JPWO2017014326A1 - Piperidine derivative, liquid crystal composition, and liquid crystal display device - Google Patents

Abstract

Problems include high upper temperature, low lower temperature, small viscosity, appropriate optical anisotropy, large negative dielectric anisotropy, high specific resistance, high stability against ultraviolet light, high stability against heat It is an object of the present invention to provide a liquid crystal composition which satisfies at least one property or has a proper balance between at least two of these properties. The advantage is that a liquid crystal composition having a compound having high solubility in a liquid crystal composition and having an effect of suppressing display defects of a liquid crystal display element as a first additive, and having negative dielectric anisotropy It is a thing. This composition comprises a specific compound having a large negative dielectric anisotropy negatively as a first component, a specific compound having a high upper temperature limit or a small viscosity as a second component, and a specific compound having a polymerizable group as a second additive And the following compounds.

Description

  The present invention relates to a piperidine derivative, a liquid crystal composition containing the compound, 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 projector, a liquid crystal television or the like.

  In a general-purpose liquid crystal display device, vertical alignment of liquid crystal molecules is achieved by a specific polyimide alignment film. In a liquid crystal display device of the polymer supported alignment (PSA) type, 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.

The following compound (A-1) is one of hindered amine light stabilizers (HALS). This compound has a polar group> N-CH _3. In this compound, the two polar groups are identical.

WO 2012/76105 specification JP, 2014-84460, A

  One object of the present invention is to provide a compound having high solubility in a liquid crystal composition and having an effect of suppressing display defects of a liquid crystal display element. Another object is high upper temperature limit of nematic phase, lower lower temperature limit of nematic phase, small viscosity, appropriate optical anisotropy, large negative dielectric anisotropy, high 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 suitable balance between at least two of these properties. Another object is to provide a liquid crystal display device containing such a composition. Another object is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long lifetime.

式（Ｓ）において、Ｒ^１は、水素、炭素数１から１２のアルキル、または炭素数１から１２のアルコキシであり；Ｒは、炭素数１から１２のアルキルである。The present invention has at least two monovalent radical of the formula (S), in these monovalent group, compound different from the group that the group represented by R ¹ is represented by the other of R ¹ The present invention relates to a liquid crystal composition containing this compound and having negative dielectric anisotropy, and a liquid crystal display device containing this composition.

In formula (S), R ¹ is hydrogen, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons; R is alkyl having 1 to 12 carbons.

  One advantage of the present invention is to provide a compound having high solubility in a liquid crystal composition and having the effect of suppressing display defects of a liquid crystal display element. Another object is high upper temperature limit of nematic phase, lower lower temperature limit of nematic phase, small viscosity, appropriate optical anisotropy, large negative dielectric anisotropy, high 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 suitable balance between at least two of these properties. Another object is to provide a liquid crystal display device containing such a composition. Another object is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long lifetime.

It is a photograph of an element which shows that spreadability is good. It is a photograph of an element which shows that spreadability is good. It is a photograph of the element which shows that spreadability is inferior.

  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 molecular structure 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 dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor and a polar compound are added to the liquid crystal composition as necessary. Ru. The proportion of the liquid crystal compound is represented by a weight percentage (% by weight) based on the weight of the liquid crystal composition without the additive even when the additive is added. The proportion of the additive is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition without the additive. That is, the proportions of the liquid crystal compound and the additive are calculated based on the total weight of the liquid crystal compound. Parts per million by weight (ppm) 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 not only at room temperature but also at a temperature close to the upper limit. It means having a retention rate. The characteristics of the composition or device may be examined by a time-lapse 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.

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 the component compounds, with symbols of terminal groups R ³ to a plurality of compounds. In these compounds, two groups represented by any two R ³ may be identical or different. For example, there is a case where R ^{3 of} compound (2-1) is ethyl and R ³ of compound (2-2) is ethyl. In some cases, R ^{3 of the} compound (2-1) is ethyl, and R ³ of the compound (2-2) is propyl. This rule also applies to other symbols. In the formula (2), when the index 'b' is 2, two rings B are present. In this compound, two rings represented by two rings B may be identical or different. This rule applies to any two rings B when the index 'b' is greater than two. This rule also applies to other symbols. 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 the compound (4), the oblique lines crossing one side of this hexagon indicate that any hydrogen on the ring may be replaced by a group such as -Sp ¹ -P ¹ . A subscript such as 'f' indicates the number of groups replaced. There is no such substitution when the subscript 'f' is 0 (zero). When the subscript 'f' is 2 or more, a plurality of -Sp ¹ -P ¹ is present on the ring G. The plurality of groups represented by -Sp ¹ -P ¹ may be identical or different. In the expression “the ring A and the ring B are independently X, Y or Z”, “separately” is used because the subject is plural. When the subject is "ring A", "independent" is not used because the subject is singular.

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-).

  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.

  The present invention includes the following items.

式（Ｓ）において、Ｒ^１は、水素、炭素数１から１２のアルキル、または炭素数１から１２のアルコキシであり；Ｒは、炭素数１から１２のアルキルである。Item 1. Having at least two monovalent radical of the formula (S), in these monovalent group, compound different from the group that the group represented by R ¹ is represented by another R ^1.

In formula (S), R ¹ is hydrogen, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons; R is alkyl having 1 to 12 carbons.

Item 2. The compound according to item 1, wherein in the monovalent group represented by formula (S) according to item 1, R is methyl.

式（１）および式（Ｓ−１）において、Ｒ^１は、水素、炭素数１から１２のアルキル、または炭素数１から１２のアルコキシであり、ここで、Ｒ^１によって表される基は他のＲ^１によって表される基とは異なり；環Ａ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、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、または式（Ｓ−１）で表される基で置き換えられてもよく；Ｚ^１およびＺ^２は独立して、単結合または炭素数１から２０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、これらの基において、少なくとも１つの水素は、フッ素、塩素、または式（Ｓ−１）で表される基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２０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、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ａは、０、１、２、または３である。Item 3. Item 3. The compound according to item 1 or 2, which is represented by the formula (1).

In Formula (1) and Formula (S-1), R ¹ is hydrogen, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons, and the group represented by R ¹ is a group other than the other Different from the group represented by R ^{1 in the following} ; ring A 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 pyridin -2,5-diyl in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, at least one hydrogen is replaced by fluorine or chlorine in these rings May be replaced by the alkyl having 1 to 12 carbon atoms, or a group represented by the formula (S-1); Z ¹ and Z ² independently represent a single bond or an alkylene having 1 to 20 carbon atoms And in this alkylene, at least one -CH ₂ -may be replaced by -O-, -COO-, -OCO-, or -OCOO-, and in these groups, at least one hydrogen is fluorine , Chlorine, or a group represented by formula (S-1); Z ³ represents a single bond or alkylene having 1 to 20 carbon atoms, and Wherein at least one -CH ₂ -may be replaced by -O-, -COO-, -OCO-, or -OCOO-, and in these groups at least one hydrogen is fluorine or chlorine May be replaced; a is 0, 1, 2 or 3.

式（１−１）から式（１−９）において、Ｒ^２は、炭素数１から１２のアルキルまたは炭素数１から１２のアルコキシであり；Ｚ^４は、炭素数１から１５のアルキレンであり；Ｚ^５およびＺ^６は独立して、炭素数１から５のアルキレンであり；Ｚ^７およびＺ^８は独立して、単結合または炭素数１から２０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、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｘ^１は、水素またはフッ素である。Item 4. Item 4. The compound according to any one of Items 1 to 3, which is represented by any one of formulas (1-1) to (1-9).

In formulas (1-1) to (1-9), R ² is alkyl having 1 to 12 carbons or alkoxy having 1 to 12 carbons; and Z ⁴ is alkylene having 1 to 15 carbons, ; Z ⁵ and Z ⁶ are independently alkylene of 1 to 5 carbon atoms; Z ⁷ and Z ⁸ are independently alkylene from a single bond or 1 to 20 carbon atoms, in the alkylene, at least One -CH ₂ -may be replaced by -O-, -COO-, -OCO-, or -OCOO-, and in these groups at least one hydrogen may be replaced by fluorine or chlorine X ¹ is hydrogen or fluorine.

Item 5. A liquid crystal composition having at least one compound according to any one of Items 1 to 4 as a first additive, and having negative dielectric anisotropy.

Item 6. Item 6. The liquid crystal composition according to item 5, wherein the proportion of the first additive is in the range of 0.005% by weight to 1% by weight.

式（２）において、Ｒ^３およびＲ^４は独立して、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Ｂおよび環Ｄは独立して、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Ｃ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、または７，８−ジフルオロクロマン−２，６−ジイルであり；Ｚ^９およびＺ^１０は独立して、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；ｂは、１、２、または３であり、ｃは０または１であり、そしてｂとｃとの和は３以下である。Item 7. 7. The liquid crystal composition according to item 5 or 6, containing at least one compound selected from the group of compounds represented by formula (2) as a first component.

In formula (2), R ³ and R ⁴ are independently 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 B and ring D are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is 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 A chroman-2,6-diyl in which hydrogen is replaced by fluorine or chlorine; ring C 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, or 7,8 Z ⁹ and Z ¹⁰ are independently a single bond, ethylene, carbonyloxy or methyleneoxy; b is 1, 2 or 3 and c is 0 or 1, and the sum of b and c is 3 or less.

式（２−１）から式（２−２２）において、Ｒ^３およびＲ^４は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、または炭素数２から１２のアルケニルオキシである。Item 8. 8. The liquid crystal composition according to any one of items 5 to 7, containing at least one compound selected from the group of compounds represented by formula (2-1) to formula (2-22) as a first component: object.

In formulas (2-1) to (2-22), R ³ and R ⁴ independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or It is alkenyloxy having 2 to 12 carbons.

