8 ° C .; Tc <−20 ° C .; Δn = 0.105; Δε = −3.4; Vth = 2.13V; LISP = 1.9%

[Example 4]
2-H1OB (2F, 3F) -O2 (2-3) 7%
3-H1OB (2F, 3F) -O2 (2-3) 7%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 8%
4-HBB (2F, 3F) -O2 (2-14) 4%
5-HBB (2F, 3F) -O2 (2-14) 7%
2-BB (2F, 3F) B-3 (2-19) 2%
2-HH-3 (3-1) 18%
3-HH-4 (3-1) 4%
3-HH-5 (3-1) 3%
3-HB-O2 (3-2) 13%
5-HB-O2 (3-2) 7%
3-HHB-3 (3-5) 2%
3-HBB-2 (3-6) 14%
Compound (1-C) was added to the composition at a rate of 0.100% by mass.
NI = 76.1 ° C .; Tc <−20 ° C .; η = 15.2 mPa · s; Δn = 0.107; Δε = −2.1; LISP = 2.1%

[Example 5]
2-H1OB (2F, 3F) -O2 (2-3) 7%
3-H1OB (2F, 3F) -O2 (2-3) 7%
3-HHB (2F, 3F) -O2 (2-8) 4%
3-HH1OB (2F, 3F) -O2 (2-10) 4%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 8%
4-HBB (2F, 3F) -O2 (2-14) 4%
5-HBB (2F, 3F) -O2 (2-14) 5%
3-dhBB (2F, 3F) -O2 (2-16) 4%
2-HH-3 (3-1) 18%
2-HH-5 (3-1) 2%
3-HH-4 (3-1) 3%
3-HH-5 (3-1) 3%
3-HB-O2 (3-2) 17%
3-HBB-2 (3-6) 10%
Compound (1-C) was added to the composition at a rate of 0.075% by mass.
NI = 77.3 ° C .; Tc <−20 ° C .; η = 16.1 mPa · s; Δn = 0.102; Δε = −2.8; LISP = 1.9%

[Example 6]
2-H1OB (2F, 3F) -O2 (2-3) 7%
3-H1OB (2F, 3F) -O2 (2-3) 7%
3-HHB (2F, 3F) -O2 (2-8) 5%
3-HDhB (2F, 3F) -O2 (2-13) 5%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 9%
4-HBB (2F, 3F) -O2 (2-14) 4%
5-HBB (2F, 3F) -O2 (2-14) 9%
3-dhBB (2F, 3F) -O2 (2-16) 4%
2-HH-3 (3-1) 18%
3-HH-4 (3-1) 3%
3-HH-5 (3-1) 3%
3-HB-O2 (3-2) 13%
3-HBB-2 (3-6) 9%
Compound (1-C) was added to the composition at a rate of 0.100% by mass.
NI = 75.9 ° C .; η = 18.4 mPa · s; Δn = 0.105; Δε = -3.4; Vth = 2.13V; LISP = 1.8%

[Example 7]
2-H1OB (2F, 3F) -O2 (2-3) 8%
3-H1OB (2F, 3F) -O2 (2-3) 8%
2O-B (2F) B (2F, 3F) -O2 (2-7) 4%
2O-B (2F) B (2F, 3F) -O4 (2-7) 6%
3-HHB (2F, 3F) -O2 (2-8) 7%
2-HBB (2F, 3F) -O2 (2-14) 3%
3-HBB (2F, 3F) -O2 (2-14) 10%
2-HH-3 (3-1) 18%
3-HH-4 (3-1) 5%
3-HH-5 (3-1) 5%
3-HB-O2 (3-2) 7%
3-HHB-1 (3-5) 5%
3-HHB-3 (3-5) 6%
3-HBB-2 (3-6) 8%
Compound (1-B) was added to the composition at a rate of 0.050% by mass.
NI = 74.0 ° C .; Tc <−20 ° C .; Δn = 0.098; Δε = −3.0; Vth = 2.17 V; LISP = 2.5%

