JP2019094368A - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

To provide a liquid crystal composition satisfying at least one of demands for characteristics such as a high maximum temperature, low minimum temperature, small viscosity, suitable optical anisotropy, negatively large dielectric anisotropy, large specific resistance, high stability to ultraviolet rays and high stability to heat or having a suitable balance in at least two of the above characteristics, and a liquid crystal display element suppressing a display failure.SOLUTION: Advantages of the present are providing: a compound as a first additive that has high solubility with a liquid crystal composition and has an effect of suppressing a display failure of a liquid crystal display element; a liquid crystal composition that contains a specific compound as a first component having negatively large dielectric anisotropy and has negative dielectric anisotropy; and a liquid crystal display element comprising the above composition. The composition may contain a specific compound having a high maximum temperature or a small viscosity as a second component, and a specific compound having a polymerizable group as a second additive.SELECTED DRAWING: None

Description

  The present invention relates to a liquid crystal composition containing a piperidine derivative, a liquid crystal display element containing the composition, and the like. In particular, the present invention relates to a liquid crystal composition having a negative dielectric anisotropy, and an element containing the composition and having a mode such as IPS, VA, FFS, or FPA. The invention also relates to a polymer-supported oriented device.

  In liquid crystal display devices, classification based on the operation mode of liquid crystal molecules is as follows: phase change (PC), twisted nematic (TN), super twisted nematic (STN), electrically controlled birefringence (ECB), optically compensated bend (OCB), IPS These modes are modes such as (in-plane switching), VA (vertical alignment), FFS (fringe field switching), and FPA (field-induced photo-reactive alignment). The classification based on the driving system of elements is PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into thin film transistor (TFT), metal insulator metal (MIM), etc. The classification of TFT is amorphous silicon and polycrystal silicon. The latter are classified into high temperature type and low temperature type according to the manufacturing process. Source based classifications are reflective based on natural light, transmissive based on back light, and semi-transmissive based on both natural light and back light.

  The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the properties of this composition, an AM element having good properties can be obtained. The associations in 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 usable temperature range of the device. The preferred upper temperature limit of the nematic phase is about 70 ° C. or higher, and the preferred lower temperature limit of the nematic phase is about -10 ° C. or lower. The viscosity of the composition is related to the response time of the device. Short response times are preferred for displaying motion pictures on the device. Even shorter response times of 1 millisecond are desirable. Thus, low viscosity in the composition is preferred. Smaller viscosities at lower 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, a large or small optical anisotropy, ie a suitable optical anisotropy, is required. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate value of the product depends on the type of operating mode. This value is in the range of about 0.30 μm to about 0.40 μm in the VA mode device and in the range of about 0.20 μm to about 0.30 μm in the IPS mode or FFS mode device. In these cases, compositions with large optical anisotropy are preferred for small cell gap devices. The large dielectric anisotropy in the composition contributes to low threshold voltage, low power consumption and high contrast ratio in the device. Therefore, large dielectric anisotropy is preferred. The large resistivity 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 at the initial stage is preferred. After prolonged use, compositions having high specific resistance are 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 element used for a liquid crystal monitor, a liquid crystal television, etc.

  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 the device. Next, the composition is irradiated with ultraviolet light 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 polymer can control the alignment of liquid crystal molecules, thereby reducing the response time of the device and improving the image sticking. Such an effect of the polymer can be expected to devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

  In an AM device having a TN mode, a composition having positive dielectric anisotropy is used. In an AM device having a VA mode, a composition having negative dielectric anisotropy is used. In an AM device having an IPS mode or an FFS mode, a composition having positive or negative dielectric anisotropy is used. In a polymer-supported oriented AM element, a composition having positive or negative dielectric anisotropy is used. Compositions containing a compound similar to the compound (1) of the present invention are disclosed in Patent Documents 1 and 2.

International Publication No. 2015/079797 International Publication No. 2015/076077

  An object of the present invention is to select a compound having high solubility in a liquid crystal composition and having an effect of suppressing a display defect of a liquid crystal display element. Other problems are: high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, appropriate optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability to ultraviolet light, heat It is an object of the present invention to provide a liquid crystal composition satisfying at least one of the high stability and the like properties. Another object is to provide a liquid crystal composition having a proper balance between at least two of these properties. Another object is to provide a liquid crystal display device containing such a composition. Another problem is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, slight display failure, and long lifetime.

式（１）において、Ｒ^１は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルであり、これらの基において、少なくとも１つの水素はフッ素または塩素で置き換えられてもよく；Ｒ^２は、水素、ヒドロキシ、オキシラジカル、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルであり、これらの基において、炭素に結合した少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；環Ａ、環Ｂ、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、３，４−ジヒドロ−２Ｈ−ピラン−２，５−ジイル、３，４−ジヒドロ−２Ｈ−ピラン−３，６−ジイル、３，６−ジヒドロ−２Ｈ−ピラン−２，５−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、１，４−フェニレン、ピリジン−２，５−ジイル、デカヒドロナフタレン−２，６−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、またはナフタレン−２，７−ジイルであり、これらの環において、芳香環上の少なくとも１つの水素は、フッ素、塩素、シアノ、炭素数１から５のアルキル、炭素数１から５のアルコキシ、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、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のアルコキシで置き換えられてもよく；Ｚ^１およびＺ^２は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ₂−は、−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−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；Ｚ^３は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ₂−は、−Ｏ−、−ＮＨ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ａおよびｂは、０または１である。 The present invention contains a liquid crystal composition having at least one compound selected from compounds represented by Formula (1) as a first additive and having negative dielectric anisotropy, and this composition. The present invention relates to a liquid crystal display device.

In Formula (1), R ¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons, and in these groups, at least one hydrogen is fluorine or chlorine. R ² is hydrogen, hydroxy, oxy radical, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons, and in these groups, At least one hydrogen bonded to carbon may be replaced by fluorine or chlorine; ring A, ring B and ring C may be 1,4-cyclohexylene, 1,4-cyclohexenylene, 3,4- Dihydro-2H-pyran-2,5-diyl, 3,4-dihydro-2H-pyran-3,6-diyl, 3,6-dihydro-2H-pyran-2,5- , Tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4-phenylene, pyridine-2,5-diyl, decahydronaphthalene-2,6-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 or naphthalene-2,7-diyl, in these rings, at least one hydrogen on the aromatic ring is fluorine, chlorine, cyano, alkyl having 1 to 5 carbon atoms C 1 to C 5 alkoxy, C 1 to C 5 alkyl in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen is Fluorine or chlorine may be replaced by alkoxy having 1 to 5 carbons; Z ¹ and Z ² are a single bond or alkylene having 1 to 10 carbons, and in this alkylene, at least one of- CH ₂ -may be replaced by -O-, -COO-, or -OCO-, and at least one -CH ₂ CH ₂ -is replaced by -CH = CH- or -C≡C- And in these groups, at least one hydrogen may be replaced by fluorine or chlorine; Z ³ is a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ -, -O -, - NH -, - COO-, or may be replaced by -OCO-, at least one _-CH 2 CH ₂ -, -CH = It may be replaced by H- or -C≡C-, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; a and b is 0 or 1.

  An advantage of the present invention is to select a compound having high solubility in a liquid crystal composition and having an effect of suppressing display defects of a liquid crystal display element. Other advantages are: high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, appropriate optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability to ultraviolet light, heat It is an object of the present invention to provide a liquid crystal composition satisfying at least one of the high stability and the like properties. 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 an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, slight display failure and long lifetime.

  The usage of the 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 generic term for liquid crystal display panels and liquid crystal display modules. The “liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase or a smectic phase and has no liquid crystal phase, but has a composition for the purpose of adjusting properties such as temperature range, viscosity and dielectric anisotropy of the nematic phase. It is a generic term for compounds mixed in a substance. This compound has, for example, a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecule (liquid crystal molecule) is rod-like. The "polymerizable compound" is a compound to be added for the purpose of forming a polymer in the composition. Liquid crystalline compounds having an alkenyl are not polymerizable in that sense.

  The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as an optically active compound, an antioxidant, an ultraviolet light absorber, a quencher, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound are optionally added to this liquid crystal composition. Is added. The proportion of the liquid crystal compound is represented by mass percentage (mass%) based on the mass of the liquid crystal composition not including the additive even when the additive is added. The proportion of the additive is represented by mass percentage (mass%) based on the mass of the liquid crystal composition containing no additive. That is, the proportions of the liquid crystal compound and the additive are calculated based on the total mass of the liquid crystal compound. Parts per million (ppm) by mass may be used. The proportions of the polymerization initiator and the polymerization inhibitor are exceptionally expressed based on the weight of the polymerizable compound.

  The “upper limit temperature of the nematic phase” may be abbreviated as the “upper limit temperature”. The “lower limit temperature of the nematic phase” may be abbreviated as the “lower limit temperature”. "High resistivity" means that the composition has high resistivity in the initial stage and has high resistivity after prolonged use. The "high voltage holding ratio" means that the device has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit at the initial stage, and after a long period of use it shows a large voltage It means having a retention rate. The characteristics of the composition or the device may be examined by a time-dependent change test. The expression "increase the dielectric anisotropy" means that in the case of a composition having a positive dielectric anisotropy, the value increases positively, and a composition having a negative dielectric anisotropy. In the case of goods, it means that the value increases negatively.

  The compound represented by Formula (1) may be abbreviated as "compound (1)." At least one compound selected from the compounds represented by formula (1) may be abbreviated as "compound (1)". "Compound (1)" means one compound represented by Formula (1), a mixture of two compounds, or a mixture of three or more compounds. The expression “at least one compound selected from the compounds represented by the formula (1) and the formula (2)” means at least one compound selected from the group of the compound (1) and the compound (2) . The expression "at least one 'A'" means that the number of 'A' is arbitrary. In the expression “at least one 'A' may be replaced by 'B'”, when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is two Even in the case of three or more, their positions can be selected without limitation. This rule also applies to the expression "at least one 'A' replaced by 'B'".

Expressions such as “at least one —CH ₂ — may be replaced by —O—” are used herein. In this case, -CH ₂ -CH ₂ -CH ₂ -may be converted to -O-CH ₂ -O- by replacing non-adjacent -CH ₂ -with -O-. However, adjacent -CH _2- is not replaced by -O-. This replacement is -O-O-CH ₂ - is because (peroxide) is produced. That is, this expression includes both "one -CH _2- may be replaced by -O-" and "at least two non-adjacent -CH _2- may be replaced by -O-" means. This rule applies not only to substitution to -O-, but also to substitution to divalent groups such as -CH = CH- and -COO-.

In the chemical formulas of component compounds, the symbol of terminal group R ¹ was used for a plurality of compounds. In these compounds, two groups represented by any two R ¹ may be identical or different. For example, there is a case where R ^{1 of} the compound (1-1) is ethyl and R ¹ of the compound (1-2) is ethyl. In some cases, R ^{1 of} compound (1-1) is ethyl and R ¹ of compound (1-2) is propyl. This rule also applies to other symbols. In the formula (2), when the index 'c' is 2, two rings D are present. In this compound, two rings represented by two rings D may be identical or different. This rule also applies to any two rings D when the index 'c' is greater than two. This rule also applies when the compounds have a substituent represented by the same symbol.

Symbols such as A, B, C and D surrounded by hexagons correspond to rings such as ring A, ring B, ring C and ring D, respectively, and represent rings such as 6-membered ring and fused ring. In Formula (4), the oblique lines crossing one side of the hexagon indicate that any hydrogen on the ring may be replaced by a group such as -Sp ¹ -P ¹ . A subscript such as 'g' indicates the number of groups replaced. There is no such substitution when the subscript 'g' is 0 (zero). When the subscript 'g' is 2 or more, a plurality of -Sp ¹ -P ¹ exists on the ring J. The plurality of groups represented by -Sp ¹ -P ¹ may be identical or different. The expression “ring A and ring B is X, Y or Z” means that ring A and ring B are independently selected from the group of X, Y and Z. This rule also applies to other symbols.