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

式（３）において、Ｒ^５およびＲ^６は独立して、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Ｅおよび環Ｆは独立して、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^１１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；ｄは、１、２、または３である。Item 10. 10. The liquid crystal composition according to any one of items 5 to 9, containing at least one compound selected from the group of compounds represented by formula (3) as a second component.

In formula (3), R ⁵ and R ⁶ independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least one hydrogen is replaced by fluorine or chlorine. C 1-12 alkyl or C 2-12 alkenyl in which at least one hydrogen is replaced by fluorine or chlorine; ring E and ring F are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ¹¹ is a single bond, ethylene, carbonyloxy or methyleneoxy; d Is one, two, or three.

式（３−１）から式（３−１３）において、Ｒ^５およびＲ^６は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルである。Item 11. Item 11. The liquid crystal composition according to any one of items 5 to 10, containing at least one compound selected from the group of compounds represented by formulas (3-1) to (3-13) as a second component: object.

In formulas (3-1) to (3-13), R ⁵ and R ⁶ independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, It is an alkyl having 1 to 12 carbons in which one hydrogen is replaced by fluorine or chlorine, or an alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.

Item 12. Item 12. The liquid crystal composition according to item 10, wherein the proportion of the second component is in the range of 10% by weight to 90% by weight.

式（４）において、環Ｇおよび環Ｊは独立して、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Ｉ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^１２およびＺ^１３は独立して、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は独立して、重合性基であり；Ｓｐ^１、Ｓｐ^２、およびＳｐ^３は独立して、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；ｅは、０、１、または２であり；ｆ、ｇ、およびｈは独立して、０、１、２、３、または４であり、そしてｆ、ｇ、およびｈの和は、１以上である。Item 13. Item 13. The liquid crystal composition according to any one of items 5 to 12, containing at least one compound selected from the group of polymerizable compounds represented by formula (4) as a second additive.

In the formula (4), ring G and ring J are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine- 2-yl or pyridin-2-yl in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen Fluorine or chlorine may be replaced by alkyl having 1 to 12 carbon atoms; ring I may be 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, -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, and in these rings, at least one hydrogen is fluorine, chlorine, carbon number 1 to 12 alkyl, C 1 to C 12 alkoxy, or at least one hydrogen may be replaced by C 1 to C 12 alkyl substituted with fluorine or chlorine; Z ¹² and Z ¹³ are independently is a single bond or alkylene having 1 to 10 carbon atoms, 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) - may be replaced by, in these groups, at least one hydrogen may be replaced by fluorine or ^chlorine; P ^{1, P} 2, And P ³ independently represent a polymerizable group; Sp ¹ , Sp ² , and Sp ³ independently represent a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH _2- may be replaced by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -is -CH = CH- or -C≡C- Even if replaced In these groups, at least one hydrogen may be replaced by fluorine or chlorine; e is 0, 1 or 2; f, g and h are independently 0, 1, And 2, 3 or 4 and the sum of f, g and h 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は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルである。Item 14. A term in which in formula (4), P ¹ , P ² and P ³ are groups independently selected from the group of polymerizable groups represented by formulas (P-1) to (P-5) 13. The liquid crystal composition according to 13.

In formulas (P-1) to (P-5), M ¹ , M ² and M ³ independently represent hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine And C 1 -C 5 alkyl substituted by

式（４−１）から式（４−２７）において、Ｐ^４、Ｐ^５、およびＰ^６は独立して、式（Ｐ−１）から式（Ｐ−３）で表される重合性基の群から選択された基であり、

ここで、Ｍ^１、Ｍ^２、およびＭ^３は独立して、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は独立して、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。Item 15. Item 15. The liquid crystal composition according to item 13 or 14, containing at least one compound selected from the group of polymerizable compounds represented by formula (4-1) to formula (4-27) as a second additive.

In formulas (4-1) to (4-27), P ⁴ , P ⁵ and P ⁶ independently represent each of the polymerizable groups represented by formulas (P-1) to (P-3) A group selected from the group

Here, M ¹ , M ² and M ³ are independently 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 independently represent 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.

Item 16. Item 16. The liquid crystal composition according to any one of items 13 to 15, wherein the proportion of the second additive is in the range of 0.03% by weight to 10% by weight.

Item 17. Item 18. A liquid crystal display device comprising the liquid crystal composition according to any one of items 5 to 16.

Item 18. Item 18. The liquid crystal display element according to item 17, 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 19. Item 19. A polymer supported alignment type liquid crystal display device, comprising the liquid crystal composition according to any one of items 13 to 16, wherein a second additive contained in the liquid crystal composition is polymerized.

Item 20. Item 17. Use of the liquid crystal composition according to any one of items 5 to 16 in a liquid crystal display device.

Item 21. Item 18. Use of the liquid crystal composition according to any one of items 5 to 16 in a polymer supported alignment type liquid crystal display device.

  The present invention also includes the following items. (A) The above-mentioned which further contains at least one of an additive such as an optically active compound, an antioxidant, an ultraviolet light absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, a polar compound 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.

式（Ｓ）において、Ｒ^１は、水素、炭素数１から１２のアルキル、または炭素数１から１２のアルコキシである。４つの基Ｒは独立して、炭素数１から１２のアルキルである。The liquid crystal composition of the present invention contains a compound having at least two monovalent groups represented by formula (S).

In formula (S), R ¹ is hydrogen, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons. The four groups R are independently alkyl having 1 to 12 carbons.

The compound of the present invention has at least two monovalent groups represented by formula (S). In these monovalent group, the group represented by R ¹ is different from the groups represented by the other R ^1. When this compound has two groups represented by formula (S), the two groups represented by R ¹ are different from each other. Even when this compound has three groups represented by formula (S), the two groups represented by R ¹ are different from each other. An example is where three groups R ¹ are hydrogen, hydrogen, methyl. Another example is a combination of hydrogen, methyl and ethyl. That is, all groups represented by R ¹ are not identical.

  This compound was found to be effective for suppressing the display defect of the device as shown in Comparative Examples 1, 2 and 3. 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 will be 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. It is important that such additives have high solubility in the liquid crystal composition in order to obtain the desired effect.

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. The compounds described in paragraph 1, in particular compound (1), are suitable for this purpose. The compound (1) has at least two groups R ¹ . The compound (1) is asymmetric since the groups represented by at least two groups R ¹ are different from one another. This asymmetry may be contributing to the appropriate polarity. See the comparative example. The composition of the present invention contains compound (1) as a first additive.

  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 components in the composition, the preferred ratio of the components 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 dye, 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 0 (zero) means extremely small.

  The main effects of the component compounds are as follows. The compound (1) contributes to the suppression of display defects. 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 components in the composition, the preferred ratio of the component compounds 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 weight or more to suppress display defects, and about 1% by weight or less to lower the lower limit temperature. A further preferred ratio is in the range of about 0.02% by weight to about 0.5% by weight. An especially desirable ratio is in the range of about 0.1% by weight to about 0.3% by weight.

  The preferred proportion of the compound (2) is about 10% by weight or more for increasing the dielectric anisotropy, and about 90% by weight or less for reducing the lower limit temperature. A further preferred ratio is in the range of about 20% by weight to about 85% by weight. An especially desirable ratio is in the range of about 30% by weight to about 85% by weight.

  The preferred proportion of the compound (3) is about 10% by weight or more to raise the upper limit temperature or to lower the viscosity, and about 90% by weight 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 weight or more for aligning liquid crystal molecules, and about 10% by weight 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 weight to about 1.0% by weight.

Fourth, the preferred embodiments of the component compounds are described. In formula (S), R ¹ is hydrogen, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons, wherein the group represented by R ¹ is represented by other R ¹ It is different from the group. R is alkyl having 1 to 12 carbons.

In Formula (1) and Formula (S-1), Z ¹ and Z ² are independently a single bond or alkylene having 1 to 20 carbon atoms, and in this alkylene, at least one —CH ₂ — is — O-, -COO-, -OCO-, or -OCOO- may be replaced, and in these groups, at least one hydrogen is fluorine, chlorine, or a group represented by formula (S-1) It may be replaced. Desirable Z ¹ or Z ² is C 1-20 alkylene in which a single bond or at least one —CH ₂ — is replaced by —COO— or —OCO—. Z ³ is a single bond or alkylene having 1 to 20 carbon atoms, and in this alkylene, at least one —CH ₂ — is replaced by —O—, —COO—, —OCO—, or —OCOO— Also, in these groups, at least one hydrogen may be replaced by fluorine or chlorine. Preferred Z ³ is alkylene having 1 to 20 carbons in which a single bond or at least one —CH ₂ — is replaced by —COO— or —OCO—.

  Ring A 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, and at least one hydrogen is replaced by fluorine or chlorine. Alkyl having 1 to 12 carbons or expression may be replaced with a group represented by (S-1),. Preferred ring A is 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, or naphthalene-2,7-diyl.

  a is 0, 1, 2 or 3. Preferred a is 0 or 1. More preferable a is 0.

In formulas (1-1) to (1-9), R ² is alkyl having 1 to 12 carbons or alkoxy having 1 to 12 carbons. Desirable R ² is alkyl having 1 to 12 carbons.

Z ⁴ is alkylene having 1 to 15 carbon atoms. Preferred Z ⁴ is alkylene having 6 to 10 carbons. More preferable Z ⁴ is alkylene having 8 carbons. Z ⁵ and Z ⁶ are independently alkylene having 1 to 5 carbons. Z ⁷ and Z ⁸ are each independently a single bond or alkylene having 1 to 20 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO—, —OCO—, or — OCOO- may be replaced and in these groups at least one hydrogen may be replaced by fluorine or chlorine. Preferred Z ⁷ or Z ⁸ is a single bond.

