JPWO2018020838A1 - Liquid crystal composition and liquid crystal display device - Google Patents

Abstract

Nematic liquid crystal composition containing at least one compound selected from the group of polar compounds having a (meth) acrylamide group represented by the formula (1) as a first additive and having negative dielectric anisotropy , And a liquid crystal display device containing this composition. In formula (1), R 1 is hydrogen, halogen, alkyl having 1 to 12 carbon atoms, and the like; ring A and ring B are independently 1,4-cyclohexylene, 1,4-phenylene and the like; Z1 is a single bond or the like; Sp1 is a single bond, an alkylene having 1 to 7 carbon atoms, or the like; a is 0 to 4; R2 and R3 are each independently hydrogen or methyl.

Description

  The present invention relates to a liquid crystal composition having a negative dielectric anisotropy and containing a polar compound (or a polymer thereof) having a (meth) acrylamide group, a liquid crystal display device containing the composition, and the like.

  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 association between the two properties is 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 an initial stage not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable. After long time use, a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable. 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. A polymer sustained alignment (PSA) type liquid crystal display device utilizes the effect of a polymer. 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.

  On the other hand, in a liquid crystal display element having no alignment film, a liquid crystal composition containing a polymer and a polar compound having no polymerizable group is used (Patent Documents 1 to 5). First, a composition to which a small amount of polymerizable compound and a small amount of polar compound are added is injected into the device. Here, the polar compound is adsorbed to the substrate surface and arranged. The liquid crystal molecules are oriented according to this arrangement. Next, the composition is irradiated with ultraviolet light while applying a voltage between the substrates of the device. Here, the polymerizable compound is polymerized to stabilize the alignment of liquid crystal molecules. In this composition, it is possible to control the alignment of liquid crystal molecules by the polymer and the polar compound, so that the response time of the device is shortened and the image sticking is improved. Furthermore, in the element having no alignment film, the process of forming the alignment film is unnecessary. Since there is no alignment film, the interaction between the alignment film and the composition does not lower the electrical resistance of the device. Such an effect of the combination of a polymer and a polar compound can be expected for devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

  In an AM device having a TN mode, a composition having 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. Examples of liquid crystal compositions having negative dielectric anisotropy are disclosed in the following Patent Documents 1 to 6. In the present invention, instead of or in combination with conventionally used polymerizable compounds and polar compounds, compositions in which a polar compound having a (meth) acrylamide group is combined with a liquid crystal compound are prepared. This composition can be suitably used for a liquid crystal display device having no alignment film.

International Publication No. 2014/090362 brochure International Publication No. 2014/094959 brochure International Publication No. 2013/004372 brochure International Publication No. 2012/104008 Pamphlet WO 2012/038026 pamphlet JP 50-35076

  One object of the present invention is to provide a liquid crystal composition containing a polar compound having a (meth) acrylamide group represented by the formula (1), wherein the polar compound having a (meth) acrylamide group is And high compatibility with liquid crystal compounds. Another object is to provide a liquid crystal composition in which vertical alignment of liquid crystal molecules can be achieved by the action of a polymer produced from a polar compound having a (meth) acrylamide group. 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 which satisfies at least one property in properties such as high stability. Another object is to provide a liquid crystal composition having a proper balance between at least two 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（１）において、Ｒ^１は、水素、ハロゲン、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Ａおよび環Ｂ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、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、ピリジン−２，５−ジイル、フルオレン−２，７−ジイル、フェナントレン−２，７−ジイル、またはアントラセン−２，６−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^１は、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、または−ＣＦ＝ＣＦ−であり；Ｓｐ^１は、単結合または炭素数１から７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−、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−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；ａは、０、１、２、３、または４であり；Ｒ^２およびＲ^３は独立して、水素またはメチルである。The present invention contains at least one compound selected from the group of polar compounds having a (meth) acrylamide group represented by the formula (1) as a first additive, and has negative dielectric anisotropy The present invention relates to a liquid crystal composition and a liquid crystal display device containing the composition.

In formula (1), R ¹ is hydrogen, halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, 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 A and ring B are independently 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, naphtha Lene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7 -Diyl, phenanthrene-2,7-diyl or anthracene-2,6-diyl, in which ring at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, 1 to 12 carbons Or an alkyl of 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine; Z ¹ is a single bond, -CH ₂ CH _2- , -CH = CH-, _{-C≡C -, - COO -, -} OCO -, - CF 2 O -, - OCF 2 -, - CH 2 O -, - OCH 2 - or a -CF = CF-,; Sp ¹ is A bond or alkylene of 1 to 7 carbon atoms, in the alkylene, at least one of _-CH 2 -, -O -, - COO-, or it may be replaced by -OCO-, at least one -CH ₂ CH ₂ -may be replaced by -CH = CH-, and in these groups at least one hydrogen may be replaced by fluorine; a is by 0, 1, 2, 3, or 4 R ² and R ³ are independently hydrogen or methyl.