2-fluoro-1,4-phenylene means the following two divalent groups. In the chemical formula, fluorine may be leftward (L) or rightward (R). This rule also applies to left-right asymmetric bivalent groups generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl. This rule also applies to divalent linking groups such as carbonyloxy (-COO- or -OCO-).

または

であり、好ましくは

である。 The alkyl of the liquid crystal compound is linear or branched and does not contain cyclic alkyl. Linear alkyls are preferred over branched alkyls. The same is true for end groups such as alkoxy and alkenyl. The configuration of 1,4-cyclohexylene is preferably trans rather than cis in order to increase the maximum temperature. Tetrahydropyran-2,5-diyl is

Or

And preferably

It is.

  The present invention includes the following items.

式（１）において、Ｒ^１は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルであり、これらの基において、少なくとも１つの水素はフッ素または塩素で置き換えられてもよく；Ｒ^２は、水素、ヒドロキシ、オキシラジカル、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルであり、これらの基において、炭素に結合した少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；環Ａ、環Ｂ、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、３，４−ジヒドロ−２Ｈ−ピラン−２，５−ジイル、３，４−ジヒドロ−２Ｈ−ピラン−３，６−ジイル、３，６−ジヒドロ−２Ｈ−ピラン−２，５−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、１，４−フェニレン、ピリジン−２，５−ジイル、デカヒドロナフタレン−２，６−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、またはナフタレン−２，７−ジイルであり、これらの環において、芳香環上の少なくとも１つの水素は、フッ素、塩素、シアノ、炭素数１から５のアルキル、炭素数１から５のアルコキシ、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、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のアルコキシで置き換えられてもよく；Ｚ^１およびＺ^２は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ₂−は、−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−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；Ｚ^３は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ₂−は、−Ｏ−、−ＮＨ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ａおよびｂは、０または１である。 Item 1. The liquid-crystal composition which contains at least 1 compound selected from the compound represented by Formula (1) as a 1st additive, and has negative dielectric constant anisotropy.

In Formula (1), R ¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons, and in these groups, at least one hydrogen is fluorine or chlorine. R ² is hydrogen, hydroxy, oxy radical, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons, and in these groups, At least one hydrogen bonded to carbon may be replaced by fluorine or chlorine; ring A, ring B and ring C may be 1,4-cyclohexylene, 1,4-cyclohexenylene, 3,4- Dihydro-2H-pyran-2,5-diyl, 3,4-dihydro-2H-pyran-3,6-diyl, 3,6-dihydro-2H-pyran-2,5- , Tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4-phenylene, pyridine-2,5-diyl, decahydronaphthalene-2,6-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 or naphthalene-2,7-diyl, in these rings, at least one hydrogen on the aromatic ring is fluorine, chlorine, cyano, alkyl having 1 to 5 carbon atoms C 1 to C 5 alkoxy, C 1 to C 5 alkyl in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen is Fluorine or chlorine may be replaced by alkoxy having 1 to 5 carbons; Z ¹ and Z ² are a single bond or alkylene having 1 to 10 carbons, and in this alkylene, at least one of- CH ₂ -may be replaced by -O-, -COO-, or -OCO-, and at least one -CH ₂ CH ₂ -is replaced by -CH = CH- or -C≡C- And in these groups, at least one hydrogen may be replaced by fluorine or chlorine; Z ³ is a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ -, -O -, - NH -, - COO-, or may be replaced by -OCO-, at least one _-CH 2 CH ₂ -, -CH = It may be replaced by H- or -C≡C-, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; a and b is 0 or 1.

Item 2. Item 2. The liquid crystal composition according to item 1, containing at least one compound selected from the compounds represented by formulas (1-1) to (1-14) as the first additive.

式（１−１）から式（１−１４）において、Ｒ^１は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルであり、これらの基において、少なくとも１つの水素はフッ素または塩素で置き換えられてもよく；Ｒ^２は、水素、ヒドロキシ、オキシラジカル、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルであり、これらの基において、炭素に結合した少なくとも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；Ｘ¹、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５、およびＸ⁶は、水素またはフッ素である。

In formulas (1-1) to (1-14), R ¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons, and in these groups, And at least one hydrogen may be replaced by fluorine or chlorine; R ² is hydrogen, hydroxy, oxy radical, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 2 to 12 carbons Alkenyl in which at least one hydrogen bonded to carbon may be replaced by fluorine or chlorine; X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are hydrogen Or fluorine.

Item 3. Item 3. The liquid crystal composition according to item 1 or 2, wherein the proportion of the first additive is in the range of 0.005% by mass to 1% by mass.

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

In Formula (2), R ³ and R ⁴ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons, Ring D and ring F each have 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene and at least one hydrogen substituted by fluorine or chlorine 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen is fluorine or Chlorine-substituted chroman-2,6-diyl; ring E is 2,3-difluoro-1,4-phenylene, 2-chloro -3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman- 2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, or 1,1,6,7-tetrafluoroindane be a 2,5-diyl; ^{Z 4} and ^{Z 5} is a single bond, ethylene, carbonyloxy or methyleneoxy,; c is 1, 2, or 3,, d is 0 or 1, And the sum of c and d is 3 or less.

Item 5. 5. The liquid crystal composition according to any one of items 1 to 4, containing at least one compound selected from the compounds represented by formula (2-1) to formula (2-33) as a first component.

式（２−１）から式（２−３３）において、Ｒ^３およびＲ^４は、水素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、または炭素数２から１２のアルケニルオキシである。

In formulas (2-1) to (2-33), R ³ and R ^{4 each} represents hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon It is alkenyloxy of the number 2-12.

Item 6. 6. The liquid crystal composition according to any one of items 1 to 5, 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^５およびＲ^６は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルであり；環Ｇおよび環Ｉは、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、または２，５−ジフルオロ−１，４−フェニレンであり；Ｚ^６は、単結合、エチレン、またはカルボニルオキシであり；ｅは、１、２、または３である。 Item 7. 7. The liquid crystal composition according to any one of items 1 to 6, containing at least one compound selected from the compounds represented by formula (3) as a second component.

In the formula (3), R ⁵ and R ^{6 each} represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon in which at least one hydrogen is replaced by fluorine or chlorine. The alkyl of the number 1 to 12 or an alkenyl of 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine; ring G and ring I are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ⁶ is a single bond, ethylene or carbonyloxy; e is 1, 2 or 3 is there.

式（３−１）から式（３−１３）において、Ｒ^５およびＲ^６は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルである。 Item 8. 8. The liquid crystal composition according to any one of items 1 to 7, containing at least one compound selected from the compounds represented by formulas (3-1) to (3-13) as a second component.

In formulas (3-1) to (3-13), R ⁵ and R ^{6 each} represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, at least one hydrogen Is C 1-12 alkyl substituted with fluorine or chlorine, or C 2-12 alkenyl in which at least one hydrogen is substituted by fluorine or chlorine.

Item 9. 9. The liquid crystal composition according to item 7 or 8, 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Ｊおよび環Ｌ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Ｋ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^７およびＺ^８は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ_３）−、または−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｐ^１、Ｐ^２、およびＰ^３は、重合性基であり；Ｓｐ^１、Ｓｐ^２、およびＳｐ^３は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ｆは、０、１、または２であり；ｇ、ｈ、およびｉは、０、１、２、３、または４であり、そしてｇ、ｈ、およびｉの和は、１以上である。 Item 10. 10. The liquid crystal composition according to any one of items 1 to 9, containing at least one compound selected from the polymerizable compounds represented by formula (4) as a second additive.

In the formula (4), the ring J and the ring L are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl Or pyridin-2-yl, in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is fluorine or chlorine May be substituted by alkyl having 1 to 12 carbon atoms, which is substituted by; ring K 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-diy , Naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl in which at least one hydrogen is fluorine, chlorine, carbon number 1 12 alkyl, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine; Z ⁷ and Z ^{8 each} represents a single bond or carbon alkylene from C 1 10, in the alkylene, at least one of _-CH 2 -, -O -, - CO -, - COO-, or May be replaced by OCO-, at least one _-CH 2 CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, or -C ( CH ₃ ) = C (CH ₃ ) — which may be replaced by at least one hydrogen in these groups may be replaced by fluorine or chlorine; P ¹ , P ² and P ³ may be polymerized Sp ¹ , Sp ² , and Sp ^{3 each} represents a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO—, -OCO-, or -OCOO- in may be replaced, 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; f is 0, 1 or 2; g, h and i are 0, 1, 2, 3 or 4 and g, The sum of h and i 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 11. Item 11. The compound according to item 10, wherein P ¹ , P ² and P ³ in the formula (4) are a group selected from the polymerizable groups represented by the formulas (P-1) to (P-5) Liquid crystal composition.

In Formula (P-1) to Formula (P-5), M ¹ , M ² and M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is replaced by fluorine or chlorine And alkyl having 1 to 5 carbon atoms.

Item 12. Item 12. The liquid crystal according to any one of items 1 to 11, containing at least one compound selected from polymerizable compounds represented by formulas (4-1) to (4-29) as a second additive: Composition.

式（４−１）から式（４−２９）において、Ｐ^４、Ｐ^５、およびＰ^６は、式（Ｐ−１）から式（Ｐ−３）で表される重合性基から選択された基であり、

ここで、Ｍ^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のアルキルであり；Ｓｐ^１、Ｓｐ^２、およびＳｐ^３は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。

In formulas (4-1) to (4-29), P ⁴ , P ⁵ and P ⁶ are selected from polymerizable groups represented by formulas (P-1) to (P-3) And

Here, M ¹ , M ² and M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine; Sp ¹ , Sp ² and Sp ^{3 each} represents 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 — OCOO-may be replaced, and at least one -CH ₂ CH ₂ -may be replaced by -CH = CH- or -C≡C-, and in these groups, at least one hydrogen is fluorine Or may be replaced by chlorine.

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

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

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

Item 16. Item 14. A polymer supported alignment type liquid crystal display device comprising the liquid crystal composition according to any one of items 10 to 13 and in which a second additive contained in the liquid crystal composition is polymerized.

Item 17. Item 14. Use of the liquid crystal composition according to any one of items 1 to 13 in a liquid crystal display device.

Item 18. Item 14. Use of the liquid crystal composition according to any one of items 1 to 13 in a polymer supported alignment type liquid crystal display device.

  The present invention also includes the following items. (A) at least one additive such as an optically active compound, an antioxidant, an ultraviolet light absorber, a quencher, a dye, an antifoamer, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound The above composition. (B) AM element containing the above composition. (C) A polymer supported orientation (PSA) type AM element containing the above composition further containing a polymerizable compound. (D) An AM element of polymer supported orientation (PSA) type containing the composition described above and in which the polymerizable compound in the composition is polymerized. (E) A device containing the composition described above and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA. (F) A transmission type 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 contains the compound (1). This compound has 2,2,6,6-tetramethyl-4-piperidinyl and has high solubility in liquid crystal compositions. This may be because the molecular structure was designed to be rod-like. This compound is classified as a polar compound because it has a partial structure of> N-. This compound was found to be effective in suppressing display defects of the device as shown in Comparative Examples and Examples. However, the causes of display defects are complex and have not been fully elucidated. Furthermore, the effect of this compound on display defects is also unclear at this stage. In such a situation, an explanation as described in the next paragraph is possible.

  When the device is used for a long time, the brightness may partially decrease. One example is a line residual image, which is a phenomenon in which the luminance between the electrodes decreases in a streak shape by applying different voltages repeatedly to two adjacent electrodes. This phenomenon is caused by accumulation of ionic impurities contained in the liquid crystal composition on the alignment film in the vicinity of the electrode. Therefore, in order to suppress the line residual image, it is effective to prevent the ionic impurities from being localized on the alignment film. For this purpose, the surface of the alignment layer is coated with an additive such as a polar compound, and the additive adsorbs ionic impurities. As a result, display defects are suppressed.

  The liquid crystal composition is injected into the device from an inlet under reduced pressure. Usually, the composition is loaded into the device without changing the proportions of its components. However, additives such as polar compounds may be adsorbed to the alignment film. When the rate of adsorption is high, the additive may not reach the back of the device. The additives are left behind because the rate of adsorption is greater than the rate of injection. In order to prevent this phenomenon, an additive having an appropriate adsorptivity to the alignment film is preferable. Therefore, it is also important to select an additive with the proper polarity. Compound (1) is suitable for this purpose.