Example 8
3-HB (2F, 3F) -O2 (2-1) 13%
3-HHB (2F, 3F) -O2 (2-8) 4%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 11%
4-HBB (2F, 3F) -O2 (2-14) 5%
V-HBB (2F, 3F) -O2 (2-14) 8%
V-HBB (2F, 3F) -O4 (2-14) 8%
3-HH-V (3-1) 30%
V-HH-V (3-1) 3%
V-HH-V1 (3-1) 3%
3-HH-V1 (3-1) 5%
1-BB-3 (3-3) 6%
Compound (1-C) was added to the composition at a rate of 0.100% by mass.
NI = 74.9 ° C .; Tc <−20 ° C .; Δn = 0.106; Δε = −2.6; LISP = 2.1%

[Example 9]
3-HB (2F, 3F) -O2 (2-1) 3%
2O-B (2F) B (2F, 3F) -O2 (2-7) 5%
2O-B (2F) B (2F, 3F) -O4 (2-7) 12%
2-HHB (2F, 3F) -O2 (2-8) 4%
3-HHB (2F, 3F) -O2 (2-8) 8%
5-HBB (2F, 3F) -O2 (2-14) 8%
3-dhBB (2F, 3F) -O2 (2-16) 8%
3-HH-V (3-1) 33%
3-HH-V1 (3-1) 5%
1-BB-3 (3-3) 6%
3-HHB-1 (3-5) 8%
Compound (1-B) was added to the composition at a rate of 0.075% by mass.
NI = 74.9 ° C .; Tc <−20 ° C .; Δn = 0.106; Δε = −2.7; LISP = 2.3%

[Example 10]
2O-B (2F) B (2F, 3F) -O2 (2-7) 6%
2O-B (2F) B (2F, 3F) -O4 (2-7) 13%
2-HHB (2F, 3F) -O2 (2-8) 4%
3-HHB (2F, 3F) -O2 (2-8) 8%
3-dhBB (2F, 3F) -O2 (2-16) 5%
3-HB (2F) B (2F, 3F) -O2 (2-18) 7%
3-H2BBB (2F, 3F) -O2 (2-25) 5%
3-HH-V (3-1) 42%
3-HH-V1 (3-1) 5%
1-BB-3 (3-3) 3%
V-HHB-1 (3-5) 2%
Compound (1-C) was added to the composition at a rate of 0.100% by mass.
NI = 75.3 ° C .; Tc <−20 ° C .; Δn = 0.106; Δε = −2.7; LISP = 1.8%

[Example 11]
3-H2B (2F, 3F) -O2 (2-2) 15%
5-H2B (2F, 3F) -O2 (2-2) 6%
3-HDhB (2F, 3F) -O2 (2-13) 7%
3-HBB (2F, 3F) -O2 (2-14) 10%
4-HBB (2F, 3F) -O2 (2-14) 7%
5-HBB (2F, 3F) -O2 (2-14) 7%
2-HH-3 (3-1) 18%
3-HH-4 (3-1) 8%
3-HB-O2 (3-2) 10%
5-HB-O2 (3-2) 3%
3-HHB-1 (3-5) 3%
3-HHB-3 (3-5) 3%
3-HHB-O1 (3-5) 3%
Compound (1-C) was added to this composition at a rate of 0.050% by mass.
NI = 75.9 ° C .; Tc <−20 ° C .; η = 17.8 mPa · s; Δn = 0.083; Δε = −2.8; LISP = 2.0%

[Example 12]
3-BB (2F, 3F) -O2 (2-6) 10%
V2-BB (2F, 3F) -O2 (2-6) 9%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 12%
V-HHB (2F, 3F) -O4 (2-8) 10%
3-HH2B (2F, 3F) -O2 (2-9) 8%
3-HH-V (3-1) 29%
3-HB-O2 (3-2) 1%
1-BB-3 (3-3) 4%
1-BB-5 (3-3) 2%
V-HHB-1 (3-5) 11% Compound (1-B) was added to this composition at a rate of 0.100% by mass.
NI = 75.0 ° C .; Tc <−20 ° C .; η = 13.8 mPa · s; Δn = 0.102; Δε = −2.7; LISP = 2.1%

Example 13
3-HB (2F, 3F) -O2 (2-1) 13%
3-HHB (2F, 3F) -1 (2-8) 2%
3-HHB (2F, 3F) -2 (2-8) 2%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 11%
4-HBB (2F, 3F) -O2 (2-14) 5%
V-HBB (2F, 3F) -O2 (2-14) 8%
V-HBB (2F, 3F) -O4 (2-14) 8%
3-HH-V (3-1) 36%
3-HH-V1 (3-1) 5%
1-BB-3 (3-3) 6%
Compound (1-B) was added to the composition at a rate of 0.075% by mass.
NI = 72.8 ° C .; Tc <−20 ° C .; Δn = 0.104; Δε = −2.4; LISP = 1.8%