  One advantage of the present invention is to provide a liquid crystal composition containing a polar compound having a (meth) acrylamide group represented by the formula (1), wherein the polar compound having a (meth) acrylamide group is And high compatibility with liquid crystal compounds. Another advantage is to provide a liquid crystal composition capable of achieving vertical alignment of liquid crystal molecules by the action of a polymer produced from a polar compound having a (meth) acrylamide group. Other advantages are: high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, appropriate optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability to ultraviolet light, heat It is an object of the present invention to provide a liquid crystal composition which satisfies at least one property in properties such as high stability. Another advantage is to provide a liquid crystal composition having a suitable balance between at least two properties. Another advantage is to provide a liquid crystal display device containing such a composition. Another advantage is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long lifetime.

  The usage of the terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "composition" and "element", respectively. "Liquid crystal display element" is a generic term for liquid crystal display panels and liquid crystal display modules. The “liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase or a smectic phase and has no liquid crystal phase, but has a composition for the purpose of adjusting properties such as temperature range, viscosity and dielectric anisotropy of the nematic phase. It is a generic term for compounds mixed in a substance. This compound has, for example, a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod like. The "polymerizable compound" is a compound to be added for the purpose of forming a polymer in the composition. The “(meth) acrylamide group” represents one or both of the “acrylamide group” and the “methacrylamide group”.

  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. Liquid crystal compounds and additives are mixed in such a procedure. The proportion (content) of the liquid crystal compound is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition not including the additive, even when the additive is added. The proportion (addition amount) of the additive is represented by a weight percentage (% by weight) based on the weight of the liquid crystal composition without the additive. 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 at the initial stage not only at room temperature but also at temperatures close to the upper temperature, and after prolonged use it has high resistivity at temperatures close to the upper temperature as well as room temperature. Is meant to have. 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 element may be examined before and after the aging test (including the accelerated aging test). The expression "increase the dielectric anisotropy" means that in the case of a composition having a positive dielectric anisotropy, the value increases positively, and a composition having a negative dielectric anisotropy. In the case of goods, it means that the value increases negatively.

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

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

In the chemical formulas of component compounds, the symbol of terminal group R ¹ is used for a plurality of compounds. In these compounds, two groups represented by any two R ¹ may be identical or different. For example, there is a case where R ^{1 of} the compound (1-1) is ethyl and R ¹ of the compound (1-2) is ethyl. In some cases, R ^{1 of} compound (1-1) is ethyl and R ¹ of compound (1-2) is propyl. This rule also applies to symbols such as other end groups. In formula (1), when a is 2, two rings A are present. In this compound, two groups represented by two rings A may be identical or different. This rule also applies to any two rings A when a is greater than two. This rule also applies to other symbols. This rule also applies to the case of ^two -Sp ³ -P ² in compound (4-27).

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. The diagonal lines across the hexagon indicate that any hydrogen on the ring may be replaced by a group such as -Sp ² -P ¹ . A subscript such as 'j' indicates the number of groups replaced. There is no such replacement when the subscript 'j' is zero. When the subscript 'j' is 2 or more, a plurality of -Sp ² -P ¹ exists on the ring J. The plurality of groups represented by -Sp ² -P ¹ may be identical or different.

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 unsymmetrical 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 generally more preferably trans than cis. Halogen means fluorine, chlorine, bromine and iodine. Preferred halogen is fluorine or chlorine. A further preferred halogen is fluorine.

  The present invention includes the following items.

式（１）において、Ｒ^１は、水素、ハロゲン、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Ａおよび環Ｂ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、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、ピリジン−２，５−ジイル、フルオレン−２，７−ジイル、フェナントレン−２，７−ジイル、またはアントラセン−２，６−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^１は、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、または−ＣＦ＝ＣＦ−であり；Ｓｐ^１は、単結合または炭素数１から７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−、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−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；ａは、０、１、２、３、または４であり；Ｒ^２およびＲ^３は独立して、水素またはメチルである。Item 1. A liquid crystal composition containing at least one compound selected from the group of polar compounds having a (meth) acrylamide group represented by the formula (1) as a first additive and having negative dielectric anisotropy.