  In the liquid crystal dropping method, a liquid crystal composition is dropped on an alignment film disposed on a substrate. At this time, a display defect called a dripping mark occurs. In general, the phenomenon is that the alignment film does not have sufficient ability to align the liquid crystal composition vertically, and some liquid crystal molecules adhere to the alignment film by some action when the liquid crystal composition is dropped. It is considered that the reason is that it does not have such mobility (refer to JP 2012-113132, paragraph 0020). The compound (1) is also effective in preventing this dripping mark.

  The composition of the present invention will be described in the following order. First, the composition of the composition will be described. Second, the main properties of the component compounds and the main effects of the compounds on the composition and the device are explained. Third, the combination of the component compounds in the composition, the preferable ratio and the basis thereof will be described. Fourth, the preferred embodiments of the component compounds are described. Fifth, preferred component compounds are shown. Sixth, additives that may be added to the composition will be described. Seventh, the synthesis methods of the component compounds will be described. Finally, the application of the composition is described.

First, the composition of the composition will be described. This composition contains a plurality of liquid crystal compounds. The composition may contain an additive. The additive is an optically active compound, an antioxidant, an ultraviolet light absorber, a quencher, a pigment, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, a polar compound and the like. This composition is classified into the composition A and the composition B from the viewpoint of the liquid crystal compound.
Composition A may further contain other liquid crystal compounds, additives, and the like in addition to the liquid crystal compound selected from compound (2) and compound (3). The “other liquid crystal compound” is a liquid crystal compound different from the compound (2) and the compound (3). Such compounds are mixed into the composition for the purpose of further adjusting the properties.

  Composition B consists essentially of the liquid crystal compound selected from compound (2) and compound (3). "Substantially" means that composition B may contain an additive, but does not contain any other liquid crystal compound. Composition B has a smaller number of components than composition A. Composition B is preferable to composition A in terms of cost reduction. Composition A is preferable to composition B from the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds.

  Second, the main properties of the component compounds and the main effects of the compounds on the composition and the device are explained. The main properties of the component compounds are summarized in Table 2 based on the effects of the present invention. In the symbols of Table 2, L means large or high, M medium, and S small or low. The symbols L, M, S are classifications based on qualitative comparisons among the component compounds, and the symbol 0 (zero) means smaller than S (small).

  The main effects of the component compounds are as follows. The compound (1) contributes to the suppression of display defects such as residual images and drip marks. The compound (1) does not affect properties such as the upper limit temperature, the optical anisotropy and the dielectric anisotropy in many cases because the amount of addition is extremely small. Compound (2) raises the dielectric anisotropy and lowers the lower limit temperature. The compound (3) lowers the viscosity or raises the upper limit temperature. The compound (4) is polymerizable to give a polymer by polymerization. The polymer stabilizes the orientation of the liquid crystal molecules, thereby reducing the response time of the device and improving the image sticking.

  Third, the combination of the component compounds in the composition, the preferable ratio and the basis thereof will be described. Preferred combinations of the components in the composition are compound (1) + compound (2), compound (1) + compound (3), compound (1) + compound (2) + compound (3), compound (1) + compound (2) + compound (4), compound (1) + compound (3) + compound (4), or compound (1) + compound (2) + compound (3) + compound (4). A further preferred combination is compound (1) + compound (2) + compound (3) or compound (1) + compound (2) + compound (3) + compound (4).

  The preferred proportion of the compound (1) is about 0.005% by mass or more to suppress display defects of the device, and about 1% by mass or less to lower the lower limit temperature. A further preferred ratio is in the range of about 0.01% by weight to about 0.5% by weight. An especially desirable ratio is in the range of about 0.05% by mass to about 0.3% by mass.

  The preferred proportion of the compound (2) is about 10% by mass or more in order to increase the dielectric anisotropy, and about 90% by mass or less in order to lower the lower limit temperature. A further preferred ratio is in the range of about 20% by weight to about 80% by weight. An especially desirable ratio is in the range of about 30% by weight to about 75% by weight. In order to lower the threshold voltage of the device, the dielectric anisotropy of the composition is preferably −2.0 or less.

  The preferred proportion of the compound (3) is about 10% by mass or more to raise the upper limit temperature or to lower the viscosity, and about 90% by mass or less to raise the dielectric anisotropy. A further preferred ratio is in the range of about 20% by weight to about 80% by weight. An especially desirable ratio is in the range of about 30% by weight to about 70% by weight.

  The compound (4) is added to the composition for the purpose of being adapted to a polymer-supported oriented device. The preferred proportion of the compound (4) is about 0.03% by mass or more for aligning liquid crystal molecules, and about 10% by mass or less for preventing display defects of the device. A further preferred ratio is in the range of about 0.1% by weight to about 2% by weight. An especially desirable ratio is in the range of about 0.2% by mass to about 1.0% by mass.

  Fourth, the preferred embodiments of the component compounds are described. First, the first additive (piperidine derivative) and the liquid crystal compound are collectively described. Next, the second additive (polymerizable compound) will be described.

(A) First Additive and Liquid Crystalline Compound In the formulas (1), (2) and (3), R ¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or carbon And in these groups, at least one hydrogen may be replaced by fluorine or chlorine. Desirable R ¹ is alkyl having 1 to 12 carbons in order to increase the stability to ultraviolet light and heat. R ² is hydrogen, hydroxy, oxy radical, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons, and in these groups, at least one of carbon bonded to carbon is Hydrogen may be replaced by fluorine or chlorine. Hydroxy is -OH and the oxy radical is an oxygen radical (> N-O.) Attached to nitrogen. Desirable R ² is hydrogen, hydroxy, oxy radical, alkyl having 1 to 3 carbons, or alkoxy having 1 to 3 carbons. More preferred R ² is hydrogen, hydroxy, oxy radical, methyl, ethyl, propyl, isopropyl, methoxy or ethoxy. Particularly preferred R ² is hydrogen, hydroxy, oxy radical, methyl or methoxy.

R ³ and R ⁴ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons. Desirable R ³ or R ⁴ is alkyl having 1 to 12 carbons to increase stability to ultraviolet light and heat, and alkoxy having 1 to 12 carbons to increase dielectric anisotropy. R ⁵ and R ^{6 each} represents an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, an alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Or at least one hydrogen is an alkenyl having 2 to 12 carbons replaced with fluorine or chlorine. Desirable R ⁵ or R ⁶ is alkenyl having 2 to 12 carbons to lower the viscosity, and alkyl having 1 to 12 carbons to increase the stability to ultraviolet light and heat.

  Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More preferred alkyl is methyl, ethyl, propyl, butyl or pentyl to lower the viscosity.

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

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

Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy or 4-pentenyloxy. Further preferred alkenyloxy is allyloxy or 3-butenyloxy to lower the viscosity.

  Preferred examples of the 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 to increase dielectric anisotropy.

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

  Ring A, ring B and ring C are each selected from 1,4-cyclohexylene, 1,4-cyclohexenylene, 3,4-dihydro-2H-pyran-2,5-diyl, 3,4-dihydro-2H- Pyrane-3,6-diyl, 3,6-dihydro-2H-pyran-2,5-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4-phenylene , Pyridine-2,5-diyl, decahydronaphthalene-2,6-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, or naphthalene-2,7-diyl, and in these rings, At least one hydrogen on the ring is fluorine, chlorine, cyano, C 1 -C 5 alkyl, C 1 -C 5 alkoxy, C 1 -C 5 alkyl in which at least one hydrogen is replaced by fluorine or chlorine. Or at least one hydrogen may be replaced by C 1 -C 5 alkoxy substituted by fluorine or chlorine. Preferred ring A, ring B or ring C is 1,4-cyclohexylene or 1,4-phenylene.

  Ring D and ring F may be 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is replaced by fluorine or chlorine 1 , 4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen is fluorine or chlorine Is substituted by chroman-2,6-diyl. Desirable ring D or ring F is 1,4-cyclohexylene to lower viscosity, and tetrahydropyran-2,5-diyl to increase dielectric anisotropy, to increase optical anisotropy It is 1,4-phenylene.

好ましい環Ｅ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 E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,4, 5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl (FLF 4), 4,6- Difluorodibenzofuran-3,7-diyl (BFF2) or 1,1,6,7-tetrafluoroindane-2,5-diyl (InF4).

Preferred ring E is 2,3-difluoro-1,4-phenylene to lower the viscosity, 2-chloro-3-fluoro-1,4-phenylene to lower the optical anisotropy, and the dielectric constant 7,8-Difluorochroman-2,6-diyl to increase anisotropy.

  Ring G and ring I are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene. Preferred ring G or ring I is 1,4-cyclohexylene to lower the viscosity or to raise the upper temperature limit, and 1,4-phenylene to lower the lower temperature limit.

Z ¹ and Z ^{2 each} represent a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —NH—, —COO—, or —OCO— And at least one —CH ₂ CH ₂ — may be replaced by —CH = CH— or —C≡C—, and in these groups, at least one hydrogen is fluorine or chlorine It may be replaced. Preferred Z ¹ or Z ² is a single bond, -CH ₂ CH _2- , -COO-, -OCO-, -CH ₂ O-, or -CH = CH-. Z ³ is a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is replaced by —O—, —NH—, —COO—, or —OCO— And at least one -CH ₂ CH ₂ -may be replaced by -CH = CH- or -C≡C-, and in these groups, at least one hydrogen is replaced by fluorine or chlorine It is also good. Preferred Z ³ is a single bond, -CH ₂ CH _2- , -O-, -COO-, or -OCO-. Further preferred Z ³ is a single bond. Z ⁴ and Z ⁵ are a single bond, ethylene, carbonyloxy or methyleneoxy. Preferred Z ⁴ or Z ⁵ is a single bond for decreasing the viscosity, an ethylene for decreasing the minimum temperature, methyleneoxy for increasing the dielectric anisotropy. Z ⁶ is a single bond, ethylene or carbonyloxy. Preferred Z ⁶ is a single bond to increase the stability to ultraviolet light and heat.

  a and b are 0 or 1; c is 1, 2 or 3; d is 0 or 1; and the sum of c and d is 3 or less. Preferred c is 1 to lower the viscosity and 2 or 3 to raise the upper temperature limit. Desirable d is 0 to lower the viscosity and 1 to lower the lower limit temperature. e is 1, 2 or 3; Preferred e is 1 to lower the viscosity and 2 or 3 to raise the upper temperature limit.

(B) Second additive (polymerizable compound)
In Formula (4), P ¹ , P ² and P ³ are polymerizable groups. Preferred P ¹ , P ² or P ³ is a polymerizable group selected from the groups represented by Formula (P-1) to Formula (P-5). Further preferred P ¹ , P ² or P ³ 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 lines in group (P-1) to group (P-5) indicate the binding site.

In groups (P-1) to (P-5), M ¹ , M ² and M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is replaced by fluorine or chlorine And alkyl having 1 to 5 carbon atoms. Preferred M ¹ , M ² or M ³ is hydrogen or methyl to increase the reactivity. Further preferred M ¹ is methyl and further preferred M ² or M ³ is hydrogen.

In formulas (4-1) to (4-29), P ⁴ , P ⁵ and P ⁶ are groups represented by formulas (P-1) to (P-3). Preferred P ⁴ , P ⁵ or P ⁶ is a group (P-1) or a group (P-2). Further preferred groups (P-1) is, -OCO-CH = CH ₂ or _{-OCO-C (CH} 3) a = CH _2. The wavy lines in group (P-1) to group (P-3) indicate the binding site.

In the formula (4), Sp ¹ , Sp ² and Sp ³ are a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO— And —OCO— or —OCOO—, and at least one —CH ₂ CH ₂ — may be replaced by —CH = CH— or —C≡C—, and in these groups, At least one hydrogen may be replaced by fluorine or chlorine. Preferred Sp ¹ , Sp ² or Sp ³ 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 ¹ , Sp ² or Sp ³ is a single bond.