[Example 14]
3-HB (2F, 3F) -O2 (2-1) 3%
2O-B (2F) B (2F, 3F) -O2 (2-7) 5%
2O-B (2F) B (2F, 3F) -O4 (2-7) 12%
2-HHB (2F, 3F) -O2 (2-8) 4%
3-HHB (2F, 3F) -O2 (2-8) 8%
5-HBB (2F, 3F) -O2 (2-14) 4%
3-dhBB (2F, 3F) -O2 (2-16) 8%
3-HB (2F, 3F) B-2 (2-17) 4%
3-HH-V (3-1) 33%
3-HH-V1 (3-1) 5%
1-BB-3 (3-3) 6%
3-HHB-1 (3-5) 6%
5-B (F) BB-2 (3-7) 2%
Compound (1-C) was added to the composition at a rate of 0.100% by mass.
NI = 71.8 ° C .; Tc <−20 ° C .; Δn = 0.105; Δε = −2.6; LISP = 1.9%

[Example 15]
3-DhB (2F, 3F) -O2 (2-4) 2%
2O-B (2F) B (2F, 3F) -O2 (2-7) 5%
2O-B (2F) B (2F, 3F) -O4 (2-7) 14%
2-HHB (2F, 3F) -O2 (2-8) 2%
3-HHB (2F, 3F) -O2 (2-8) 5%
2-HBB (2F, 3F) -O2 (2-14) 2%
3-HBB (2F, 3F) -O2 (2-14) 9%
3-HH-V (3-1) 32%
3-HH-V1 (3-1) 5%
1-BB-3 (3-3) 5%
3-HHB-1 (3-5) 2%
3-HBB-2 (3-6) 17%
Compound (1-C) was added to the composition at a rate of 0.075% by mass.
NI = 74.2 ° C .; Tc <−20 ° C .; Δn = 0.115; Δε = −2.1; LISP = 2.3%

[Example 16]
3-HB (2F, 3F) -O2 (2-1) 7%
V-HB (2F, 3F) -O2 (2-1) 15%
3-BB (2F, 3F) -O2 (2-6) 3%
3-HHB (2F, 3F) -O2 (2-8) 6%
V-HHB (2F, 3F) -O2 (2-8) 11%
V-HHB (2F, 3F) -O4 (2-8) 4%
3-HBB (2F, 3F) -O2 (2-14) 10%
4-HBB (2F, 3F) -O2 (2-14) 5%
V-HBB (2F, 3F) -O2 (2-14) 5%
2-HH-3 (3-1) 15%
3-HH-4 (3-1) 7%
1-BB-3 (3-3) 3%
3-HBB-2 (3-6) 7%
V-HBB-2 (3-6) 2%
Compound (1-C) was added to the composition at a rate of 0.100% by mass.
NI = 79.5 ° C .; Tc <−30 ° C .; Δn = 0.110; Δε = −3.8; LISP = 2.3%

この組成物に化合物（１−Ａ）を０．０９０質量％の割合で添加した。
ＮＩ＝７５．１℃；Δｎ＝０．１０５；Δε＝−２．４；ＬＩＳＰ＝２．４％

[Example 17]
3-H1OB (2F, 3F) -O2 (2-3) 8%
3-HHB (2F, 3F) -O2 (2-8) 4%
3-HH2B (2F, 3F) -O2 (2-9) 12%
3-HH1OB (2F, 3F) -O2 (2-10) 14%
3-HB (2F) B (2F, 3F) -O2 (2-18) 6%
2-HH-3 (3-1) 18%
2-HH-5 (3-1) 2.5%
3-HH-4 (3-1) 3%
3-HH-5 (3-1) 4%
1-BB-3 (3-3) 4%
1-BB-5 (3-3) 16%
3-HBB-2 (3-6) 8.5%
Compound (4-25-1) was added to this composition at a rate of 0.36% by mass.