X ¹ is hydrogen or fluorine. Preferred X ¹ is hydrogen.

In formulas (2) and (3), R ³ and R ⁴ independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 12 alkenyloxy. 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 independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, 1 having carbons in which at least one hydrogen is replaced by fluorine or chlorine. 12 alkyl, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced by 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 desirable alkoxy is methoxy or ethoxy for decreasing 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. More 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.

または

であり、好ましくは

である。Ring B and ring D are independently 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 Chromane-2,6-diyl substituted with fluorine or chlorine. Preferred ring B or ring D 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. Ring C 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 or 7,8-difluorochroman-2,6-diyl. Preferred ring C 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. Tetrahydropyran-2,5-diyl is

Or

And preferably

It is.

  Ring E and ring F are each independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene. Preferred ring E or ring F 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 ⁹ and Z ¹⁰ are independently a single bond, ethylene, carbonyloxy or methyleneoxy. Desirable Z ⁹ or Z ¹⁰ is a single bond to lower the viscosity, ethylene to lower the lower limit temperature, and methyleneoxy to increase the dielectric anisotropy. Z ¹¹ is a single bond, ethylene, carbonyloxy or methyleneoxy. Desirable Z ¹¹ is a single bond to increase the stability to ultraviolet light and heat.

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

In Formula (4), P ¹ , P ² and P ³ are independently a polymerizable group. Preferred P ¹ , P ² or P ³ is a polymerizable group selected from the group of 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 the groups (P-1) to (P-5), M ¹ , M ² and M ³ independently represent hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine And C 1 -C 5 alkyl substituted by 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 (4-27), P ⁴ , P ⁵ and P ⁶ are independently groups represented by formula (P-1) to formula (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 independently 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-, and at least one -CH ₂ CH ₂ -may be replaced by -CH = CH- or -C≡C-; In 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 G and ring J are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl or pyridine -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 replaced by fluorine or chlorine May be substituted with alkyl having 1 to 12 carbon atoms. Preferred ring G or ring J is phenyl. Ring I 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 I is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ¹² and Z ¹³ are each independently 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 — 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 ) — may be replaced, and in these groups at least one hydrogen may be replaced by fluorine or chlorine. Preferred ^{Z 12} or ^{Z 13} is a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or -OCO-. Further preferred Z ¹² or Z ¹³ is a single bond.

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

  Fifth, preferred component compounds are shown. The preferred compound (1) is the compound (1-1) to the compound (1-9) described in Item 4. More preferable compounds (1) are the compounds (1-1) to (1-3). Particularly preferred compound (1) is compound (1-1).

  The preferable compound (2) is a compound (2-1) to a compound (2-22) described in item 8. 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 the compound (3-1) to the compound (3-13) described in Item 11. 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 (4-27) described in item 15. 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). In groups (P-1) to (P-3), preferred M ¹ , M ² or M ³ is hydrogen or methyl. 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-.

  Sixth, additives that may be added to the composition will be described. Such additives include optically active compounds, antioxidants, ultraviolet light absorbers, 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 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 weight 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 are compounds (6) in which n is an integer of 1 to 9, and the like.

  In the compound (6), preferred n is 1, 3, 5, 7 or 9. More preferably, n is 7. Since the compound (6) in which n is 7 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. 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.

  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% 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% by weight to about 5% by weight 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, 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 methods of the compound (1-1-1) and the compound (1-1-2) are described in the section of Examples. You may refer to the synthesis method described in Unexamined-Japanese-Patent No. 2016-037605. The compound (2-6) 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 temperature limit of about -10 ° C. or lower, an upper temperature limit of about 70 ° C. or higher, and an optical anisotropy in the range of about 0.07 to about 0.20. A composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the 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 weight), 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 ratio (weight ratio) of the liquid crystalline 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 (% by weight) 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 characteristics of the compound, a sample for measurement was prepared by mixing this compound (15% by weight) with the base liquid crystal (85% by weight). 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 wt%: 90 wt%, 5 wt%: 95 wt%, 1 wt%: 99 wt% 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 shown in% by weight.

  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): Measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995) I obeyed. A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 20 μm. The device was applied stepwise in the range of 39 to 50 volts in increments of 1 volt. After 0.2 seconds of no application, application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of transient current generated by this application were measured. These measurements and M. The rotational viscosity was obtained from the paper of Imai et al., Calculation formula (8) on page 40. The dielectric anisotropy required for this calculation was measured in the item (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.
1) Measurement of dielectric constant (‖): 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.

2) 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. A pulse voltage (60 microseconds at 5 V) was applied to the TN device to charge it. The decaying voltage was measured with a high-speed voltmeter for 16.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit 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.

(10) Voltage holding ratio (VHR-3; measured at 25 ° C .;%): After irradiation with ultraviolet light, the voltage holding ratio was measured to evaluate the stability to 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 20 minutes. The light source was an ultra-high pressure mercury lamp USH-500D (manufactured by Ushio Inc.), and the distance between the element and the light source was 20 cm. In the measurement of VHR-3, the decaying voltage was measured for 16.7 milliseconds. Compositions with large VHR-3 have high stability to ultraviolet light. 90% or more is preferable and 95% or more of VHR-3 is more preferable.

(11) Voltage holding ratio (VHR-4; measured at 25 ° C .;%): The TN device injected with the sample is heated in a thermostatic chamber at 80 ° C. for 500 hours, and then the voltage holding ratio is measured and stability to heat Was evaluated. In the measurement of VHR-4, the decaying voltage was measured for 16.7 milliseconds. Compositions having large VHR-4 have great stability to heat.

(12) 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.

(13) 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)}.

(14) 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.

14a) 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).

14b) Setting of stress voltage: A sample is placed in an FFS element (16 cells of 4 vertical cells × 4 horizontal cells) having a cell gap of 3.5 μm and having a matrix structure, and an adhesive for curing this element with ultraviolet light is used 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.

14c) 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.

14d) Calculation of line afterimage: 4 cells in the central part (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.

(15) 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 14a described above. The setting of the voltage (V127) was performed in the same manner as the item 14b described above. 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.

  Figures 1 to 3 are photographs of the device, showing the state of brightness. In FIGS. 1 and 2, although the magnitudes of the luminances are different from each other, the luminances are generally uniform. These show that the spreadability is good. In FIG. 3, a convex curve is observed upward. This indicates that the liquid crystal composition was injected into the whole of the device from the inlet at the bottom of the photograph, but the additives contained in the composition did not reach the top of the device. .

Synthesis example 1
The compound (1-1-1) was synthesized by the following route.

First step:
Under a nitrogen atmosphere, sebacoyl chloride (532.0 g, 2.225 mol) and diethyl ether (1500 ml) were charged to the reactor and cooled to -70.degree. Thereto, benzyl alcohol (158.8 g, 1.468 mol) was dropped over 1.5 hours, and then triethylamine (225.1 g, 2.225 mol) was dropped over 1 hour. The temperature was raised to room temperature and stirred for 18 hours. The reaction mixture was cooled to 0 ° C. and 1N hydrochloric acid (500 ml) was added dropwise. The organic layer was separated, and the aqueous layer was extracted with diethyl ether. The combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel column chromatography. As a developing solvent, first, toluene and then a mixed solvent of toluene / ethyl acetate = 9/1 (volume ratio) were used. Recrystallization from a mixed solvent of heptane / toluene = 1/1 (volume ratio) gave a compound (T-1) (206.5 g, yield 31.7%).

Second step:
Compound (T-1) (60.00 g, 204.8 mmol), 4-hydroxy-1,2,2,6,6-pentamethylpiperidine (36.83 g, 215.1 mmol), and dichloromethane (under nitrogen atmosphere), and dichloromethane 600 ml) was charged into the reactor and cooled to 0 ° C. Thereto was added DMAP (4-dimethylaminopyridine) (7.51 g, 61.44 mmol) followed by DCC (N, N'-dicyclohexylcarbodiimide) (46.48 g, 225.3 mmol). The temperature was raised to room temperature and stirred for 24 hours. The precipitated colorless solid was removed, and the filtrate was washed successively with saturated aqueous sodium hydrogen carbonate solution and water, and dried over anhydrous magnesium sulfate. The solution is concentrated under reduced pressure, and the residue is purified by silica gel column chromatography (toluene / ethyl acetate = 8/2 to 0/10 (volume ratio)) to give compound (T-2) (69.44 g, Rate of 75.9%).

Third step:
Compound (T-2) (69.44 g, 155.5 mmol), 20% palladium hydroxide on carbon (3.47 g), IPA (2-propanol) (700 ml) were put in a reactor, and 18 at room temperature under a hydrogen atmosphere. Stir for hours. 20% palladium hydroxide on carbon is removed, the filtrate is concentrated, and the residue is purified by silica gel column chromatography (acetone) to give compound (T-3) (55.01 g, yield 99.5%) The

Fourth step:
Compound (T-3) (56.43 g, 158.7 mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine (26.21 g, 166.7 mmol), and dichloromethane (600 ml) under a nitrogen atmosphere Was placed in the reactor and cooled to 0.degree. Thereto DMAP (5.82 g, 47.62 mmol) was added, followed by DCC (36.03 g, 174.6 mmol). The temperature was raised to room temperature and stirred for 16 hours. The precipitated colorless solid was removed, and the filtrate was washed successively with saturated aqueous sodium hydrogen carbonate solution and water, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (acetone). Recrystallization from heptane gave the compound (1-1-1) (25.51 g, 32.4% yield).