  Ring J and ring L may be cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl or pyridine-2- In these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or the number of carbons in which at least one hydrogen is replaced by fluorine or chlorine. It may be substituted with 1 to 12 alkyl. Preferred ring J or ring L is phenyl.

  Ring K 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 fluorine or chlorine. From the obtained 1 carbon atoms may be replaced by alkyl of 12. Preferred ring K is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁷ and Z ^{8 each} represent a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —CO—, —COO—, or —OCO— And at least one —CH ₂ CH ₂ — may be replaced by —CH = CH—, —C (CH ₃ ) = CH—, —CH = C (CH ₃ ) —, or —C (CH ₃ ). = C (CH ₃ ) — may be replaced, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine. Preferred Z ⁶ or Z ⁷ is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. Further preferred Z ⁷ or Z ⁸ is a single bond.

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

  Fifth, preferred component compounds are shown. The preferred compound (1) is the compound (1-1) to the compound (1-14) described in Item 2. Further preferable compound (1) is compound (1-2), compound (1-3), compound (1-9) or compound (1-10).

  The preferable compound (2) is a compound (2-1) to a compound (2-33) described in item 5. In these compounds, at least one of the first components is a compound (2-1), a compound (2-3), a compound (2-4), a compound (2-6), a compound (2-8), or a compound It is preferable that it is (2-10). At least two of the first components are compound (2-1) and compound (2-6), compound (2-1) and compound (2-10), compound (2-3) and compound (2-6), It is preferable that it is a combination of a compound (2-3) and a compound (2-10), a compound (2-4) and a compound (2-6), or a compound (2-4) and a compound (2-8).

  The preferred compound (3) is a compound (3-1) to a compound (3-13) described in item 8. 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 It is preferable that it is (3-9). At least two of the second components are the compound (3-1) and the compound (3-3), the compound (3-1) and the compound (3-5), or the compound (3-1) and the compound (3-6) It is preferable that it is a combination of

  The preferred compound (4) is a compound (4-1) to a compound (4-29) described in Item 12. In these compounds, at least one of the second additives is a compound (4-1), a compound (4-2), a compound (4-24), a compound (4-25), a compound (4-26), or It is preferable that it is a compound (4-27). At least two of the second additives are the compound (4-1) and the compound (4-2), the compound (4-1) and the compound (4-18), the compound (4-2) and the compound (4-24) A compound (4-2) and a compound (4-25), a compound (4-2) and a compound (4-26), a compound (4-25) and a compound (4-26), or a compound (4-18) It is preferable that it is a combination of and a compound (4-24).

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

In order to prevent the decrease in specific resistance due to heating in the atmosphere, or after using the device for a long time, in order to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature, Is added to the Preferred examples of the antioxidant include compound (6-1) to compound (6-3).

  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. The preferred proportion of the antioxidant is about 50 ppm or more to obtain its effect, and is about 600 ppm or less so as not to lower the upper temperature limit or to raise the lower temperature limit. A further preferred ratio is in the range of about 100 ppm to about 300 ppm.

  Preferred examples of the UV absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Also preferred are light stabilizers such as sterically hindered amines. Preferred examples of the light stabilizer include compound (7-1) to compound (7-16). The preferred proportion of these absorbents and stabilizers is about 50 ppm or more to obtain the effect, and about 10000 ppm or less so as not to lower the upper temperature limit or to raise the lower temperature limit. A further preferred ratio is in the range of about 100 ppm to about 10000 ppm.

  A quencher is a compound which receives the light energy absorbed by the liquid crystal compound and converts it into heat energy to prevent the decomposition of the liquid crystal compound. Preferred examples of the quencher include compound (8-1) to compound (8-7). The preferred proportion of these quenchers is about 50 ppm or more to obtain the effect, and about 20000 ppm or less to lower the lower limit temperature. A further preferred ratio is in the range of about 100 ppm to about 10000 ppm.

  In order to conform to a guest host (GH) mode device, a dichroic dye such as an azo dye or an anthraquinone dye is added to the composition. The preferred proportion of dye is in the range of about 0.01% by weight to about 10% by weight. In order to prevent foaming, an antifoam agent such as dimethyl silicone oil, methylphenyl silicone oil or the like is added to the composition. The preferable proportion of the antifoaming agent is about 1 ppm or more in order to obtain the effect, and is about 1000 ppm or less in order to prevent display defects. A further preferred ratio is in the range of about 1 ppm to about 500 ppm.

  Polymerizable compounds are used to make them compatible with polymer-supported oriented (PSA) type devices. Compound (4) is suitable for this purpose. Along with the compound (4), a polymerizable compound different from the compound (4) may be added to the composition. Instead of the compound (4), a polymerizable compound different from the compound (4) may be added to the composition. Preferred examples of such polymerizable compounds are compounds such as acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes) and vinyl ketones. Further preferred examples are derivatives of acrylate or methacrylate. Adjusting the reactivity of polymerization and the pretilt angle of liquid crystal molecules by changing the kind of the compound (4) or by combining the compound (4) with a polymerizable compound different from the compound (4) in an appropriate ratio can do. By optimizing the pretilt angle, short response times of the device can be achieved. Since the alignment of liquid crystal molecules is stabilized, a large contrast ratio and a long lifetime can be achieved.

  The polymerizable compound is polymerized by ultraviolet irradiation. It may be polymerized in the presence of an initiator such as a photopolymerization initiator. Appropriate conditions for polymerization, as well as suitable types and amounts of initiators are known to the person skilled in the art and are described in the literature. For example, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF), which are photoinitiators, are suitable for radical polymerization. The preferred proportion of the photoinitiator is in the range of about 0.1 wt% to about 5 wt% based on the weight of the polymerizable compound. A further preferred ratio is in the range of about 1% by weight to about 3% by weight.

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

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

  Seventh, the synthesis methods of the component compounds will be described. These compounds can be synthesized by known methods. The synthesis method is illustrated. The synthesis method of compound (1) is described in the section of Examples. The compound (2-8) is synthesized by the method described in JP-A-2000-53602. The compound (3-1) is synthesized by the method described in JP-A-59-176221. The compound (4-18) is synthesized by the method described in JP-A-7-101900. Compounds of formula (6) wherein n is 1 are available from Aldrich (Sigma-Aldrich Corporation). The compound (6) and the like in which n is 7 are synthesized by the method described in US Pat. No. 3,660,505.

  Compounds that did not describe the method of synthesis were organic syntheses (John Wiley & Sons, Inc.), Organic Reactions (John Wiley & Sons, Inc.), complementary organic syntheses ( It can be synthesized by the method described in the book of Comprehensive Organic Synthesis, Pergamon Press), New Experimental Chemistry Lecture (Maruzen) and the like. The compositions are prepared from the compounds thus obtained by known methods. For example, the component compounds are mixed and dissolved together by heating.

  Finally, the application of the composition is described. Most compositions have a lower limit temperature of about -10 ° C or lower, an upper temperature limit of about 70 ° C or higher, an optical anisotropy in the range of about 0.07 to about 0.20, and a dielectric of about -2.0 or less It has rate anisotropy. A composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the proportions of the component compounds, or by mixing other liquid crystal compounds. Furthermore, compositions having optical anisotropy in the range of about 0.10 to about 0.30 may be prepared by trial and error. Devices containing this composition have a large voltage holding ratio. This composition is suitable for an AM device. This composition is particularly suitable for transmissive AM devices. This composition can be used as a composition having a nematic phase or as an optically active composition by adding an optically active compound.

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

  An example of the method for producing a polymer-supported oriented device is as follows. An element having two substrates called an array substrate and a color filter substrate is assembled. This substrate has an alignment film. At least one of the substrates has an electrode layer. A liquid crystal compound is mixed to prepare a liquid crystal composition. A polymerizable compound is added to this composition. Additives may be further added as needed. The composition is injected into the device. Light is irradiated in a state where a voltage is applied to this element. UV light is preferred. The polymerizable compound is polymerized by light irradiation. This polymerization produces a composition containing a polymer. A polymer-supported oriented device is manufactured by such a procedure.

  In this procedure, when a voltage is applied, liquid crystal molecules are aligned by the action of an alignment film and an electric field. The molecules of the polymerizable compound are also oriented according to this orientation. In this state, since the polymerizable compound is polymerized by ultraviolet light, a polymer maintaining this orientation is formed. The effect of the polymer reduces the response time of the device. Since image sticking is a malfunction of liquid crystal molecules, the effect of the polymer is to simultaneously improve the sticking. In addition, it is also possible to pre-polymerize the polymerizable compound in the composition and arrange this composition between the substrates of the liquid crystal display element.

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

NMR analysis: For measurement, DRX-500 manufactured by Bruker Biospin Ltd. was used. ^In the measurement of ¹ H-NMR, the sample was dissolved in a deuterated solvent such as CDCl _3, and the measurement was performed at room temperature under conditions of 500 MHz and 16 integrations. Tetramethylsilane was used as an internal standard. ^{In 19} F-NMR measurement, CFCl ₃ was used as an internal standard, and the number of integrations was 24 times. In the description of nuclear magnetic resonance spectrum, s is singlet, d is doublet, t is triplet, q is quartet, quin is quintet, sex is sextet, m is multiplet, br is broad.

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

  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. HP-1 (30 m in length, 0.32 mm in inner diameter, 0.25 μm in thickness) manufactured by Agilent Technologies Inc., Rtx-1 (30 m in length, 0.32 mm in inner diameter, 0.25 μm in film thickness) manufactured by Restek Corporation, BP-1 (30 m in length, 0.32 mm in inner diameter, 0.25 μm in film thickness) manufactured by SGE International Pty. Ltd. A capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Shimadzu Corporation may be used for the purpose of preventing overlapping of compound peaks.

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

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

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

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

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

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

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

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

(5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25 ° C.): Measurement was performed using an Abbe refractometer with a polarizing plate attached to the ocular, using light of wavelength 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 polarization direction was parallel to the rubbing direction. The refractive index n⊥ was measured when the polarization direction was perpendicular to the rubbing direction. The value of optical anisotropy was calculated from the formula of Δn = n‖-n⊥.

(6) Dielectric anisotropy (Δε; measured at 25 ° C.): The value of dielectric anisotropy was calculated from the equation of Δε = εΔ−ε⊥. The dielectric constants (ε‖ and ε⊥) were measured as follows.

6a) Measurement of dielectric constant (ε‖): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a well-cleaned glass substrate. The glass substrate was rotated by a spinner and then heated at 150 ° C. for 1 hour. A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 4 μm, and this device was sealed with an adhesive cured with ultraviolet light. Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant (‖) in the major axis direction of liquid crystal molecules was measured.

6b) Measurement of dielectric constant (ε⊥): A polyimide solution was applied to a well-cleaned glass substrate. After firing the glass substrate, the obtained alignment film was rubbed. The 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 this device, and after 2 seconds, the dielectric constant (⊥) in the minor axis direction of liquid crystal molecules was measured.

(7) Threshold voltage (Vth; measured at 25 ° C .; V): An LCD-5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for 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 for curing this device with ultraviolet light is used. Used and sealed. The voltage (60 Hz, rectangular wave) applied to this element was gradually increased by 0.02 V from 0 V to 20 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The threshold voltage was represented by the voltage at 10% transmittance.

(8) Voltage holding ratio (VHR-1; measured at 25 ° C .;%): The TN device used for measurement had a polyimide alignment film, and the distance between two glass substrates (cell gap) was 5 μm. . The element was sealed with an adhesive that cures with ultraviolet light after the sample was placed. The TN device was charged by applying a pulse voltage (60 microseconds at 1 V). The decaying voltage was measured with a high speed voltmeter for 166.7 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 it did not decay. The voltage holding ratio was expressed as a percentage of the area A to the area B.

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

(12) Voltage holding ratio (VHR-3; measured at 60 ° C .;%): After irradiation with ultraviolet light, the voltage holding ratio was measured to evaluate the stability against ultraviolet light. 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 light for 167 minutes. The light source was a black light (peak wavelength 369 nm), and the distance between the device and the light source was 5 mm. In the measurement of VHR-3, the decaying voltage was measured for 166.7 milliseconds. Compositions with large VHR-3 have high stability to ultraviolet light.