Compound (1-A) was added to this composition at a rate of 0.090% by mass.
NI = 75.1 ° C; Δn = 0.105; Δε = -2.4; LISP = 2.4%

[Example 18]
3-HB (2F, 3F) -O2 (2-1) 2%
2-BB (2F, 3F) -O2 (2-6) 5%
3-BB (2F, 3F) -O2 (2-6) 6%
V2-BB (2F, 3F) -O2 (2-6) 8%
2-HHB (2F, 3F) -O2 (2-8) 5%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 10%
3-HDhB (2F, 3F) -O2 (2-13) 10%
3-dhBB (2F, 3F) -O2 (2-16) 5%
3-HB (2F) B (2F, 3F) -O2 (2-18) 2%
3-HH-V (3-1) 29%
3-HH-V1 (3-1) 5%
V-HHB-1 (3-5) 9%
Compound (1-B) was added to the composition at a rate of 0.075% by mass.
NI = 76.8 ° C .; Δn = 0.100; Δε = −3.4; LISP = 1.8%

[Example 19]
2-BB (2F, 3F) -O2 (2-6) 5%
3-BB (2F, 3F) -O2 (2-6) 9%
V2-BB (2F, 3F) -O2 (2-6) 6%
2-HHB (2F, 3F) -O2 (2-8) 4%
3-HHB (2F, 3F) -O2 (2-8) 6%
V-HHB (2F, 3F) -O1 (2-8) 3%
V-HHB (2F, 3F) -O2 (2-8) 8%
3-dhBB (2F, 3F) -O2 (2-16) 7%
3-HB (2F) B (2F, 3F) -O2 (2-18) 10%
3-HH-V (3-1) 29%
3-HH-V1 (3-1) 7%
V-HBB-2 (3-6) 6%
Compound (1-C) was added to this composition at a rate of 0.050% by mass.
NI = 78.5 ° C .; Tc <−30 ° C .; Δn = 0.112; Δε = −3.2; LISP = 2.0%

[Example 20]
2-BB (2F, 3F) -O2 (2-6) 5%
3-BB (2F, 3F) -O2 (2-6) 7%
V2-BB (2F, 3F) -O2 (2-6) 8%
2-HHB (2F, 3F) -O2 (2-8) 4%
3-HHB (2F, 3F) -O2 (2-8) 8%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 10%
3-dhBB (2F, 3F) -O2 (2-16) 10%
3-HH-V (3-1) 28%
V-HHB-1 (3-5) 7.5%
V-HBB-2 (3-6) 8.5%
Compound (1-C) was added to this composition at a rate of 0.080% by mass.
NI = 86.5 ° C .; Tc <−30 ° C .; Δn = 0.114; Δε = −3.0; LISP = 2.3%

[Example 21]
2-BB (2F, 3F) -O2 (2-6) 5%
3-BB (2F, 3F) -O2 (2-6) 10%
V2-BB (2F, 3F) -O2 (2-6) 7%
5-BB (2F, 3F) -O2 (2-6) 3%
2-HHB (2F, 3F) -O2 (2-8) 3%
3-HHB (2F, 3F) -O2 (2-8) 7.5%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 8%
V-HHB (2F, 3F) -O4 (2-8) 2%
3-HDhB (2F, 3F) -O2 (2-13) 3.5%
3-HH-V (3-1) 29%
V-HHB-1 (3-5) 11%
V-HBB-2 (3-6) 7%
Compound (1-A) was added to the composition at a rate of 0.100% by mass.
NI = 76.1 ° C .; Tc <−30 ° C .; Δn = 0.107; Δε = −2.8; LISP = 2.4%

[Example 22]
3-H2B (2F, 3F) -O2 (2-2) 15%
5-H2B (2F, 3F) -O2 (2-2) 6%
V2-BB (2F, 3F) -O2 (2-6) 2%
3-HHB (2F, 3F) -O2 (2-8) 5%
3-HH2B (2F, 3F) -O2 (2-9) 8%
3-HDhB (2F, 3F) -O2 (2-13) 12%
3-HH-V (3-1) 2.5%
1V2-HH-1 (3-1) 8%
1V2-HH-3 (3-1) 8%
1-BB-3 (3-3) 6.5%
V-HHB-1 (3-5) 14%
V2-HHB-1 (3-5) 9%
V-HBB-2 (3-6) 4%
Compound (1-B) was added to the composition at a rate of 0.075% by mass.
NI = 85.2 ° C .; Tc <−30 ° C .; Δn = 0.100; Δε = −2.7; LISP = 2.3%