¹ H-NMR (ppm; CDCl ₃ ): δ 5.19 (tt, J = 11.5 Hz, J = 4.2 Hz, 1 H), 5.09 (tt, J = 11.7 Hz, J = 4.2 Hz, 1H), 2.27 (t, J = 7.5 Hz, 2 H), 2.26 (t, J = 7.4 Hz, 2 H), 2.24 (s, 3 H), 1.91 (ddd, J = 10.9 Hz, J = 4.2 Hz, J = 1.4 Hz, 2H, 1.83 (ddd, J = 11.0 Hz, J = 4.2 Hz, J = 1.4 Hz, 2H), 1.59 quin, J = 6.9 Hz, 4 H), 1.47 (dd, J = 11.6 Hz, J = 11.6 Hz, 2 H), 1.36-1.28 (m, 8 H), 1.24 (s) , 6H), 1.16 (s, 6H), 1.15 (s, 6H), 1.13 (dd, J = 11.7 Hz, J = 11.7 Hz, 2H), .07 (s, 6H), 0.88-0.50 (br, 1H).

Synthesis example 2
The compound (1-1-2) was synthesized by the following route.

First step:
4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (25.00 g, 145.1 mmol) and t-butanol (50 ml) / water (25 ml) were charged into the reactor, Thereto was added nonanal (72.26 g, 508.0 mmol) and copper (I) chloride (0.36 g, 3.63 mmol). Further, hydrogen peroxide (30% aqueous solution; 49.37 g, 435.4 mmol) was added dropwise over 1.5 hours, and the mixture was stirred at room temperature for 18 hours. The reaction mixture was extracted with heptane, and the extract was washed successively with 10% aqueous ascorbic acid solution, 10% aqueous sodium bisulfite solution, 1N aqueous sodium hydroxide solution, water, saturated brine and dried over anhydrous magnesium sulfate. The solution is concentrated under reduced pressure, and the residue is purified by silica gel column chromatography (heptane / acetone = 8/1 (volume ratio)) to give compound (T-4) (25.00 g, yield 60.3% Got).

Second step:
In a nitrogen atmosphere, the compound (T-4) (2.56 g, 8.98 mmol), the compound (T-1) obtained in Synthesis Example 1 (2.63 g, 8.98 mmol), and dichloromethane (250 ml) were reacted. And cooled to 0.degree. Thereto DMAP (0.33 g, 2.69 mmol) was added followed by DCC (2.04 g, 9.88 mmol). The temperature was raised to room temperature and stirred for 22 hours. The precipitated colorless solid was removed, and the filtrate was washed successively with saturated aqueous sodium hydrogen carbonate solution and water, and dried over anhydrous magnesium sulfate. The solution is concentrated under reduced pressure, and the residue is purified by silica gel column chromatography (heptane / ethyl acetate = 4/1 (volume ratio)) to give compound (T-5) (3.64 g, yield 72.4) %) Got.

Third step:
Compound (T-5) (3.64 g, 6.50 mmol), 20% palladium hydroxide on carbon (0.18 g), and toluene (35 ml) / IPA (35 ml) were charged into a reactor and stirred at room temperature under a hydrogen atmosphere Stir for 18 hours. The 20% palladium hydroxide on carbon is removed, the filtrate is concentrated, and the residue is purified by silica gel column chromatography (heptane / ethyl acetate = 4/1 (volume ratio)) to give compound (T-6) (2. 40 g, yield 78.6%) were obtained.

Fourth step:
Compound (T-6) (2.83 g, 6.03 mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine (0.99 g, 6.33 mmol), and dichloromethane (50 ml) under a nitrogen atmosphere Was placed in the reactor and cooled to 0.degree. Thereto, DMAP (0.22 g, 1.81 mmol) was added, followed by DCC (1.37 g, 6.63 mmol). The temperature was raised to room temperature and stirred for 24 hours. The precipitated colorless solid was removed, and the filtrate was washed successively with saturated aqueous sodium hydrogen carbonate solution and water, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate) to give compound (1-1-2) (1.62 g, yield 44.2%).

¹ H-NMR (ppm; CDCl ₃ ): δ 5.19 (tt, J = 11.4 Hz, J = 4.2 Hz, 1 H), 5.01 (tt, J = 11.5 Hz, J = 4.4 Hz, 1 H), 3.72 (t, J = 6.7 Hz, 2 H), 2.27 (t, J = 7.5 Hz, 2 H), 2. 25 (t, J = 7.7 Hz, 2 H), 91 (dd, J = 12.5 Hz, J = 4.2 Hz, 2 H), 1.80 (dd, J = 11.1 Hz, J = 3.7 Hz, 2 H), 1.61 (quin, J = 7. 2 Hz, 4 H), 1.56 to 1.48 (m, 4 H), 1.37 to 1.28 (m, 18 H), 1.24 (s, 6 H), 1.18 (s, 12 H), 1 .15 (s, 6 H), 1. 14 (dd, J = 11.9 Hz, J = 11.9 Hz, 2 H), 0.88 (t, J = 6.9 Hz, 3 H), 0.8 -0.65 (br, 1H).

  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 weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive. Finally, the characteristic values of the composition were summarized.

Example 1
V-HB (2F, 3F) -O2 (2-1) 7%
V2-BB (2F, 3F) -O2 (2-4) 10%
V-HHB (2F, 3F) -O1 (2-6) 7%
V-HHB (2F, 3F) -O2 (2-6) 9%
V2-HHB (2F, 3F) -O2 (2-6) 8%
3-HH2B (2F, 3F)-O2 (2-7) 9%
V-HBB (2F, 3F) -O2 (2-10) 8%
V-HBB (2F, 3F) -O4 (2-10) 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 above composition (1) was prepared. The compound (1-1-1) was added to this composition at a rate of 0.15% by weight. It was 2.2% when the line afterimage (LISP) was measured according to the method described in the measurement (14).
Tc <-20 ° C; Δn = 0.100; Δε = -3.4; Vth = 2.02 V; = 1 = 18.9 mPa · s.

Comparative Example 1
The comparison compound (A-1) was added to the composition (1) described in Example 1 in a proportion of 0.15% by weight. The line afterimage (LISP) was 4.4%. The results of Example 1 are summarized in Table 4. From Table 4, it can be seen that the compound (1-1-1) is superior to the comparative compound.

Example 2
The compound (1-1-2) was added to the composition (1) described in Example 1 at a ratio of 0.15% by weight. The lower limit temperature (Tc) was <−20 ° C. This result was identical to that of Example 1.

Comparative Example 2
The following comparison compound (A-2) was added to the composition (1) described in Example 1 at a ratio of 0.15% by weight. The lower limit temperature (Tc) was <0 ° C. The results of Examples 1 and 2 are summarized in Table 5. If the solubility of the additive in the composition is good, the nematic phase is likely to be maintained. If the solubility is poor, it is likely to be transformed to a crystal (or smectic phase). By this method, the solubility at low temperature can be compared. From Table 5, it can be seen that the compound (1) is more excellent in solubility than the comparative compound.

[Example 3]
3-HB (2F, 3F) -O2 (2-1) 7%
5-HB (2F, 3F)-O2 (2-1) 7%
3-BB (2F, 3F)-O2 (2-4) 8%
3-HHB (2F, 3F) -O2 (2-6) 4%
5-HHB (2F, 3F) -O2 (2-6) 5%
3-HH1OB (2F, 3F) -O2 (2-8) 5%
2-BB (2F, 3F) B-3 (2-9) 4%
2-HBB (2F, 3F) -O2 (2-10) 3%
3-HBB (2F, 3F) -O2 (2-10) 8%
4-HBB (2F, 3F) -O2 (2-10) 5%
5-HBB (2F, 3F) -O2 (2-10) 8%
3-HH-V (3-1) 33%
V-HHB-1 (3-5) 3%
The compound (1-1-1) was added to the composition at a ratio of 0.10% by weight.
Tc <−20 ° C .; Δn = 0.104; Δε = −3.2; Vth = 2.06 V; = 1 = 15.6 mPa · s; LISP = 2.4%.

Example 4
2-H1OB (2F, 3F) -O2 (2-3) 6%
3-H1OB (2F, 3F) -O2 (2-3) 4%
3-BB (2F, 3F)-O2 (2-4) 3%
2-HH1OB (2F, 3F)-O2 (2-8) 14%
2-HBB (2F, 3F) -O2 (2-10) 7%
3-HBB (2F, 3F) -O2 (2-10) 11%
5-HBB (2F, 3F) -O2 (2-10) 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 (1-1-1) was added to the composition at a ratio of 0.10% by weight.
Tc <-20 ° C; Δn = 0.103; Δε = -3.2; Vth = 2.17 V; = 1 = 17.7 mPa · s; LISP = 2.2%.

[Example 5]
3-HB (2F, 3F)-O2 (2-1) 5%
5-HB (2F, 3F)-O2 (2-1) 7%
3-BB (2F, 3F)-O2 (2-4) 8%
3-HHB (2F, 3F) -O2 (2-6) 5%
5-HHB (2F, 3F) -O2 (2-6) 4%
3-HH1OB (2F, 3F) -O2 (2-8) 5%
2-BB (2F, 3F) B-3 (2-9) 4%
2-HBB (2F, 3F) -O2 (2-10) 3%
3-HBB (2F, 3F) -O2 (2-10) 9%
4-HBB (2F, 3F) -O2 (2-10) 4%
5-HBB (2F, 3F) -O2 (2-10) 8%
3-HH-V (3-1) 27%
3-HH-V1 (3-1) 6%
V-HHB-1 (3-5) 5%
The compound (1-1-2) was added to the composition at a ratio of 0.10% by weight.
Tc <−20 ° C .; Δn = 0.107; Δε = −3.2; Vth = 2.11 V; = 1 = 15.5 mPa · s.