(10) Voltage holding ratio (VHR-4; measured at 60 ° C .;%): The TN device injected with the sample is heated in a 120 ° C. constant temperature bath for 20 hours, and then the voltage holding ratio is measured to be stable against heat. Was evaluated. In the measurement of VHR-4, the decaying voltage was measured for 166.7 milliseconds. Compositions having large VHR-4 have great stability to heat.

(11) Response time (τ; measured at 25 ° C .; ms): For measurement, LCD Evaluation System Model LCD-5100 made by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. The low pass filter (Low-pass filter) was set to 5 kHz. The sample was placed in a normally black mode VA element in which the distance between two glass substrates (cell gap) was 4 μm and the rubbing direction was antiparallel. The device was sealed using an adhesive that cures with ultraviolet light. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to this element. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. It was considered that the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The response time is represented by the time (fall time; milliseconds) taken to change from 90% transmittance to 10% transmittance.

(12) Specific resistance (ρ; measured at 25 ° C .; Ω cm): 1.0 mL of a sample was injected into a container equipped with an electrode. A direct current voltage (10 V) was applied to the container, and a direct current after 10 seconds was measured. The specific resistance was calculated from the following equation. (Specific resistance) = {(voltage) × (electric capacity of container)} / {(direct current) × (dielectric constant of vacuum)}.

(13) Line Image Sticking Parameter (LISP;%): A line afterimage was generated by applying electrical stress to the liquid crystal display element. The luminance of the area with a line afterimage and the luminance of the remaining area were measured. The rate at which the luminance decreased due to the line afterimage was calculated, and the size of the line afterimage was represented by this rate.

13a) Measurement of luminance: An image of the device was photographed using an imaging color luminance meter (PM-1433F-0, manufactured by Radiant Zemax). The brightness of each area of the device was calculated by analyzing this image using software (Prometric 9.1, manufactured by Radiant Imaging).

13b) Setting of stress voltage: A sample is placed in an FFS device (16 cells of 4 vertical cells × 4 horizontal cells) having a cell gap of 3.5 μm and having a matrix structure, and using an adhesive that cures the devices with ultraviolet light Sealed. Polarizers were disposed on the upper and lower surfaces of the device, respectively, such that the polarization axes were orthogonal to each other. The device was irradiated with light and a voltage (square wave, 60 Hz) was applied. The voltage was increased stepwise from 0.1 V in the range of 0 V to 7.5 V, and the brightness of the transmitted light at each voltage was measured. The voltage at which the luminance is maximized is abbreviated V255. The voltage when the luminance was 21.6% of V255 (that is, 127 gradations) was abbreviated as V127.

13c) Stress conditions: V255 (square wave, 30 Hz) and 0.5 V (square wave, 30 Hz) were applied to the device under conditions of 60 ° C. and 23 hours to display a checkered pattern. Next, V127 (a square wave, 0.25 Hz) was applied, and the luminance was measured under the condition of an exposure time of 4000 milliseconds.

13d) Calculation of line afterimage: 4 cells in the central portion (2 vertical cells × 2 horizontal cells) of 16 cells were used for calculation. The four cells were divided into 25 areas (5 cells vertically × 5 cells horizontally). The average luminance of four regions (two vertical cells × two horizontal cells) at four corners is abbreviated as luminance A. The area excluding the four corner areas from the 25 area was a cruciform. The minimum value of the luminance is abbreviated as luminance B in four regions excluding the central intersection region from the cruciform region. The line afterimage was calculated from the following equation. (Line afterimage) = (brightness A−brightness B) / brightness A × 100.

(14) Spreadability: The spreadability of the additive was evaluated qualitatively by applying a voltage to the device and measuring the luminance. The measurement of the luminance was performed in the same manner as the item 16a described above. The setting of the voltage (V127) was performed in the same manner as in the above item 16b. However, a VA element was used instead of the FFS element. The luminance was measured as follows. First, a DC voltage (2 V) was applied to the device for 2 minutes. Next, V127 (square wave, 0.05 Hz) was applied, and the luminance was measured under the condition of exposure time of 4000 milliseconds. The spreadability was evaluated from this result.

Synthesis Example 1
The compound (1-2-1) was synthesized by the method described below.

First step:
In a 300 ml three-necked flask, 2,2,6,6-tetramethylpiperidin-4-one (15.0 g, 96.6 mmol), benzyl bromide (BnBr) (19.83 g, 116.0 mmol), potassium carbonate 26.71 g, 193.3 mmol), potassium iodide (1.49 g, 8.99 mmol), and acetonitrile (120 ml) were added and stirred at 80 ° C. to 85 ° C. for 24 hours. The reaction solution was returned to room temperature, poured into water, and extracted three times with toluene (100 ml). The extract was washed with water until it reached pH 7, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. To the residue is added petroleum ether (24 ml) and ethanol (24 ml) is added at -25 ° C for 2 hours, followed by recrystallization at -25 ° C for 1 hour to obtain compound (T-1) (10.8 g, yield) 45.6%).

Second step:
In a 200-ml three-necked flask, magnesium (1.67 g, 72.7 mmol) and tetrahydrofuran (THF) (20 ml) were placed, and compound (T-2) (18.6 g, 66.1 mmol) was added at 55 ° C to 65 ° C. The mixture was added dropwise and stirred for 1 hour. A solution of compound (T-1) (10.8 g, 44.1 mmol) in THF (30 ml) was added dropwise and stirred for 1 hour. Diluted hydrochloric acid was added dropwise to the reaction solution cooled in an ice bath to adjust pH 4 to pH 5. Next, saturated sodium bicarbonate aqueous solution was added dropwise to adjust pH 8 to pH 9. The solution was extracted three times with toluene (50 ml). The extract was washed with water until pH7. After drying over anhydrous magnesium sulfate, concentration under reduced pressure gave a compound (T-3) (29.6 g, yield 100%).

Third step:
After dissolving the compound (T-3) (29.6 g, 44.1 mmol) in toluene (150 ml), p-toluenesulfonic acid monohydrate (p-TsOH · H ₂ O) (2.96 g) is added The mixture was stirred at 75 ° C. to 110 ° C. for 2 hours. After the reaction solution was returned to room temperature, saturated aqueous sodium bicarbonate solution was added dropwise to adjust pH 8 to pH 9. The solution was washed with water until pH 7, dried over anhydrous magnesium sulfate and concentrated in vacuo. The residue was recrystallized from a mixed solvent of toluene (15 ml) and heptane (30 ml) to give compound (T-4) (15.2 g, yield 80.2%).

Fourth step:
Compound (T-4) (15.2 g, 35.4 mmol) is dissolved in a mixed solvent of toluene (90 ml) and ethanol (30 ml), palladium carbon (0.75 g, 0.05 wt%) is added, and hydrogen is added. The mixture was stirred at 55 to 60 ° C. for 24 hours under an atmosphere. The insolubles were filtered off and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate). Recrystallization from a mixed solvent of ethanol (20 ml) and heptane (40 ml) gave compound (1-2-1) (6.09 g, yield 50.4%).

¹ H-NMR (ppm; CDCl ₃ ): δ 7.17 to 7.13 (m, 4 H), 2.99 (tt, J = 10.1 Hz, J = 3.1 Hz, 1 H), 2.44 (tt , J = 12.1 Hz, J = 3.1 Hz, 1 H), 1.90 to 1.83 (m, 4 H), 1.77 (dd, J = 13.3 Hz, J = 3.2 Hz, 2 H), 1.59 (brs, 1H) 1.48 to 1.18 (m, 16H) 1.14 (s, 6H), 0.90 (t, J = 7.2 Hz, 3H).

  Examples of compositions are given below. Component compounds are represented by symbols based on the definition of Table 3 below. In Table 3, the configuration for 1,4-cyclohexylene is trans. The number in parenthesis after the symbolized compound represents the chemical formula to which the compound belongs. The symbol (-) means other liquid crystal compounds. The proportion (percentage) of the liquid crystal compound is a mass percentage (mass%) based on the mass of the liquid crystal composition not including the additive. Finally, the characteristic values of the composition were summarized.

Example 1
The following composition (M1) was prepared.
V-HB (2F, 3F) -O2 (2-1) 7%
V2-BB (2F, 3F) -O2 (2-6) 10%
V-HHB (2F, 3F) -O1 (2-8) 7%
V-HHB (2F, 3F) -O2 (2-8) 9%
V2-HHB (2F, 3F) -O2 (2-8) 8%
3-HH2B (2F, 3F) -O2 (2-9) 9%
V-HBB (2F, 3F) -O2 (2-14) 8%
V-HBB (2F, 3F) -O4 (2-14) 6%
3-HH-V (3-1) 15%
3-HH-V1 (3-1) 6%
2-HH-3 (3-1) 9%
3-HH-5 (3-1) 3%
1V2-HH-3 (3-1) 3%
Tc <-20 ° C; Δn = 0.100; Δε = -3.4; Vth = 2.02 V; = 1 = 18.9 mPa · s.
The compound (1-2-1) was added to the composition (M1) in a proportion of 0.15% by mass. The lower limit temperature (Tc) was <−20 ° C.

Example 2
The compound (1-3-1) was added to the composition (M1) in a proportion of 0.15% by mass. The lower limit temperature (Tc) was <−20 ° C.

Comparative Example 1
The comparison compound (A) was added to the composition (M1) in a proportion of 0.15% by mass. The lower limit temperature (Tc) was <0 ° C.

Comparative Example 2
The comparative compound (B) was added to the composition (M1) in a proportion of 0.15% by mass. The lower limit temperature (Tc) was <0 ° C.

The results of Examples 1 and 2 and Comparative Examples 1 and 2 are summarized in Table 4. It can be seen from Table 4 that the compound (1) is superior to the comparative compound in terms of solubility at a lower limit temperature, that is, low temperature.

Comparative Example 3
The following composition (M2) was prepared.
3-BB (2F, 3F)-O2 (2-6) 13%
2-HH1OB (2F, 3F) -O2 (2-10) 20%
3-HH1OB (2F, 3F) -O2 (2-10) 14%
3-HH-V (3-1) 29%
1-BB-3 (3-3) 10%
3-HHB-1 (3-5) 8%
5-B (F) BB-2 (3-7) 6%
Tc <−20 ° C .; Δn = 0.106; Δε = −3.0; = 1 = 14.7 mPa · s.
The line afterimage (LISP) of this composition (M2) was 9.1%.

[Example 3]
The compound (1-3-1) was added to the composition (M2) in a proportion of 0.07% by mass. The line afterimage (LISP) was 3.4%.

ＮＩ＝８７．６℃；Ｔｃ＜−２０℃；Δｎ＝０．１２６；Δε＝−４．５；η＝２５．３ｍＰａ・ｓ；ＬＩＳＰ＝１．８％． Example 4
3-HB (2F, 3F)-O4 (2-1) 6%
3-H 2 B (2F, 3F) -O 2 (2-2) 8%
3-H1OB (2F, 3F) -O2 (2-3) 5%
3-BB (2F, 3F)-O2 (2-6) 10%
2-HHB (2F, 3F) -O2 (2-8) 7%
3-HHB (2F, 3F) -O2 (2-8) 7%
5-HHB (2F, 3F) -O2 (2-8) 7%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 7%
5-HBB (2F, 3F) -O2 (2-14) 6%
3-HH-V (3-1) 11%
1-BB-3 (3-3) 6%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 4%
3-HBB-2 (3-6) 4%
3-B (F) BB-2 (3-7) 4%
The compound (1-2-1) was added to the composition at a rate of 0.07% by mass.

Tc <−20 ° C .; Δn = 0.126; Δε = −4.5; = 2 = 25.3 mPa · s; LISP = 1.8%.