[Example 23]
3-HB (2F, 3F) -O2 (2-1) 10%
V-HB (2F, 3F) -O2 (2-1) 10%
3-BB (2F, 3F) -O2 (2-6) 4%
2-HHB (2F, 3F) -O2 (2-8) 2%
3-HHB (2F, 3F) -O2 (2-8) 7%
5-HHB (2F, 3F) -O2 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 3%
2-HBB (2F, 3F) -O2 (2-14) 2%
3-HBB (2F, 3F) -O2 (2-14) 7%
4-HBB (2F, 3F) -O2 (2-14) 5%
V-HBB (2F, 3F) -O2 (2-14) 6%
V-HBB (2F, 3F) -O4 (2-14) 5%
2-HH-3 (3-1) 15%
3-HH-4 (3-1) 5%
3-HH-5 (3-1) 2%
3-HH-VFF (3-1) 5%
V-HBB-2 (3-6) 8%
Compound (1-C) was added to this composition at a rate of 0.050% by mass.
NI = 81.5 ° C .; Tc <−30 ° C .; Δn = 0.108; Δε = −3.6; LISP = 2.0%

[Example 24]
2-BB (2F, 3F) -O2 (2-6) 10%
3-BB (2F, 3F) -O2 (2-6) 2%
V2-BB (2F, 3F) -O2 (2-6) 9.5%
2-HHB (2F, 3F) -O2 (2-8) 3.5%
3-HHB (2F, 3F) -O2 (2-8) 8%
5-HHB (2F, 3F) -O2 (2-8) 4%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 10%
3-HDhB (2F, 3F) -O2 (2-13) 7%
3-dhBB (2F, 3F) -O2 (2-16) 7%
3-HH-V (3-1) 29%
3-HH-V1 (3-1) 2%
V-HHB-1 (3-5) 4%
Compound (1-C) was added to the composition at a rate of 0.075% by mass.
NI = 80.9 ° C .; Tc <−40 ° C .; η = 17.7 mPa · s; Δn = 0.104; Δε = −4.0; LISP = 2.1%

[Example 25]
3-BB (2F, 3F) -O2 (2-6) 8%
5-BB (2F, 3F) -O2 (2-6) 7%
V2-BB (2F, 3F) -O2 (2-6) 6%
2-HHB (2F, 3F) -O2 (2-8) 3%
3-HHB (2F, 3F) -O2 (2-8) 7%
5-HHB (2F, 3F) -O2 (2-8) 7%
V-HHB (2F, 3F) -O1 (2-8) 3%
V-HHB (2F, 3F) -O2 (2-8) 6%
3-dhBB (2F, 3F) -O2 (2-16) 5%
3-HB (2F) B (2F, 3F) -O2 (2-18) 14%
3-HH-V (3-1) 29%
V-HH-V1 (3-1) 5%
Compound (1-B) was added to this composition at a rate of 0.080% by mass.
NI = 80.1 ° C .; Tc <−30 ° C .; η = 17.3 mPa · s; Δn = 0.110; Δε = −3.7; LISP = 2.0%

  The LISP of the composition of Comparative Example 1 was 28.4%. On the other hand, the LISP of the compositions of Examples 1 to 25 ranged from 1.5% to 2.5%. Further, from the observation result of the line afterimage, in the device containing the composition of Comparative Example 1, line afterimage and image sticking were observed, whereas in the devices containing the compositions of Example 1 and Example 2, No line afterimage or image sticking was observed. Therefore, it is concluded that the liquid crystal composition of the present invention has more excellent properties, and that a liquid crystal display device with excellent display quality can be obtained by using the liquid crystal composition of the present invention.

  The specific resistances of the liquid crystal compositions of Comparative Example 1, Example 1, and Example 2 were measured. Further, these liquid crystal compositions were put into a liquid crystal display device, and the resistance value of the liquid crystal display device was measured. The results are summarized in Table 5.