[Example 6]
3-H 2 B (2F, 3F) -O 2 (2-2) 7%
3-HHB (2F, 3F) -O2 (2-6) 8%
3-HH1OB (2F, 3F) -O2 (2-8) 5%
2-BB (2F, 3F) B-3 (2-9) 7%
2-BB (2F, 3F) B-4 (2-9) 7%
3-HD h B (2F, 3F)-O2 (2-16) 3%
5-HDhB (2F, 3F)-O2 (2-16) 4%
2-HchB (2F, 3F)-O2 (2-19) 8%
4-HH-V (3-1) 15%
3-HH-V1 (3-1) 6%
1-HH-2V1 (3-1) 6%
3-HH-2V1 (3-1) 4%
V2-BB-1 (3-3) 5%
1V2-BB-1 (3-3) 5%
3-HHB-1 (3-5) 6%
3-HB (F) BH-3 (3-12) 4%
The compound (1-1-1) was added to this composition at a rate of 0.15% by weight.
Tc <−20 ° C .; Δn = 0.115; Δε = −1.9; Vth = 2.82 V; = 1 = 17.3 mPa · s; LISP = 2.1%.

[Example 7]
V2-H2B (2F, 3F) -O2 (2-2) 8%
V2-H1OB (2F, 3F) -O4 (2-3) 4%
3-BB (2F, 3F)-O2 (2-4) 7%
2-HHB (2F, 3F) -O2 (2-6) 7%
3-HHB (2F, 3F) -O2 (2-6) 7%
3-HH2B (2F, 3F)-O2 (2-7) 7%
5-HH2B (2F, 3F)-O2 (2-7) 4%
V-HH2B (2F, 3F)-O2 (2-7) 6%
V2-HBB (2F, 3F) -O2 (2-10) 5%
V-HBB (2F, 3F) -O2 (2-10) 5%
V-HBB (2F, 3F) -O4 (2-10) 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 (1-1-1) was added to the composition at a ratio of 0.10% by weight.
Tc <−20 ° C .; Δn = 0.122; Δε = −4.2; Vth = 2.16 V; = 2 = 23.4 mPa · s; LISP = 2.3%.

[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 (2-4) 3%
1V2-BB (2F, 3F) -O2 (2-4) 3%
3-HHB (2F, 3F) -O2 (2-6) 6%
V-HHB (2F, 3F) -O2 (2-6) 6%
V-HHB (2F, 3F)-O 4 (2-6) 5%
V2-HHB (2F, 3F) -O2 (2-6) 4%
V2-BB (2F, 3F) B-1 (2-9) 4%
V2-HBB (2F, 3F) -O2 (2-10) 5%
V-HBB (2F, 3F) -O2 (2-10) 4%
V-HBB (2F, 3F) -O4 (2-10) 5%
V-HHB (2F, 3Cl) -O2 (2-12) 3%
3-HH-V (3-1) 27%
3-HH-V1 (3-1) 6%
V-HHB-1 (3-5) 3%
The compound (1-1-1) was added to the composition at a ratio of 0.10% by weight.
Tc <−20 ° C .; Δn = 0.101; Δε = −3.0; Vth = 2.04 V; = 1 = 13.9 mPa · s; LISP = 2.2%.

[Example 9]
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 (2-4) 3%
V2-BB (2F, 3F) -O2 (2-4) 8%
V2-HHB (2F, 3F) -O2 (2-6) 5%
2-HBB (2F, 3F) -O2 (2-10) 3%
3-HBB (2F, 3F) -O2 (2-10) 3%
V-HBB (2F, 3F) -O2 (2-10) 6%
V-HBB (2F, 3F) -O4 (2-10) 8%
V-HHB (2F, 3Cl) -O2 (2-12) 7%
3-HH-4 (3-1) 14%
V-HHB-1 (3-5) 10%
3-HBB-2 (3-6) 7%
The compound (1-1-2) was added to the composition at a ratio of 0.10% by weight.
Tc <-20 ° C; Δn = 0.114; Δε = -3.9; Vth = 2.20 V; = 2 = 24.7 mPa · s.

[Example 10]
3-HB (2F, 3F)-O2 (2-1) 10%
5-HB (2F, 3F)-O2 (2-1) 7%
2-BB (2F, 3F)-O2 (2-4) 7%
3-BB (2F, 3F)-O2 (2-4) 7%
3-B (2F, 3F) B (2F, 3F)-O2 (2-5) 3%
2-HHB (2F, 3F) -O2 (2-6) 5%
3-HHB (2F, 3F) -O2 (2-6) 10%
2-HBB (2F, 3F) -O2 (2-10) 8%
3-HBB (2F, 3F) -O2 (2-10) 10%
2-HH-3 (3-1) 14%
3-HB-O1 (3-2) 5%
3-HHB-1 (3-5) 3%
3-HHB-O1 (3-5) 3%
3-HHB-3 (3-5) 4%
2-BB (F) B-3 (3-8) 4%
The compound (1-1-1) was added to the composition at a ratio of 0.10% by weight.
Tc <−20 ° C .; Δn = 0.113; Δε = −4.0; Vth = 2.18 V; = 2 = 22.6 mPa · s; LISP = 2.1%.

[Example 11]
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 (2-4) 7%
2-HHB (2F, 3F) -O2 (2-6) 7%
3-HHB (2F, 3F) -O2 (2-6) 7%
3-HH2B (2F, 3F)-O2 (2-7) 7%
5-HH2B (2F, 3F)-O2 (2-7) 4%
2-HBB (2F, 3F) -O2 (2-10) 5%
3-HBB (2F, 3F) -O2 (2-10) 5%
4-HBB (2F, 3F) -O2 (2-10) 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 (1-1-1) was added to the composition at a ratio of 0.10% by weight.
Tc <−20 ° C .; Δn = 0.118; Δε = −4.4; Vth = 2.13 V; = 2 = 22.5 mPa · s; LISP = 2.0%.

[Example 12]
3-HB (2F, 3F) -O2 (2-1) 7%
5-HB (2F, 3F)-O2 (2-1) 7%
3-BB (2F, 3F)-O2 (2-4) 8%
3-HHB (2F, 3F) -O2 (2-6) 5%
5-HHB (2F, 3F) -O2 (2-6) 4%
3-HH1OB (2F, 3F) -O2 (2-8) 4%
2-BB (2F, 3F) B-3 (2-9) 5%
2-HBB (2F, 3F) -O2 (2-10) 3%
3-HBB (2F, 3F) -O2 (2-10) 8%
4-HBB (2F, 3F) -O2 (2-10) 5%
5-HBB (2F, 3F) -O2 (2-10) 8%
3-HH-V (3-1) 27%
3-HH-V1 (3-1) 6%
V-HHB-1 (3-5) 3%
The compound (1-1-1) was added to this composition at a rate of 0.15% by weight.
Tc <−20 ° C .; Δn = 0.107; Δε = −3.2; Vth = 2.02 V; = 1 = 15.9 mPa · s; LISP = 2.2%.

[Example 13]
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%
2-HBB (2F, 3F) -O2 (2-10) 6%
3-HBB (2F, 3F) -O2 (2-10) 8%
4-HBB (2F, 3F) -O2 (2-10) 7%
5-HBB (2F, 3F) -O2 (2-10) 7%
3-HD h B (2F, 3F)-O2 (2-16) 5%
3-HH-4 (3-1) 14%
V-HHB-1 (3-5) 10%
3-HBB-2 (3-6) 7%
The compound (1-1-1) was added to the composition at a ratio of 0.10% by weight.
Tc <−20 ° C .; Δn = 0.108; Δε = −3.8; Vth = 2.25 V; = 2 = 24.6 mPa · s; LISP = 2.1%.

Example 14
3-HB (2F, 3F) -O2 (2-1) 7%
3-HB (2F, 3F)-O4 (2-1) 8%
3-H 2 B (2F, 3F) -O 2 (2-2) 8%
3-BB (2F, 3F)-O2 (2-4) 10%
2-HHB (2F, 3F) -O2 (2-6) 4%
3-HHB (2F, 3F) -O2 (2-6) 7%
3-HHB (2F, 3F) -1 (2-6) 6%
2-HBB (2F, 3F) -O2 (2-10) 6%
3-HBB (2F, 3F) -O2 (2-10) 6%
4-HBB (2F, 3F) -O2 (2-10) 5%
5-HBB (2F, 3F) -O2 (2-10) 4%
3-HEB (2F, 3F) B (2F, 3F)-O2 (2-11) 3%
3-H1OCro (7F, 8F) -5 (2-14) 3%
3-HD h B (2F, 3F)-O2 (2-16) 5%
3-HH-O1 (3-1) 5%
1-BB-5 (3-3) 4%
V-HHB-1 (3-5) 4%
5-HB (F) BH-3 (3-12) 5%
The compound (1-1-1) was added to this composition at a rate of 0.15% by weight.
Tc <−20 ° C .; Δn = 0.119; Δε = −4.5; Vth = 1.69 V; = 3 = 31.4 mPa · s; LISP = 2.4%.

[Example 15]
3-HB (2F, 3F)-O4 (2-1) 15%
3-HBB (2F, 3F) -O2 (2-10) 8%
4-HBB (2F, 3F) -O2 (2-10) 5%
5-HBB (2F, 3F) -O2 (2-10) 7%
3-dhBB (2F, 3F) -O2 (2-17) 5%
3-chB (2F, 3F)-O2 (2-18) 7%
2-HchB (2F, 3F)-O2 (2-19) 8%
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 (1-1-1) was added to the composition at a ratio of 0.10% by weight.
Tc <−20 ° C .; Δn = 0.111; Δε = −3.2; Vth = 2.47 V; Vth = 23.9 mPa · s; LISP = 2.1%.