ＮＩ＝８１．２℃；Ｔｃ＜−２０℃；Δｎ＝０．１０７；Δε＝−３．２；η＝１５．５ｍＰａ・ｓ；ＬＩＳＰ＝２．０％． [Example 5]
3-HB (2F, 3F)-O2 (2-1) 5%
5-HB (2F, 3F)-O2 (2-1) 7%
3-BB (2F, 3F)-O2 (2-6) 8%
3-HHB (2F, 3F) -O2 (2-8) 5%
5-HHB (2F, 3F) -O2 (2-8) 4%
3-HH1OB (2F, 3F) -O2 (2-10) 5%
2-HBB (2F, 3F) -O2 (2-14) 3%
3-HBB (2F, 3F) -O2 (2-14) 9%
4-HBB (2F, 3F) -O2 (2-14) 4%
5-HBB (2F, 3F) -O2 (2-14) 8%
2-BB (2F, 3F) B-3 (2-19) 4%
3-HH-V (3-1) 27%
3-HH-V1 (3-1) 6%
V-HHB-1 (3-5) 5%
The compound (1-2-1) was added to this composition in the ratio of 0.10 mass%.

Tc <−20 ° C .; Δn = 0.107; Δε = −3.2; = 1 = 15.5 mPa · s; LISP = 2.0%.

ＮＩ＝８８．２℃；Ｔｃ＜−２０℃；Δｎ＝０．１１５；Δε＝−２．１；η＝１８．３ｍＰａ・ｓ；ＬＩＳＰ＝３．２％． [Example 6]
3-H 2 B (2F, 3F) -O 2 (2-2) 7%
3-HHB (2F, 3F) -O2 (2-8) 8%
3-HH1OB (2F, 3F) -O2 (2-10) 8%
2-HchB (2F, 3F)-O2 (2-12) 8%
3-HD h B (2F, 3F)-O2 (2-13) 3%
5-HDhB (2F, 3F) -O2 (2-13) 4%
2-BB (2F, 3F) B-3 (2-19) 7%
2-BB (2F, 3F) B-4 (2-19) 7%
4-HH-V (3-1) 15%
3-HH-V1 (3-1) 6%
1-HH-2V1 (3-1) 6%
3-HH-2V1 (3-1) 4%
V2-BB-1 (3-3) 5%
1V2-BB-1 (3-3) 5%
3-HHB-1 (3-5) 3%
3-HB (F) BH-3 (3-12) 4%
The compound (1-3-1) was added to this composition in the ratio of 0.10 mass%.

Tc <−20 ° C .; Δn = 0.115; Δε = −2.1; = 1 = 18.3 mPa · s; LISP = 3.2%.

ＮＩ＝８９．９℃；Ｔｃ＜−２０℃；Δｎ＝０．１２２；Δε＝−４．２；η＝２３．４ｍＰａ・ｓ；ＬＩＳＰ＝３．５％． [Example 7]
V2-H2B (2F, 3F) -O2 (2-2) 8%
V2-H1OB (2F, 3F) -O4 (2-3) 4%
3-BB (2F, 3F)-O2 (2-6) 7%
2-HHB (2F, 3F) -O2 (2-8) 7%
3-HHB (2F, 3F) -O2 (2-8) 7%
3-HH2B (2F, 3F)-O2 (2-9) 7%
5-HH2B (2F, 3F)-O2 (2-9) 4%
V-HH2B (2F, 3F)-O2 (2-9) 6%
V2-HBB (2F, 3F) -O2 (2-14) 5%
V-HBB (2F, 3F) -O2 (2-14) 5%
V-HBB (2F, 3F) -O4 (2-14) 6%
2-HH-3 (3-1) 12%
1-BB-5 (3-3) 12%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 3%
3-HBB-2 (3-6) 3%
The compound (1-3-1) was added to this composition at a ratio of 0.08% by mass.

Tc <−20 ° C .; Δn = 0.122; Δε = −4.2; = 2 = 23.4 mPa · s; LISP = 3.5%.

ＮＩ＝７７．１℃；Ｔｃ＜−２０℃；Δｎ＝０．１０１；Δε＝−３．０；η＝１３．９ｍＰａ・ｓ；ＬＩＳＰ＝２．５％． [Example 8]
3-HB (2F, 3F) -O2 (2-1) 3%
V-HB (2F, 3F) -O2 (2-1) 3%
V2-HB (2F, 3F) -O2 (2-1) 5%
5-H2B (2F, 3F)-O2 (2-2) 5%
V2-BB (2F, 3F) -O2 (2-6) 3%
1V2-BB (2F, 3F) -O2 (2-6) 3%
3-HHB (2F, 3F) -O2 (2-8) 6%
V-HHB (2F, 3F) -O2 (2-8) 6%
V-HHB (2F, 3F) -O4 (2-8) 5%
V2-HHB (2F, 3F) -O2 (2-8) 4%
V-HHB (2F, 3Cl) -O2 (2-11) 3%
V2-HBB (2F, 3F) -O2 (2-14) 5%
V-HBB (2F, 3F) -O2 (2-14) 4%
V-HBB (2F, 3F) -O4 (2-14) 5%
V2-BB (2F, 3F) B-1 (2-19) 4%
3-HH-V (3-1) 27%
3-HH-V1 (3-1) 6%
V-HHB-1 (3-5) 3%
The compound (1-2-1) was added to this composition at a ratio of 0.05% by mass.

Tc <−20 ° C .; Δn = 0.101; Δε = −3.0; = 1 = 13.9 mPa · s; LISP = 2.5%.

ＮＩ＝９３．０℃；Ｔｃ＜−２０℃；Δｎ＝０．１２４；Δε＝−４．５；η＝２５．０ｍＰａ・ｓ；ＬＩＳＰ＝２．１％． [Example 9]
3-HB (2F, 3F)-O4 (2-1) 6%
3-H 2 B (2F, 3F) -O 2 (2-2) 8%
3-H1OB (2F, 3F) -O2 (2-3) 4%
3-BB (2F, 3F)-O2 (2-6) 7%
2-HHB (2F, 3F) -O2 (2-8) 6%
3-HHB (2F, 3F) -O2 (2-8) 10%
5-HHB (2F, 3F) -O2 (2-8) 8%
2-HBB (2F, 3F) -O2 (2-14) 5%
3-HBB (2F, 3F) -O2 (2-14) 7%
5-HBB (2F, 3F) -O2 (2-14) 5%
2-HH-3 (3-1) 12%
1-BB-3 (3-3) 6%
3-HHB-1 (3-5) 3%
3-HHB-O1 (3-5) 4%
3-HBB-2 (3-6) 6%
3-B (F) BB-2 (3-7) 3%
The compound (1-2-1) was added to this composition in the ratio of 0.08 mass%.

NI = 93.0 ° C .; Tc <−20 ° C .; Δn = 0.124; Δε = −4.5; = 2 = 25.0 mPa · s; LISP = 2.1%.

ＮＩ＝８７．５℃；Ｔｃ＜−２０℃；Δｎ＝０．１００；Δε＝−３．４；η＝１８．９ｍＰａ・ｓ；ＬＩＳＰ＝２．６％． [Example 10]
V-HB (2F, 3F) -O2 (2-1) 7%
V2-BB (2F, 3F) -O2 (2-6) 10%
V-HHB (2F, 3F) -O1 (2-8) 7%
V-HHB (2F, 3F) -O2 (2-8) 9%
V2-HHB (2F, 3F) -O2 (2-8) 8%
3-HH2B (2F, 3F) -O2 (2-9) 9%
V-HBB (2F, 3F) -O2 (2-14) 8%
V-HBB (2F, 3F) -O4 (2-14) 6%
3-HH-V (3-1) 15%
3-HH-V1 (3-1) 6%
2-HH-3 (3-1) 9%
3-HH-5 (3-1) 3%
1V2-HH-3 (3-1) 3%
The compound (1-2-1) was added to this composition at a ratio of 0.05% by mass.

Tc <−20 ° C .; Δn = 0.100; Δε = −3.4; = 1 = 18.9 mPa · s; LISP = 2.6%.

ＮＩ＝７６．４℃；Ｔｃ＜−２０℃；Δｎ＝０．１０４；Δε＝−３．２；η＝１５．６ｍＰａ・ｓ；ＬＩＳＰ＝１．７％． [Example 11]
3-HB (2F, 3F) -O2 (2-1) 7%
5-HB (2F, 3F)-O2 (2-1) 7%
3-BB (2F, 3F)-O2 (2-6) 8%
3-HHB (2F, 3F) -O2 (2-8) 4%
5-HHB (2F, 3F) -O2 (2-8) 5%
3-HH1OB (2F, 3F) -O2 (2-10) 5%
2-HBB (2F, 3F) -O2 (2-14) 3%
3-HBB (2F, 3F) -O2 (2-14) 8%
4-HBB (2F, 3F) -O2 (2-14) 5%
5-HBB (2F, 3F) -O2 (2-14) 8%
2-BB (2F, 3F) B-3 (2-19) 4%
3-HH-V (3-1) 33%
V-HHB-1 (3-5) 3%
The compound (1-2-1) was added to this composition in the ratio of 0.10 mass%.

Tc <−20 ° C .; Δn = 0.104; Δε = −3.2; = 1 = 15.6 mPa · s; LISP = 1.7%.

ＮＩ＝７８．３℃；Ｔｃ＜−２０℃；Δｎ＝０．１０３；Δε＝−３．２；η＝１７．７ｍＰａ・ｓ；ＬＩＳＰ＝３．５％． [Example 12]
2-H1OB (2F, 3F) -O2 (2-3) 6%
3-H1OB (2F, 3F) -O2 (2-3) 4%
3-BB (2F, 3F)-O2 (2-6) 3%
2-HH1OB (2F, 3F) -O2 (2-10) 14%
2-HBB (2F, 3F) -O2 (2-14) 7%
3-HBB (2F, 3F) -O2 (2-14) 11%
5-HBB (2F, 3F) -O2 (2-14) 9%
2-HH-3 (3-1) 5%
3-HH-VFF (3-1) 30%
1-BB-3 (3-3) 5%
3-HHB-1 (3-5) 3%
3-HBB-2 (3-6) 3%
The compound (1-3-1) was added to the composition at a rate of 0.07% by mass.

Tc <−20 ° C .; Δn = 0.103; Δε = −3.2; = 1 = 17.7 mPa · s; LISP = 3.5%.

ＮＩ＝７５．９℃；Ｔｃ＜−２０℃；Δｎ＝０．１１４；Δε＝−３．９；η＝２４．７ｍＰａ・ｓ；ＬＩＳＰ＝１．８％． [Example 13]
V-HB (2F, 3F) -O2 (2-1) 10%
V2-HB (2F, 3F) -O2 (2-1) 10%
2-H1OB (2F, 3F) -O2 (2-3) 3%
3-H1OB (2F, 3F) -O2 (2-3) 3%
2O-BB (2F, 3F) -O2 (2-6) 3%
V2-BB (2F, 3F) -O2 (2-6) 8%
V2-HHB (2F, 3F) -O2 (2-8) 5%
V-HHB (2F, 3Cl) -O2 (2-11) 7%
2-HBB (2F, 3F) -O2 (2-14) 3%
3-HBB (2F, 3F) -O2 (2-14) 3%
V-HBB (2F, 3F) -O2 (2-14) 6%
V-HBB (2F, 3F) -O4 (2-14) 8%
3-HH-4 (3-1) 14%
V-HHB-1 (3-5) 10%
3-HBB-2 (3-6) 7%
The compound (1-2-1) was added to the composition at a rate of 0.07% by mass.

Tc <−20 ° C .; Δn = 0.114; Δε = −3.9; = 2 = 24.7 mPa · s; LISP = 1.8%.

ＮＩ＝７２．６℃；Ｔｃ＜−２０℃；Δｎ＝０．１０５；Δε＝−２．５；η＝１５．７ｍＰａ・ｓ；ＬＩＳＰ＝３．１％． 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%
3-HB-O2 (3-2) 3%
1-BB-3 (3-3) 3%
3-HHB-1 (3-5) 6%
2-BB (F) B-3 (3-8) 2%
The compound (1-3-1) was added to this composition in the ratio of 0.09 mass%.

Tc <−20 ° C .; Δn = 0.105; Δε = −2.5; = 1 = 15.7 mPa · s; LISP = 3.1%.