実施例１および実施例２の比抵抗値は、比較例１と比較して若干低いが、実施例１および実施例２の液晶表示素子の抵抗値は、比較例１と比較して顕著に低いことがわかる。したがって、本発明の液晶組成物を用いることにより、より帯電が抑制された液晶表示素子が得られると結論付けられる。 Table 5. Comparison of specific resistance of composition and resistance of device

The specific resistance values of Examples 1 and 2 are slightly lower than that of Comparative Example 1, but the resistance values of the liquid crystal display elements of Examples 1 and 2 are significantly lower than that of Comparative Example 1. You can see that. Therefore, it can be concluded that the use of the liquid crystal composition of the present invention can provide a liquid crystal display device with further suppressed charging.

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

Claims (19)

A liquid crystal composition comprising at least one compound selected from compounds having a monovalent group represented by the formula (S) as a first additive, and having a nematic phase and negative dielectric anisotropy.

In the formula (S), ^Ra is hydrogen, O., OH, alkyl having 1 to 20 carbons, alicyclic hydrocarbon group having 3 to 20 carbons, or aromatic hydrocarbon group having 6 to 20 carbons. and, in these groups, at least one _-CH 2 is - is, -O -, - NH -, - CO -, - COO-, or may be replaced by -OCO-, at least one -CH ₂ —CH ₂ — may be replaced by —CH ＝ CH— or —C≡C—, and in these groups, at least one hydrogen is an alkyl having 1 to 10 carbons, an alkoxy having 1 to 10 carbons. , Halogen, OH, NHR ^1b , or NR ^1c R ^1d ;
Here, R ^1b , R ^1c and R ^1d are alkyl having 1 to 10 carbons. The liquid crystal composition according to claim 1, comprising at least one compound selected from the compounds represented by the formula (1) as a first additive.

In the formula (1), R ^b is hydrogen, fluorine, alkyl having 1 to 20 carbons, an alicyclic hydrocarbon group having 3 to 20 carbons, or an aromatic hydrocarbon group having 6 to 20 carbons, in these groups, at least one of _-CH 2 -, -O -, - NH -, - CO -, - COO-, or may be replaced by -OCO-, at least one _-CH 2 -CH ₂ -May be replaced by -CH = CH- or -C≡C-, in which at least one hydrogen is an alkyl having 1 to 10 carbons, an alkoxy having 1 to 10 carbons, a halogen, R ^1b , R ^1c , and R ^1d may be substituted with OH, NHR ^1b , or NR ^1c R ^1d ; R ^1b , R ^1c , and R ^1d are alkyl having 1 to 10 carbons; M is a single bond, 1 to 20 carbons Tetravalent fat A family hydrocarbon group or a tetravalent aromatic hydrocarbon group having 6 to 20 carbon atoms, in these groups, at least one -CH 2 _- may be replaced by -O- or -S- , one or two -CH = CH- may be replaced by -CH = N-, at least one hydrogen may be replaced by fluorine or chlorine; ^{Z a} and ^{Z b} is a single bond, -O-, -COO-, -OCO-, alkylene having 1 to 20 carbons or alkenylene having 2 to 20 carbons, in which at least one hydrogen is replaced by fluorine, chlorine, OH Q ^a is a monovalent group represented by the formula (S); n is 1, 2, 3, or 4; m is 4-n; In the case of a bond, n and m are 1;

In the formula (S), ^Ra is hydrogen, O., OH, alkyl having 1 to 20 carbons, alicyclic hydrocarbon group having 3 to 20 carbons, or aromatic hydrocarbon group having 6 to 20 carbons. and, in these groups, at least one _-CH 2 is - is, -O -, - NH -, - CO -, - COO-, or may be replaced by -OCO-, at least one -CH ₂ —CH ₂ — may be replaced by —CH ＝ CH— or —C≡C—, and in these groups, at least one hydrogen is an alkyl having 1 to 10 carbons, an alkoxy having 1 to 10 carbons. , Halogen, OH, NHR ^1b , or NR ^1c R ^1d ;
Here, R ^1b , R ^1c and R ^1d are alkyl having 1 to 10 carbons. The liquid crystal composition according to claim 1, comprising at least one compound selected from the compounds represented by Formulas (1-1) to (1-5) as a first additive.