[Example 16]
3-H 2 B (2F, 3F) -O 2 (2-2) 18%
5-H2B (2F, 3F)-O2 (2-2) 17%
3-HHB (2F, 3Cl) -O2 (2-12) 5%
3-HBB (2F, 3Cl) -O2 (2-13) 8%
5-HBB (2F, 3Cl) -O2 (2-13) 7%
3-HD h B (2F, 3F)-O2 (2-16) 5%
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 (1-1-1) was added to this composition at a rate of 0.15% by weight.
Tc <−20 ° C .; Δn = 0.084; Δε = −2.6; Vth = 2.43 V; = 2 = 22.8 mPa · s; LISP = 2.5%.

[Example 17]
3-HB (2F, 3F)-O2 (2-1) 8%
3-H 2 B (2F, 3F) -O 2 (2-2) 10%
3-BB (2F, 3F)-O2 (2-4) 10%
2O-BB (2F, 3F) -O2 (2-4) 3%
2-HHB (2F, 3F) -O2 (2-6) 4%
3-HHB (2F, 3F) -O2 (2-6) 7%
2-HHB (2F, 3F) -1 (2-6) 5%
2-BB (2F, 3F) B-3 (2-9) 6%
2-BB (2F, 3F) B-4 (2-9) 6%
2-HBB (2F, 3F) -O2 (2-10) 4%
3-HBB (2F, 3F) -O2 (2-10) 7%
3-HH1OCro (7F, 8F) -5 (2-15) 4%
3-HD h B (2F, 3F)-O2 (2-16) 6%
3-dhBB (2F, 3F) -O2 (2-17) 4%
3-HH-V (3-1) 11%
1-BB-5 (3-3) 5%
The compound (1-1-2) was added to the composition at a ratio of 0.10% by weight.
Tc <−20 ° C .; Δn = 0.129; Δε = −4.3; Vth = 1.69 V; = 2 = 27.0 mPa · s.

[Example 18]
3-HB (2F, 3F)-O4 (2-1) 14%
3-H1OB (2F, 3F) -O2 (2-3) 3%
3-BB (2F, 3F)-O2 (2-4) 10%
2-HHB (2F, 3F) -O2 (2-6) 7%
3-HHB (2F, 3F) -O2 (2-6) 7%
3-HH1OB (2F, 3F) -O2 (2-8) 6%
2-HBB (2F, 3F) -O2 (2-10) 4%
3-HBB (2F, 3F) -O2 (2-10) 6%
4-HBB (2F, 3F) -O2 (2-10) 4%
3-HH-V (3-1) 14%
1-BB-3 (3-3) 3%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 4%
V-HBB-2 (3-6) 4%
1-BB (F) B-2V (3-8) 6%
5-HBBH-1O1 (-) 4%
The compound (1-1-1) was added to this composition at a ratio of 0.12% by weight.
Tc <−20 ° C .; Δn = 0.123; Δε = −4.0; Vth = 2.27 V; = 2 = 29.6 mPa · s; LISP = 2.2%.

[Example 19]
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 (2-4) 10%
2-HHB (2F, 3F) -O2 (2-6) 7%
3-HHB (2F, 3F) -O2 (2-6) 7%
5-HHB (2F, 3F) -O2 (2-6) 7%
2-HBB (2F, 3F) -O2 (2-10) 4%
3-HBB (2F, 3F) -O2 (2-10) 7%
5-HBB (2F, 3F) -O2 (2-10) 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 (1-1-1) was added to this composition at a rate of 0.15% by weight.
Tc <−20 ° C .; Δn = 0.126; Δε = −4.5; Vth = 2.21 V; = 2 = 25.3 mPa · s; LISP = 2.3%.

[Example 20]
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 (2-4) 7%
2-HHB (2F, 3F) -O2 (2-6) 6%
3-HHB (2F, 3F) -O2 (2-6) 10%
5-HHB (2F, 3F) -O2 (2-6) 8%
2-HBB (2F, 3F) -O2 (2-10) 5%
3-HBB (2F, 3F) -O2 (2-10) 7%
5-HBB (2F, 3F) -O2 (2-10) 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 (1-1-1) was added to the composition at a ratio of 0.10% by weight.
NI = 93.0 ° C .; Tc <−20 ° C .; Δn = 0.124; Δε = −4.5; Vth = 2.22 V; L = 25.0 mPa · s; LISP = 2.2%.

[Example 21]
3-H 2 B (2F, 3F) -O 2 (2-2) 10%
3-BB (2F, 3F)-O2 (2-4) 10%
5-BB (2F, 3F)-O2 (2-4) 5%
V-HHB (2F, 3F)-O1 (2-6) 5%
V-HHB (2F, 3F) -O2 (2-6) 12%
V-HHB (2F, 3F) -O4 (2-6) 8%
3-HD h B (2F, 3F)-O2 (2-16) 8%
3-HH-V (3-1) 23%
3-HH-4 (3-1) 11%
3-HHB-1 (3-5) 4%
3-HHB-3 (3-5) 2%
3-HHB-O1 (3-5) 2%
The compound (1-1-1) was added to the composition at a ratio of 0.10% by weight.
Tc <−20 ° C .; Δn = 0.089; Δε = −3.3; Vth = 2.14 V; = 1 = 16.3 mPa · s; LISP = 2.4%.

Example 22
3-BB (2F, 3F)-O2 (2-4) 13%
5-BB (2F, 3F)-O2 (2-4) 12%
V-HHB (2F, 3F)-O1 (2-6) 5%
V-HHB (2F, 3F) -O2 (2-6) 12%
V-HHB (2F, 3F) -O4 (2-6) 14%
3-HH-V (3-1) 16%
3-HH-4 (3-1) 11%
1-BB-3 (3-3) 4%
3-HHB-O1 (3-5) 2%
3-HHB-1 (3-5) 7%
3-HHB-3 (3-5) 4%
The compound (1-1-1) was added to the composition at a ratio of 0.10% by weight.
Tc <−20 ° C .; Δn = 0.103; Δε = −2.9; Vth = 2.24 V; = 1 = 16.4 mPa · s; LISP = 2.1%.

[Example 23]
3-H 2 B (2F, 3F) -O 2 (2-2) 13%
5-H2B (2F, 3F)-O2 (2-2) 14%
V-HHB (2F, 3F)-O1 (2-6) 5%
V-HHB (2F, 3F) -O2 (2-6) 12%
V-HHB (2F, 3F) -O4 (2-6) 14%
3-HH2B (2F, 3F)-O2 (2-7) 4%
3-HH-V (3-1) 16%
1-BB-3 (3-3) 4%
1-BB-5 (3-3) 4.5%
3-HHB-1 (3-5) 1.5%
3-HBB-2 (3-6) 12%
The compound (1-1-1) was added to the composition at a ratio of 0.10% by weight.
Tc <−20 ° C .; Δn = 0.103; Δε = −3.1; Vth = 2.30 V; = 1 = 18.1 mPa · s; LISP = 2.0%.

[Example 24]
3-HB (2F, 3F) -O2 (2-1) 6%
3-H1OB (2F, 3F) -O2 (2-3) 11%
2-HH1OB (2F, 3F)-O2 (2-8) 13%
3-HH1OB (2F, 3F) -O2 (2-8) 8%
3-HH-5 (3-1) 5%
2-HH-3 (3-1) 11%
3-HH-4 (3-1) 11%
3-HB-O2 (3-2) 3%
1-BB-3 (3-3) 4%
1-BB-5 (3-3) 4%
3-HHB-1 (3-5) 5.5%
3-HBB-2 (3-6) 6.5%
5-B (F) BB-2 (3-7) 12%
The compound (1-1-1) was added to the composition at a ratio of 0.10% by weight.
NI = 75.3 ° C .; Tc <−20 ° C .; Δn = 0.105; Δε = −2.4; Vth = 2.43 V; == 16.7 mPa · s; LISP = 2.3%.

[Example 25]
2-H1OB (2F, 3F) -O2 (2-3) 7%
3-H1OB (2F, 3F) -O2 (2-3) 7%
2-HHB (2F, 3F) -O2 (2-6) 3%
3-HHB (2F, 3F) -O2 (2-6) 4%
5-HHB (2F, 3F) -O2 (2-6) 4%
2-HBB (2F, 3F) -O2 (2-10) 3%
3-HBB (2F, 3F) -O2 (2-10) 8%
4-HBB (2F, 3F) -O2 (2-10) 3%
5-HBB (2F, 3F) -O2 (2-10) 4%
3-HD h B (2F, 3F)-O2 (2-16) 6%
2-HH-3 (3-1) 18%
2-HH-5 (3-1) 3%
3-HH-4 (3-1) 4%
3-HH-5 (3-1) 3%
3-HB-O2 (3-2) 17.5%
3-HHB-3 (3-5) 3.5%
3-HHB-O1 (3-5) 2%
To this composition, 0.10% by weight of compound (1-1-1) and 0.43% by weight of compound (4-25-1) were added.
NI = 75.2 ° C .; Δn = 0.089; Δε = −3.0; Vth = 2.24 V; LISP = 2.2%.

[Example 26]
2-H1OB (2F, 3F) -O2 (2-3) 7%
3-H1OB (2F, 3F) -O2 (2-3) 7%
2-HHB (2F, 3F) -O2 (2-6) 3%
3-HHB (2F, 3F) -O2 (2-6) 4%
5-HHB (2F, 3F) -O2 (2-6) 4%
2-HBB (2F, 3F) -O2 (2-10) 3%
3-HBB (2F, 3F) -O2 (2-10) 8%
4-HBB (2F, 3F) -O2 (2-10) 3%
5-HBB (2F, 3F) -O2 (2-10) 4%
3-HD h B (2F, 3F)-O2 (2-16) 6%
2-HH-3 (3-1) 18%
2-HH-5 (3-1) 3%
3-HH-4 (3-1) 4%
3-HH-5 (3-1) 3%
3-HB-O2 (3-2) 17.5%
3-HHB-3 (3-5) 3.5%
3-HHB-O1 (3-5) 2%
To this composition, 0.10% by weight of compound (1-1-1) and 0.80% by weight of compound (4-25-1) were added.
NI = 74.9 ° C; Δn = 0.089; Δε = -3.3; Vth = 2.24 V; LISP = 2.1%.