ＮＩ＝８２．８℃；Ｔｃ＜−２０℃；Δｎ＝０．１１８；Δε＝−４．４；η＝２２．５ｍＰａ・ｓ；ＬＩＳＰ＝２．９％． [Example 15]
3-HB (2F, 3F)-O4 (2-1) 6%
3-H 2 B (2F, 3F) -O 2 (2-2) 8%
3-H1OB (2F, 3F) -O2 (2-3) 4%
3-BB (2F, 3F)-O2 (2-6) 7%
2-HHB (2F, 3F) -O2 (2-8) 7%
3-HHB (2F, 3F) -O2 (2-8) 7%
3-HH2B (2F, 3F)-O2 (2-9) 7%
5-HH2B (2F, 3F)-O2 (2-9) 4%
2-HBB (2F, 3F) -O2 (2-14) 5%
3-HBB (2F, 3F) -O2 (2-14) 5%
4-HBB (2F, 3F) -O2 (2-14) 6%
2-HH-3 (3-1) 12%
1-BB-5 (3-3) 12%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 3%
3-HBB-2 (3-6) 3%
The compound (1-3-1) was added to this composition in the ratio of 0.10 mass%.

Tc <−20 ° C .; Δn = 0.118; Δε = −4.4; = 2 = 22.5 mPa · s; LISP = 2.9%.

ＮＩ＝７８．１℃；Ｔｃ＜−２０℃；Δｎ＝０．１０７；Δε＝−３．２；η＝１５．９ｍＰａ・ｓ；ＬＩＳＰ＝１．７％． [Example 16]
3-HB (2F, 3F) -O2 (2-1) 7%
5-HB (2F, 3F)-O2 (2-1) 7%
3-BB (2F, 3F)-O2 (2-6) 8%
3-HHB (2F, 3F) -O2 (2-8) 5%
5-HHB (2F, 3F) -O2 (2-8) 4%
3-HH1OB (2F, 3F) -O2 (2-10) 4%
2-HBB (2F, 3F) -O2 (2-14) 3%
3-HBB (2F, 3F) -O2 (2-14) 8%
4-HBB (2F, 3F) -O2 (2-14) 5%
5-HBB (2F, 3F) -O2 (2-14) 8%
2-BB (2F, 3F) B-3 (2-19) 5%
3-HH-V (3-1) 27%
3-HH-V1 (3-1) 6%
V-HHB-1 (3-5) 3%
The compound (1-2-1) was added to this composition in the ratio of 0.15 mass%.

Tc <−20 ° C .; Δn = 0.107; Δε = −3.2; = 1 = 15.9 mPa · s; LISP = 1.7%.

ＮＩ＝８８．５℃；Ｔｃ＜−２０℃；Δｎ＝０．１０８；Δε＝−３．８；η＝２４．６ｍＰａ・ｓ；ＬＩＳＰ＝３．４％． [Example 17]
3-HB (2F, 3F)-O2 (2-1) 10%
5-HB (2F, 3F)-O2 (2-1) 10%
3-H 2 B (2F, 3F) -O 2 (2-2) 8%
5-H2B (2F, 3F)-O2 (2-2) 8%
3-HD h B (2F, 3F)-O2 (2-13) 5%
2-HBB (2F, 3F) -O2 (2-14) 6%
3-HBB (2F, 3F) -O2 (2-14) 8%
4-HBB (2F, 3F) -O2 (2-14) 7%
5-HBB (2F, 3F) -O2 (2-14) 7%
3-HH-4 (3-1) 14%
V-HHB-1 (3-5) 10%
3-HBB-2 (3-6) 7%
The compound (1-3-1) was added to this composition at a ratio of 0.08% by mass.

Tc <−20 ° C .; Δn = 0.108; Δε = −3.8; = 2 = 24.6 mPa · s; LISP = 3.4%.

ＮＩ＝７１．８℃；Ｔｃ＜−２０℃；Δｎ＝０．１０３；Δε＝−２．５；η＝１４．２ｍＰａ・ｓ；ＬＩＳＰ＝１．８％． [Example 18]
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) 4%
3-HHB (2F, 3F) -1 (2-8) 4%
3-dhBB (2F, 3F) -O2 (2-16) 5%
3-HB (2F) B (2F, 3F) -O2 (2-18) 7%
V-H2 BBB (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%
The compound (1-2-1) was added to the composition at a rate of 0.07% by mass.

Tc <−20 ° C .; Δn = 0.103; Δε = −2.5; = 1 = 14.2 mPa · s;

ＮＩ＝９８．８℃；Ｔｃ＜−２０℃；Δｎ＝０．１１１；Δε＝−３．２；η＝２３．９ｍＰａ・ｓ；ＬＩＳＰ＝２．０％． [Example 19]
3-HB (2F, 3F)-O4 (2-1) 15%
3-chB (2F, 3F)-O2 (2-5) 7%
2-HchB (2F, 3F)-O2 (2-12) 8%
3-HBB (2F, 3F) -O2 (2-14) 8%
4-HBB (2F, 3F) -O2 (2-14) 5%
5-HBB (2F, 3F) -O2 (2-14) 7%
3-dhBB (2F, 3F) -O2 (2-16) 5%
5-HH-V (3-1) 18%
7-HB-1 (3-2) 5%
V-HHB-1 (3-5) 7%
V2-HHB-1 (3-5) 7%
3-HBB (F) B-3 (3-13) 8%
The compound (1-2-1) was added to this composition in the ratio of 0.06 mass%.

NI = 98.8 ° C .; Tc <−20 ° C .; Δn = 0.111; Δε = −3.2; = 2 = 23.9 mPa · s; LISP = 2.0%.

ＮＩ＝７７．５℃；Ｔｃ＜−２０℃；Δｎ＝０．０８４；Δε＝−２．６；η＝２２．８ｍＰａ・ｓ；ＬＩＳＰ＝２．９％． [Example 20]
3-H 2 B (2F, 3F) -O 2 (2-2) 18%
5-H2B (2F, 3F)-O2 (2-2) 17%
3-HHB (2F, 3Cl) -O2 (2-11) 5%
3-HD h B (2F, 3F)-O2 (2-13) 5%
3-HBB (2F, 3Cl) -O2 (2-15) 8%
5-HBB (2F, 3Cl) -O2 (2-15) 7%
3-HH-V (3-1) 11%
3-HH-VFF (3-1) 7%
F3-HH-V (3-1) 10%
3-HHEH-3 (3-4) 4%
3-HB (F) HH-2 (3-10) 4%
3-HHEBH-3 (3-11) 4%
The compound (1-3-1) was added to this composition at a ratio of 0.15% by mass.

Tc <−20 ° C .; Δn = 0.084; Δε = −2.6; = 2 = 22.8 mPa · s; LISP = 2.9%.

ＮＩ＝７０．６℃；Ｔｃ＜−２０℃；Δｎ＝０．１２９；Δε＝−４．３；η＝２７．０ｍＰａ・ｓ；ＬＩＳＰ＝３．０％． [Example 21]
3-HB (2F, 3F)-O2 (2-1) 8%
3-H 2 B (2F, 3F) -O 2 (2-2) 10%
3-BB (2F, 3F)-O2 (2-6) 10%
2O-BB (2F, 3F) -O2 (2-6) 3%
2-HHB (2F, 3F) -O2 (2-8) 4%
3-HHB (2F, 3F) -O2 (2-8) 7%
2-HHB (2F, 3F) -1 (2-8) 5%
3-HD h B (2F, 3F)-O2 (2-13) 6%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 7%
3-dhBB (2F, 3F) -O2 (2-16) 4%
2-BB (2F, 3F) B-3 (2-19) 6%
2-BB (2F, 3F) B-4 (2-19) 6%
3-HH1OCro (7F, 8F) -5 (2-27) 4%
3-HH-V (3-1) 11%
1-BB-5 (3-3) 5%
The compound (1-3-1) was added to this composition in the ratio of 0.10 mass%.

Tc <−20 ° C .; Δn = 0.129; Δε = −4.3; = 2 = 27.0 mPa · s; LISP = 3.0%.

ＮＩ＝７３．５℃；Ｔｃ＜−２０℃；Δｎ＝０．１０６；Δε＝−２．７；η＝１７．０ｍＰａ・ｓ；ＬＩＳＰ＝１．４％． Example 22
3-HB (2F, 3F)-O2 (2-1) 5%
V2-BB (2F, 3F) -O2 (2-6) 8%
3-HHB (2F, 3F) -O2 (2-8) 6%
V-HHB (2F, 3F) -O2 (2-8) 7%
V-HHB (2F, 3F) -O4 (2-8) 4%
2-HBB (2F, 3F) -O2 (2-14) 2%
3-HBB (2F, 3F) -O2 (2-14) 6%
V-HBB (2F, 3F) -O2 (2-14) 7%
V-HBB (2F, 3F) -O4 (2-14) 6%
2-BB (2F, 3F) B-3 (2-19) 5%
V-HH-V (3-1) 24%
V-HH-V1 (3-1) 20%
The compound (1-2-1) was added to this composition in the ratio of 0.10 mass%.

Tc <−20 ° C .; Δn = 0.106; Δε = −2.7; = 1 = 17.0 mPa · s; LISP = 1.4%.

ＮＩ＝８６．０℃；Ｔｃ＜−２０℃；Δｎ＝０．１１０；Δε＝−３．８；η＝２２．９ｍＰａ・ｓ；ＬＩＳＰ＝３．７％． [Example 23]
3-DhB (2F, 3F) -O2 (2-4) 5%
2-BB (2F, 3F)-O2 (2-6) 9%
3-BB (2F, 3F)-O2 (2-6) 9%
3-HH2B (2F, 3F)-O2 (2-9) 6%
3-HD h B (2F, 3F)-O2 (2-13) 14%
2-HBB (2F, 3F) -O2 (2-14) 2%
3-HBB (2F, 3F) -O2 (2-14) 6%
V-HBB (2F, 3F) -O2 (2-14) 7%
2-HH-3 (3-1) 19%
3-HHB-1 (3-5) 3%
V-HHB-1 (3-5) 10%
V2-HHB-1 (3-5) 10%
The compound (1-3-1) was added to this composition at a ratio of 0.05% by mass.

Tc <-20 ° C; Δn = 0.110; Δε = -3.8; = 2 = 22.9 mPa · s; LISP = 3.7%.

ＮＩ＝８０．８℃；Ｔｃ＜−２０℃；Δｎ＝０．１００；Δε＝−２．７；γ１＝９４．０ｍＰａ・ｓ；ＬＩＳＰ＝１．７％． [Example 24]
2-H1OB (2F, 3F) -O2 (2-3) 7%
3-H1OB (2F, 3F) -O2 (2-3) 8%
3-BB (2F, 3F)-O2 (2-6) 7%
3-HH1OB (2F, 3F) -O2 (2-10) 2%
3-HD h B (2F, 3F)-O2 (2-13) 6%
2-HBB (2F, 3F) -O2 (2-14) 3%
3-HBB (2F, 3F) -O2 (2-14) 3%
4-HBB (2F, 3F) -O2 (2-14) 3%
V-HBB (2F, 3F) -O2 (2-14) 4%
2-HH-3 (3-1) 14%
3-HH-4 (3-1) 5%
3-HH-5 (3-1) 5%
3-HB-O2 (3-2) 8%
3-HHB-1 (3-5) 6%
3-HHB-3 (3-5) 6%
3-HHB-O1 (3-5) 4%
3-HBB-2 (3-6) 9%
The compound (1-2-1) was added to this composition in the ratio of 0.10 mass%.

Tc <−20 ° C .; Δn = 0.100; Δε = −2.7; γ1 = 94.0 mPa · s; LISP = 1.7%.