In the formulas (1-1) to (1-5), Z ^c is a single bond, an alkylene having 1 to 5 carbons or an alkenylene having 2 to 5 carbons. In these groups, at least one hydrogen is , OH; R ^c is hydrogen, alkyl having 1 to 20 carbons, alicyclic hydrocarbon having 3 to 20 carbons, or aromatic hydrocarbon having 6 to 20 carbons. , In these groups, at least one —CH ₂ — may be replaced by —O—, —CO—, —COO—, or —OCO—, and at least one —CH ₂ —CH ₂ — —CH ＝ CH— or —C≡C—, in which at least one hydrogen is OH, alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, or carbon having 1 to 10 carbons. 6 to 2 Is s, be of 1 to 20 integer; may be replaced by an aromatic hydrocarbon group Q ^b is a monovalent group represented by the formula (S-1);

In the formula (S-1), R ^d is hydrogen, O., OH, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkoxy having 1 to 10 carbons. , At least one hydrogen may be replaced by halogen.   The liquid crystal composition according to claim 1, wherein a ratio of the first additive is in a range of 0.001% by mass to 2% by mass. The liquid crystal composition according to any one of claims 1 to 4, comprising at least one compound selected from the compounds represented by the formula (2) as the first component.

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

In the formulas (2-1) to (2-35), R ^2a and R ^2b represent hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon number. It is an alkenyloxy having 2 to 12 carbons or an alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.   The liquid crystal composition according to claim 5, wherein a ratio of the first 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 7, further comprising at least one compound selected from the compounds represented by the formula (3) as the second component.

In the formula (3), R ^3a and R ^3b 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 D and ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4 -Phenylene; Z ^3a is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; c is 1, 2, or 3. The liquid crystal composition according to any one of claims 1 to 8, wherein the liquid crystal composition comprises at least one compound selected from the compounds represented by Formulas (3-1) to (3-13) as the second component. .

In the formulas (3-1) to (3-13), R ^3a and R ^3b represent 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 8, 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 10, further comprising at least one compound selected from the polymerizable compounds represented by Formula (4) as the second additive.

In the formula (4), ring F and ring I 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. Ring G may be substituted with 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, 1 carbon atom or less. 12 alkyl, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen has been replaced by fluorine or chlorine; Z ^4a and Z ^4b 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, 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 ^{4a, P 4b} and ^{P 4c,} Is a polymerizable group; Sp ^4a , Sp ^4b , and Sp ^4c are a single bond or an alkylene having 1 to 10 carbon atoms, in which at least one -CH ₂ -is -O-,- COO—, —OCO—, or —OCOO—, and at least one of —CH ₂ —CH ₂ — may be replaced by —CH ＝ CH— or —C 、 C— Group Wherein at least one hydrogen may be replaced by fluorine or chlorine; d is 0, 1, or 2; e, f, and g are 0, 1, 2, 3, or 4 Yes; and the sum of e, f, and g is 1 or more. The liquid crystal according to claim 11, wherein in formula (4), P ^4a , P ^4b , and P ^4c are groups selected from the polymerizable groups represented by formulas (P-1) to (P-5). Composition.

In Formulas (P-1) to (P-5), M ¹ , M ² , and M ³ represent hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen replaced with fluorine or chlorine. Alkyl having 1 to 5 carbon atoms. The method according to any one of claims 1 to 12, wherein the second additive contains at least one compound selected from polymerizable compounds represented by the formulas (4-1) to (4-29). Liquid crystal composition.

In the formulas (4-1) to (4-29), Sp ^4a , Sp ^4b , and Sp ^4c are a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — May be replaced by —O—, —COO—, —OCO—, or —OCOO—, and at least one of —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; P ^4d , P ^4e , and P ^4f are represented by the formulas (P-1) to (P-3) A polymerizable group selected from the groups represented by

In the formulas (P-1) to (P-3), M ¹ , M ² , and M ³ represent hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen replaced with fluorine or chlorine. Alkyl having 1 to 5 carbon atoms.   The liquid crystal composition according to any one of claims 11 to 13, 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.   The liquid crystal display element according to claim 15, wherein the operation mode of the liquid crystal display element is one of an IPS mode, a VA mode, an FFS mode, and an FPA mode, and the driving method of the liquid crystal display element is an active matrix method.   A liquid crystal display device of a polymer-supported alignment type, comprising the liquid crystal composition according to claim 11, wherein a polymerizable compound in the liquid crystal composition is polymerized.   Use of the liquid crystal composition according to any one of claims 1 to 14 in a liquid crystal display device.   Use of the liquid crystal composition according to any one of claims 11 to 14 in a liquid crystal display device of a polymer supported alignment type.