[Example 27]
V-HB (2F, 3F) -O2 (2-1) 7%
V2-BB (2F, 3F) -O2 (2-4) 10%
V-HHB (2F, 3F) -O1 (2-6) 7%
V-HHB (2F, 3F) -O2 (2-6) 9%
V2-HHB (2F, 3F) -O2 (2-6) 8%
3-HH2B (2F, 3F)-O2 (2-7) 9%
V-HBB (2F, 3F) -O2 (2-10) 7%
V-HBB (2F, 3F) -O4 (2-10) 7%
3-HH-V (3-1) 15%
3-HH-V1 (3-1) 6%
2-HH-3 (3-1) 9%
3-HH-4 (3-1) 3%
1V2-HH-3 (3-1) 3%
The compound (1-1-1) was added to the composition at a ratio of 0.10% by weight.
NI = 87.5 ° C .; Δn = 0.100; Δε = −3.4; Vth = 2.25 V; LISP = 2.2%.

[Example 28]
3-H1OB (2F, 3F) -O2 (2-3) 10%
2-BB (2F, 3F)-O2 (2-4) 5%
V2-BB (2F, 3F) -O2 (2-4) 11%
2-HH1OB (2F, 3F)-O2 (2-8) 6%
3-HH1OB (2F, 3F) -O2 (2-8) 18%
3-HH-VFF (3-1) 30%
1-BB-3 (3-3) 2.5%
3-HHB-1 (3-5) 5%
3-HHB-O1 (3-5) 4%
3-HBB-2 (3-6) 8.5%
The compound (1-1-1) was added to the composition at a ratio of 0.10% by weight.
Δn = 0.101; Δε = −3.3; Vth = 2.22 V; = 1 = 15.8 mPa · s; LISP = 2.4%.

[Example 29]
3-H1OB (2F, 3F) -O2 (2-3) 11.5%
2-BB (2F, 3F)-O2 (2-4) 5%
V2-BB (2F, 3F) -O2 (2-4) 11%
V-HHB (2F, 3F) -O1 (2-6) 6%
V-HHB (2F, 3F) -O2 (2-6) 10%
2-HH1OB (2F, 3F)-O2 (2-8) 6%
3-HH1OB (2F, 3F) -O2 (2-8) 3%
3-HH-VFF (3-1) 30%
3-HHB-1 (3-5) 5%
3-HHB-O1 (3-5) 4%
3-HBB-2 (3-6) 8.5%
The compound (1-1-1) was added to the composition at a ratio of 0.10% by weight.
Δn = 0.101; Δε = −3.3; Vth = 2.21 V; = 1 = 15.9 mPa · s; LISP = 2.6%.

[Example 30]
3-H 2 B (2F, 3F) -O 2 (2-2) 13%
2-BB (2F, 3F)-O2 (2-4) 3.5%
3-BB (2F, 3F)-O2 (2-4) 4%
3-HH2B (2F, 3F)-O2 (2-7) 11%
2-HBB (2F, 3F) -O2 (2-10) 3%
3-HBB (2F, 3F) -O2 (2-10) 9%
4-HBB (2F, 3F) -O2 (2-10) 2%
V-HBB (2F, 3F) -O2 (2-10) 8%
V-HBB (2F, 3F) -O4 (2-10) 4%
2-HH-3 (3-1) 21%
3-HH-VFF (3-1) 9%
3-HB-O2 (3-2) 2.5%
3-HHB-1 (3-5) 5%
3-HHB-3 (3-5) 5%
The compound (1-1-1) was added to the composition at a ratio of 0.10% by weight.
Tc <−20 ° C .; Δn = 0.102; Δε = −2.8; Vth = 2.43 V; = 1 = 14.2 mPa · s; LISP = 2.1%.

[Example 31]
2-H1OB (2F, 3F) -O2 (2-3) 6%
3-H1OB (2F, 3F) -O2 (2-3) 7%
V2-BB (2F, 3F) -O2 (2-4) 3%
2-BB (2F, 3F)-O2 (2-4) 4%
3-BB (2F, 3F)-O2 (2-4) 6%
3-HH2B (2F, 3F)-O2 (2-7) 7%
3-HH1OB (2F, 3F) -O2 (2-8) 5%
2-HBB (2F, 3F) -O2 (2-10) 3%
3-HBB (2F, 3F) -O2 (2-10) 7%
4-HBB (2F, 3F) -O2 (2-10) 3%
V-HBB (2F, 3F) -O2 (2-10) 7%
V-HBB (2F, 3F) -O4 (2-10) 5%
2-HH-3 (3-1) 13%
3-HH-4 (3-1) 10%
3-HHB-1 (3-5) 4%
3-HHB-3 (3-5) 5%
3-HHB-O1 (3-5) 3%
3-HBB-2 (3-6) 2%
The compound (1-1-1) was added to the composition at a ratio of 0.10% by weight.
Tc <−20 ° C .; Δn = 0.111; Δε = −4.0; Vth = 2.08 V; = 2 = 21.8 mPa · s; LISP = 2.2%.

[Example 32]
3-H 2 B (2F, 3F) -O 2 (2-2) 17%
5-H2B (2F, 3F)-O2 (2-2) 12%
3-H1OB (2F, 3F) -O2 (2-3) 8%
3-HH1OB (2F, 3F) -O2 (2-8) 3%
2-HBB (2F, 3F) -O2 (2-10) 3%
3-HBB (2F, 3F) -O2 (2-10) 7%
4-HBB (2F, 3F) -O2 (2-10) 4%
5-HBB (2F, 3F) -O2 (2-10) 8%
V-HBB (2F, 3F) -O2 (2-10) 4%
V-HBB (2F, 3F) -O4 (2-10) 5%
3-HD h B (2F, 3F)-O2 (2-16) 8%
2-HH-3 (3-1) 6%
3-HH-4 (3-1) 3%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 2%
3-HBB-2 (3-6) 6%
The compound (1-1-1) was added to the composition at a ratio of 0.10% by weight.
Tc <−20 ° C .; Δn = 0.114; Δε = −5.5; Vth = 1.81 V; = 2 = 29.4 mPa · s; LISP = 2.3%.

[Example 33]
3-BB (2F, 3F)-O2 (2-4) 10%
V2-BB (2F, 3F) -O2 (2-4) 6%
2-HH1OB (2F, 3F)-O2 (2-8) 13%
3-HH1OB (2F, 3F) -O2 (2-8) 14%
2-HBB (2F, 3F) -O2 (2-10) 2%
3-HBB (2F, 3F) -O2 (2-10) 6%
V-HBB (2F, 3F) -O2 (2-10) 6%
V-HBB (2F, 3F) -O4 (2-10) 3%
2-HH-3 (3-1) 7%
3-HH-VFF (3-1) 25%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 2%
3-HBB-2 (3-6) 2%
The compound (1-1-1) was added to the composition at a ratio of 0.10% by weight.
Tc <−20 ° C .; Δn = 0.108; Δε = −3.8; Vth = 2.11 V; = 2 = 20.2 mPa · s; LISP = 2.1%.

[Example 34]
3-H 2 B (2F, 3F) -O 2 (2-2) 9%
3-BB (2F, 3F)-O2 (2-4) 9%
V2-BB (2F, 3F) -O2 (2-4) 8%
3-HH2B (2F, 3F)-O2 (2-7) 15%
3-HD h B (2F, 3F)-O2 (2-16) 18%
3-HH-V (3-1) 29%
V-HHB-1 (3-5) 10%
3-HBB-2 (3-6) 2%
The compound (1-1-1) was added to the composition at a ratio of 0.10% by weight.
NI = 74.6 ° C; Δn = 0.095; Δε = -3.5; Vth = 2.16 V; LISP = 2.2%.

[Example 35]
3-HB (2F, 3F)-O2 (2-1) 8%
5-HB (2F, 3F)-O2 (2-1) 3%
2-BB (2F, 3F)-O2 (2-4) 8%
V2-BB (2F, 3F) -O2 (2-4) 7%
3-HHB (2F, 3F) -O2 (2-6) 10%
V-HHB (2F, 3F)-O1 (2-6) 4%
V-HHB (2F, 3F) -O2 (2-6) 10%
3-HD h B (2F, 3F)-O2 (2-16) 10%
3-HH-V (3-1) 29%
V-HHB-1 (3-5) 11%
The compound (1-1-1) was added to the composition at a ratio of 0.10% by weight.
NI = 75.4 ° C .; Δn = 0.094; Δε = −3.6; Vth = 2.05 V; LISP = 2.0%.

[Example 36]
V-HB (2F, 3F) -O2 (2-1) 5%
2-BB (2F, 3F)-O2 (2-4) 6%
3-BB (2F, 3F)-O2 (2-4) 11%
V-HHB (2F, 3F) -O1 (2-6) 6%
V-HHB (2F, 3F) -O2 (2-6) 12%
V-HHB (2F, 3F) -O4 (2-6) 6%
V2-HHB (2F, 3F) -O2 (2-6) 10%
V-HBB (2F, 3F) -O2 (2-10) 7%
V-HBB (2F, 3F) -O4 (2-10) 7%
3-HH-V (3-1) 27.5%
3-HH-V1 (3-1) 2.5%
The compound (1-1-1) was added to this composition at a rate of 0.15% by weight.
Tc <−30 ° C .; Δn = 0.107; Δε = −4.1; Vth = 1.94 V; LISP = 2.5%.