ＮＩ＝８５．６℃；Ｔｃ＜−２０℃；Δｎ＝０．１０７；Δε＝−３．５；η＝１９．３ｍＰａ・ｓ；ＬＩＳＰ＝３．６％． [Example 25]
3-HB (2F, 3F) -O2 (2-1) 7%
V-HB (2F, 3F) -O2 (2-1) 14%
2-HHB (2F, 3F) -O2 (2-8) 2%
3-HHB (2F, 3F) -O2 (2-8) 7%
V-HHB (2F, 3F) -O1 (2-8) 2%
V-HHB (2F, 3F) -O2 (2-8) 3%
2-HBB (2F, 3F) -O2 (2-14) 3%
3-HBB (2F, 3F) -O2 (2-14) 9%
V-HBB (2F, 3F) -O2 (2-14) 9%
5-HBB (2F, 3F) -O2 (2-14) 6%
2-HH-3 (3-1) 19.5%
3-HH-VFF (3-1) 6%
3-HHB-1 (3-5) 4.5%
V-HBB-2 (3-6) 8%
The compound (1-3-1) was added to this composition at a ratio of 0.05% by mass.

Tc <−20 ° C .; Δn = 0.107; Δε = −3.5; = 1 = 19.3 mPa · s; LISP = 3.6%.

ＮＩ＝８５．４℃；Ｔｃ＜−２０℃；Δｎ＝０．１０４；Δε＝−３．７；η＝２０．２ｍＰａ・ｓ；ＬＩＳＰ＝１．８％． [Example 26]
3-HB (2F, 3F) -O2 (2-1) 14%
3-H 2 B (2F, 3F) -O 2 (2-2) 5%
V2-BB (2F, 3F) -O2 (2-6) 6%
2-HHB (2F, 3F) -O2 (2-8) 2%
3-HHB (2F, 3F) -O2 (2-8) 11.5%
V-HHB (2F, 3F) -O2 (2-8) 6.5%
3-HH2B (2F, 3F)-O2 (2-9) 4%
3-HBB (2F, 3F) -O2 (2-14) 10%
V-HBB (2F, 3F) -O2 (2-14) 6.5%
2-HH-3 (3-1) 18.5%
3-HH-VFF (3-1) 5.5%
V-HHB-1 (3-5) 5%
V-HBB-2 (3-6) 5.5%
The compound (1-2-1) was added to this composition in the ratio of 0.10 mass%.

Tc <−20 ° C .; Δn = 0.104; Δε = −3.7; = 2 = 20.2 mPa · s; LISP = 1.8%.

ＮＩ＝８５．４℃；Ｔｃ＜−２０℃；Δｎ＝０．１０８；Δε＝−３．４；γ１＝１２１．５ｍＰａ・ｓ；ＬＩＳＰ＝３．５％． [Example 27]
2-HH-3 (3-1) 16%
3-HH-4 (3-1) 4%
3-HB-O2 (3-2) 5%
3-BB (2F, 3F)-O2 (2-6) 6%
3-HB (2F, 3F)-O2 (2-1) 10%
5-HB (2F, 3F)-O2 (2-1) 8%
2-HBB (2F, 3F) -O2 (2-14) 2%
3-HBB (2F, 3F) -O2 (2-14) 6%
4-HBB (2F, 3F) -O2 (2-14) 3%
V-HBB (2F, 3F) -O4 (2-14) 6%
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-HHB-1 (3-5) 2%
3-HBB-2 (3-6) 10%
The compound (1-3-1) was added to this composition at a ratio of 0.08% by mass.

Tc <−20 ° C .; Δn = 0.108; Δε = −3.4; γ1 = 121.5 mPa · s; LISP = 3.5%.

ＮＩ＝７８．１℃；Ｔｃ＜−２０℃；Δｎ＝０．１０５；Δε＝−２．７；η＝１６．２ｍＰａ・ｓ；ＬＩＳＰ＝２．０％． [Example 28]
2-H1OB (2F, 3F) -O2 (2-3) 7%
3-H1OB (2F, 3F) -O2 (2-3) 7%
3-HHB (2F, 3F) -O2 (2-8) 4%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 8%
4-HBB (2F, 3F) -O2 (2-14) 4%
5-HBB (2F, 3F) -O2 (2-14) 9%
3-dhBB (2F, 3F) -O2 (2-16) 4%
2-HH-3 (3-1) 18%
3-HH-4 (3-1) 3%
3-HH-5 (3-1) 3%
2-HH-5 (3-1) 2%
3-HB-O2 (3-2) 17%
3-HBB-2 (3-6) 10%
To this composition, 0.07% by mass of the compound (1-2-1) and 0.43% by mass of the compound (4-25-1) were added.

Tc <−20 ° C .; Δn = 0.105; Δε = −2.7; = 1 = 16.2 mPa · s; LISP = 2.0%.

  The lower limit temperature of the composition of Comparative Example 1 and Comparative Example 2 was <0 ° C. On the other hand, the lower limit temperature of the composition of Example 1 and Example 2 was <−20 ° C. Therefore, it can be said that the first additive has better solubility at lower temperatures than similar piperidine derivatives. The line afterimage of the composition of Comparative Example 3 was 9.1%. On the other hand, the line afterimage of the compositions of Examples 3 to 28 was in the range of 1.7% to 3.7%. Therefore, it can be said that the first additive has the effect of suppressing line afterimage. Thus, it is concluded that the composition of the present invention has excellent properties.

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

Claims (18)

The liquid-crystal composition which contains at least 1 compound selected from the compound represented by Formula (1) as a 1st additive, and has negative dielectric constant anisotropy.

In Formula (1), R ¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons, and in these groups, at least one hydrogen is fluorine or chlorine. R ² is hydrogen, hydroxy, oxy radical, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons, and in these groups, At least one hydrogen bonded to carbon may be replaced by fluorine or chlorine; ring A, ring B and ring C may be 1,4-cyclohexylene, 1,4-cyclohexenylene, 3,4- Dihydro-2H-pyran-2,5-diyl, 3,4-dihydro-2H-pyran-3,6-diyl, 3,6-dihydro-2H-pyran-2,5- , Tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4-phenylene, pyridine-2,5-diyl, decahydronaphthalene-2,6-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 or naphthalene-2,7-diyl, in these rings, at least one hydrogen on the aromatic ring is fluorine, chlorine, cyano, alkyl having 1 to 5 carbon atoms C 1 to C 5 alkoxy, C 1 to C 5 alkyl in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen is Fluorine or chlorine may be replaced by alkoxy having 1 to 5 carbons; Z ¹ and Z ² are a single bond or alkylene having 1 to 10 carbons, and in this alkylene, at least one of- CH ₂ -may be replaced by -O-, -COO-, or -OCO-, and at least one -CH ₂ CH ₂ -is replaced by -CH = CH- or -C≡C- And in these groups, at least one hydrogen may be replaced by fluorine or chlorine; Z ³ is a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ -, -O -, - NH -, - COO-, or may be replaced by -OCO-, at least one _-CH 2 CH ₂ -, -CH = It may be replaced by H- or -C≡C-, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; a and b is 0 or 1. The liquid crystal composition according to claim 1, containing at least one compound selected from the compounds represented by formulas (1-1) to (1-14) as the first additive.

In formulas (1-1) to (1-14), R ¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons, and in these groups, And at least one hydrogen may be replaced by fluorine or chlorine; R ² is hydrogen, hydroxy, oxy radical, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or 2 to 12 carbons Alkenyl in which at least one hydrogen bonded to carbon may be replaced by fluorine or chlorine; X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are hydrogen Or fluorine.   The liquid crystal composition according to claim 1 or 2, wherein the proportion of the first additive is in the range of 0.005% by mass to 1% by mass. The liquid crystal composition according to any one of claims 1 to 3, containing at least one compound selected from the compounds represented by Formula (2) as a first component.

In Formula (2), R ³ and R ⁴ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons, Ring D and ring F each have 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene and at least one hydrogen substituted by fluorine or chlorine 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen is fluorine or Chlorine-substituted chroman-2,6-diyl; ring E is 2,3-difluoro-1,4-phenylene, 2-chloro -3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman- 2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, or 1,1,6,7-tetrafluoroindane be a 2,5-diyl; ^{Z 4} and ^{Z 5} is a single bond, ethylene, carbonyloxy or methyleneoxy,; c is 1, 2, or 3,, d is 0 or 1, And the sum of c and d is 3 or less. The liquid crystal composition according to any one of claims 1 to 4, containing at least one compound selected from the compounds represented by formulas (2-1) to (2-33) as a first component. .

In formulas (2-1) to (2-33), R ³ and R ^{4 each} represents hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon It is alkenyloxy of the number 2-12.   The liquid crystal composition according to any one of claims 1 to 5, wherein the proportion of the first component is in the range of 10% by mass to 90% by mass. The liquid crystal composition according to any one of claims 1 to 6, containing at least one compound selected from the compounds represented by Formula (3) as a second component.

In the formula (3), R ⁵ and R ^{6 each} represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon in which at least one hydrogen is replaced by fluorine or chlorine. The alkyl of the number 1 to 12 or an alkenyl of 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine; ring G and ring I are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ⁶ is a single bond, ethylene or carbonyloxy; e is 1, 2 or 3 is there. The liquid crystal composition according to any one of claims 1 to 7, containing at least one compound selected from the compounds represented by formulas (3-1) to (3-13) as a second component. .

In formulas (3-1) to (3-13), R ⁵ and R ^{6 each} represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, at least one hydrogen Is C 1-12 alkyl substituted with fluorine or chlorine, or C 2-12 alkenyl in which at least one hydrogen is substituted by fluorine or chlorine.   The liquid crystal composition according to claim 7 or 8, wherein the proportion of the second component is in the range of 10% by mass to 90% by mass. The liquid crystal composition according to any one of claims 1 to 9, containing at least one compound selected from the polymerizable compounds represented by formula (4) as a second additive.

In the formula (4), the ring J and the ring L are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl Or pyridin-2-yl, in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is fluorine or chlorine May be substituted by alkyl having 1 to 12 carbon atoms, which is substituted by; ring K 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-diy , Naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl in which at least one hydrogen is fluorine, chlorine, carbon number 1 12 alkyl, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine; Z ⁷ and Z ^{8 each} represents a single bond or carbon alkylene from C 1 10, in the alkylene, at least one of _-CH 2 -, -O -, - CO -, - COO-, or May be replaced by OCO-, at least one _-CH 2 CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, or -C ( CH ₃ ) = C (CH ₃ ) — which may be replaced by at least one hydrogen in these groups may be replaced by fluorine or chlorine; P ¹ , P ² and P ³ may be polymerized Sp ¹ , Sp ² , and Sp ^{3 each} represents a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO—, -OCO-, or -OCOO- in may be replaced, 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; f is 0, 1 or 2; g, h and i are 0, 1, 2, 3 or 4 and g, The sum of h and i is 1 or more. The compound according to claim ¹⁰ , wherein in the formula (4), P ¹ , P ² and P ³ are groups selected from the polymerizable groups represented by the formulas (P-1) to (P-5). Liquid crystal composition.

In Formula (P-1) to Formula (P-5), M ¹ , M ² and M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is replaced by fluorine or chlorine And alkyl having 1 to 5 carbon atoms. The second additive according to any one of claims 1 to 11, which contains at least one compound selected from polymerizable compounds represented by formulas (4-1) to (4-29) as a second additive. Liquid crystal composition.

In formulas (4-1) to (4-29), P ⁴ , P ⁵ and P ⁶ are selected from polymerizable groups represented by formulas (P-1) to (P-3) And

Here, M ¹ , M ² and M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine; Sp ¹ , Sp ² and Sp ^{3 each} represents 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 — OCOO-may be replaced, and at least one -CH ₂ CH ₂ -may be replaced by -CH = CH- or -C≡C-, and in these groups, at least one hydrogen is fluorine Or may be replaced by chlorine.   The liquid crystal composition according to any one of claims 10 to 12, wherein the proportion of the second additive is in the range of 0.03% by mass to 10% by mass.   A liquid crystal display device comprising the liquid crystal composition according to any one of claims 1 to 13.   The liquid crystal display element according to claim 14, 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.   A polymer supported alignment type liquid crystal display device, comprising the liquid crystal composition according to any one of claims 10 to 13, wherein a second additive contained in the liquid crystal composition is polymerized.   Use of the liquid crystal composition according to any one of claims 1 to 13 in a liquid crystal display device.   Use of the liquid crystal composition according to any one of claims 1 to 13 in a polymer supported alignment type liquid crystal display device.