[Example 37]
2-H1OB (2F, 3F) -O2 (2-3) 10%
3-H1OB (2F, 3F) -O2 (2-3) 10%
2-HHB (2F, 3F) -O2 (2-6) 4%
3-HHB (2F, 3F) -O2 (2-6) 6%
5-HHB (2F, 3F) -O2 (2-6) 2%
2-HBB (2F, 3F) -O2 (2-10) 2%
3-HBB (2F, 3F) -O2 (2-10) 8%
4-HBB (2F, 3F) -O2 (2-10) 8%
5-HBB (2F, 3F) -O2 (2-10) 3%
2-HH-3 (3-1) 22%
3-HH-4 (3-1) 4%
3-HB-O2 (3-2) 10%
3-HBB-2 (3-6) 11%
To this composition, 0.10% by weight of compound (1-1-1) and 0.30% by weight of compound (4-25-1) were added.
NI = 75.9 ° C; Δn = 0.098; Δε = -3.2; Vth = 2.09 V; LISP = 2.2%.

[Example 38]
3-BB (2F, 3F)-O2 (2-4) 13%
2-HH1OB (2F, 3F)-O2 (2-8) 20%
3-HH1OB (2F, 3F) -O2 (2-8) 14%
3-HH-V (3-1) 31%
1-BB-5 (3-3) 8%
3-HHB-1 (3-5) 4%
3-HHB-3 (3-5) 3%
5-B (F) BB-2 (3-7) 7%
Finally, the spreadability was evaluated. The above composition (38) was prepared. The compound (1-1-1) was added to this composition at a rate of 0.01% by weight. Spreadability was measured by the method described in the measurement (15) and was qualitatively evaluated from FIG. 1 (Table 6).

[Example 39]
The compound (1-1-2) was added to the composition (38) described in Example 38 in a proportion of 0.01% by weight. The spreadability of this compound was evaluated from FIG. 2 (Table 6).

Comparative Example 3
The comparison compound (A-2) was added to the composition (38) described in Example 38 in a proportion of 0.01 wt%. The spreadability of this compound was evaluated from FIG. The results are summarized in Table 6 together with the results of Examples 38 and 39.

  Figures 1 to 3 are photographs of the device. The inlet was located on the lower side of the photograph, from which the composition containing the additive was injected. In FIGS. 1 and 2, although the magnitudes of the luminances are different from each other, the luminances are generally uniform. These show that the spreadability is good. In FIG. 3, an upward convex curve was observed. This indicates that the device was filled with the liquid crystal composition, but the additive contained in the composition did not reach the top of the device. From these results, in Examples 38 and 39, it was found that the spreadability was good. On the other hand, in Comparative Example 3, the spreadability was poor.

  A comparative experiment of line afterimage, lower limit temperature (solubility at low temperature) and spreadability was conducted, and the results are summarized in Tables 4, 5 and 6. In each case, compound (1) gave superior results as compared with the comparative compound. Thus, it is concluded that the composition of the 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 (21)

Having at least two monovalent radical of the formula (S), in these monovalent group, compound different from the group that the group represented by R ¹ is represented by another R ^1.

In formula (S), R ¹ is hydrogen, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons; R is alkyl having 1 to 12 carbons.   The compound according to claim 1, wherein in the monovalent group represented by formula (S) according to claim 1, R is methyl. The compound of Claim 1 or 2 represented by Formula (1).

In Formula (1) and Formula (S-1), R ¹ is hydrogen, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons, and the group represented by R ¹ is a group other than the other Different from the group represented by R ^{1 in the following} ; ring A 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 pyridin -2,5-diyl in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, at least one hydrogen is replaced by fluorine or chlorine in these rings May be replaced by the alkyl having 1 to 12 carbon atoms, or a group represented by the formula (S-1); Z ¹ and Z ² independently represent a single bond or an alkylene having 1 to 20 carbon atoms And in this alkylene, at least one -CH ₂ -may be replaced by -O-, -COO-, -OCO-, or -OCOO-, and in these groups, at least one hydrogen is fluorine , Chlorine, or a group represented by formula (S-1); Z ³ represents a single bond or alkylene having 1 to 20 carbon atoms, and Wherein at least one -CH ₂ -may be replaced by -O-, -COO-, -OCO-, or -OCOO-, and in these groups at least one hydrogen is fluorine or chlorine May be replaced; a is 0, 1, 2 or 3. The compound according to any one of claims 1 to 3, which is represented by any one of formulas (1-1) to (1-9).

In formulas (1-1) to (1-9), R ² is alkyl having 1 to 12 carbons or alkoxy having 1 to 12 carbons; and Z ⁴ is alkylene having 1 to 15 carbons, ; Z ⁵ and Z ⁶ are independently alkylene of 1 to 5 carbon atoms; Z ⁷ and Z ⁸ are independently alkylene from a single bond or 1 to 20 carbon atoms, in the alkylene, at least One -CH ₂ -may be replaced by -O-, -COO-, -OCO-, or -OCOO-, and in these groups at least one hydrogen may be replaced by fluorine or chlorine X ¹ is hydrogen or fluorine.   A liquid crystal composition having at least one compound according to any one of claims 1 to 4 as a first additive and having negative dielectric anisotropy.   The liquid crystal composition according to claim 5, wherein the proportion of the first additive is in the range of 0.005% by weight to 1% by weight. The liquid crystal composition according to claim 5 or 6, containing at least one compound selected from the group of compounds represented by formula (2) as a first component.

In formula (2), R ³ and R ⁴ are independently 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 B and ring D are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is 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 A chroman-2,6-diyl in which hydrogen is replaced by fluorine or chlorine; ring C 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, or 7,8 Z ⁹ and Z ¹⁰ are independently a single bond, ethylene, carbonyloxy or methyleneoxy; b is 1, 2 or 3 and c is 0 or 1, and the sum of b and c is 3 or less. The liquid crystal according to any one of claims 5 to 7, containing at least one compound selected from the group of compounds represented by formula (2-1) to formula (2-22) as a first component. Composition.

In formulas (2-1) to (2-22), R ³ and R ⁴ independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or It is alkenyloxy having 2 to 12 carbons.   The liquid crystal composition according to claim 7 or 8, wherein the proportion of the first component is in the range of 10% by weight to 90% by weight. The liquid crystal composition according to any one of claims 5 to 9, containing at least one compound selected from the group of compounds represented by formula (3) as a second component.

In formula (3), R ⁵ and R ⁶ independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least one hydrogen is replaced by fluorine or chlorine. C 1-12 alkyl or C 2-12 alkenyl in which at least one hydrogen is replaced by fluorine or chlorine; ring E and ring F are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ¹¹ is a single bond, ethylene, carbonyloxy or methyleneoxy; d Is one, two, or three. The liquid crystal according to any one of claims 5 to 10, which contains at least one compound selected from the group of compounds represented by formulas (3-1) to (3-13) as a second component. Composition.

In formulas (3-1) to (3-13), R ⁵ and R ⁶ independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, It is an alkyl having 1 to 12 carbons in which one hydrogen is replaced by fluorine or chlorine, or an alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.   The liquid crystal composition according to claim 10, wherein the proportion of the second component is in the range of 10% by weight to 90% by weight. The liquid crystal composition according to any one of claims 5 to 12, containing at least one compound selected from the group of polymerizable compounds represented by Formula (4) as a second additive.

In the formula (4), ring G and ring J are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine- 2-yl or pyridin-2-yl in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen Fluorine or chlorine may be replaced by alkyl having 1 to 12 carbon atoms; ring I may be 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, -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, and in these rings, at least one hydrogen is fluorine, chlorine, carbon number 1 to 12 alkyl, C 1 to C 12 alkoxy, or at least one hydrogen may be replaced by C 1 to C 12 alkyl substituted with fluorine or chlorine; Z ¹² and Z ¹³ are independently is a single bond or alkylene having 1 to 10 carbon atoms, 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) - may be replaced by, in these groups, at least one hydrogen may be replaced by fluorine or ^chlorine; P ^{1, P} 2, And P ³ independently represent a polymerizable group; Sp ¹ , Sp ² , and Sp ³ independently represent a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH _2- may be replaced by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -is -CH = CH- or -C≡C- Even if replaced In these groups, at least one hydrogen may be replaced by fluorine or chlorine; e is 0, 1 or 2; f, g and h are independently 0, 1, And 2, 3 or 4 and the sum of f, g and h is 1 or more. In the formula (4), P ¹ , P ² and P ³ independently represent a group selected from the group of polymerizable groups represented by the formulas (P-1) to (P-5) Item 14. A liquid crystal composition according to item 13.

In formulas (P-1) to (P-5), M ¹ , M ² and M ³ independently represent hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine And C 1 -C 5 alkyl substituted by The liquid crystal composition according to claim 13 or 14, containing at least one compound selected from the group of polymerizable compounds represented by formula (4-1) to formula (4-27) as a second additive. .

In formulas (4-1) to (4-27), P ⁴ , P ⁵ and P ⁶ independently represent each of the polymerizable groups represented by formulas (P-1) to (P-3) A group selected from the group

Here, M ¹ , M ² and M ³ are independently 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 independently represent 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.   The liquid crystal composition according to any one of claims 13 to 15, wherein the proportion of the second additive is in the range of 0.03% by weight to 10% by weight.   A liquid crystal display device comprising the liquid crystal composition according to any one of claims 5 to 16.   The liquid crystal display element according to claim 17, 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 13 to 16, wherein a second additive contained in the liquid crystal composition is polymerized.   Use of the liquid crystal composition according to any one of claims 5 to 16 in a liquid crystal display device.   Use of the liquid crystal composition according to any one of claims 5 to 16 in a polymer supported alignment type liquid crystal display device.

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