In formula (1), R ¹ is hydrogen, halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, 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 A and ring B are independently 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, naphtha Lene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7 -Diyl, phenanthrene-2,7-diyl or anthracene-2,6-diyl, in which ring at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, 1 to 12 carbons Or an alkyl of 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine; Z ¹ is a single bond, -CH ₂ CH _2- , -CH = CH-, _{-C≡C -, - COO -, -} OCO -, - CF 2 O -, - OCF 2 -, - CH 2 O -, - OCH 2 - or a -CF = CF-,; Sp ¹ is A bond or alkylene of 1 to 7 carbon atoms, in the alkylene, at least one of _-CH 2 -, -O -, - COO-, or it may be replaced by -OCO-, at least one -CH ₂ CH ₂ -may be replaced by -CH = CH-, and in these groups at least one hydrogen may be replaced by fluorine; a is by 0, 1, 2, 3, or 4 R ² and R ³ are independently hydrogen or methyl.

式（１−１）から式（１−１２）において、Ｒ^１は、水素、ハロゲン、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；Ｚ^１、Ｚ^２、およびＺ^３は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、または−ＣＦ＝ＣＦ−であり；Ｓｐ^１は、単結合または炭素数１から７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−、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−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；Ｌ^１、Ｌ^２、Ｌ^３、Ｌ^４、Ｌ^５、Ｌ^６、Ｌ^７、Ｌ^８、Ｌ^９、Ｌ^１０、Ｌ^１１、Ｌ^１２、Ｌ^１３、およびＬ^１４は独立して、水素、フッ素、メチル、またはエチルであり；Ｒ^２およびＲ^３は独立して、水素またはメチルである。Item 2. Item 2. The item according to item 1, containing at least one compound selected from the group of polar compounds having a (meth) acrylamide group represented by Formula (1-1) to Formula (1-12) as a first additive: Liquid crystal composition.

In formulas (1-1) to (1-12), R ¹ represents hydrogen, halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, at least one of C 1 to C 12 alkyl in which hydrogen is replaced by fluorine or chlorine, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; Z ¹ , Z ² and Z ³ are independently represent a single _{bond, -CH 2 CH 2 -, -} CH = CH -, - C≡C -, - COO -, - OCO -, - CF 2 O -, - OCF 2 -, - CH 2 O- , -OCH _2- , or -CF = CF-; Sp ¹ is a single bond or an alkylene having 1 to 7 carbon atoms, and in this alkylene, at least one -CH ₂ -is -O-,- COO , Or may be replaced by -OCO-, at least one _-CH 2 CH ₂ - may be replaced by -CH = CH-, in these groups, at least one hydrogen is replaced by fluorine L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ , L ⁸ , L ⁹ , L ¹⁰ , L ¹¹ , L ¹² , L ¹³ , and L ¹⁴ are independently , Hydrogen, fluorine, methyl or ethyl; R ² and R ³ are independently hydrogen or methyl.

Item 3. The liquid crystal composition according to item 1 or 2, wherein the proportion of the first additive is in the range of 0.05% by weight to 10% by weight.

式（２）において、Ｒ^４およびＲ^５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Ｃおよび環Ｅ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、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、またはテトラヒドロピラン−２，５−ジイルであり；環Ｄ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^４およびＺ^５は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、または−ＯＣＯ−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 4. Item 4. The liquid crystal composition according to any one of items 1 to 3, containing at least one compound selected from the group of compounds represented by formula (2) as a first component.

In formula (2), R ⁴ and R ⁵ 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 C and ring E are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine Or tetrahydropyran-2,5-diyl; ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5 - methyl-1,4-phenylene, it is a 3,4,5-trifluoro-2,6-diyl or 7,8-difluoro-chroman-2,6-diyl,; ^{Z 4} Oyo Z ⁵ is independently a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or a -OCO-; b is 1, 2 or 3, , 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^４およびＲ^５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 5. 5. The liquid crystal composition according to any one of items 1 to 4, 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 ⁴ and R ⁵ 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 6. 6. The liquid crystal composition according to item 4 or 5, 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^６およびＲ^７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Ｆおよび環Ｇ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^６は、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、または−ＯＣＯ−であり；ｄは、１、２、または３である。Item 7. 7. The liquid crystal composition according to any one of items 1 to 6, containing at least one compound selected from the group of compounds represented by formula (3) as a second component.

In formula (3), R ⁶ and R ⁷ 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 to C 12 alkyl or C 2 to C 12 alkenyl in which at least one hydrogen is replaced by fluorine or chlorine; ring F and ring G are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ⁶ represents a single bond, -CH ₂ CH _2- , -CH ₂ O- , -OCH _2- , -COO-, or -OCO-; d is 1, 2 or 3;

式（３−１）から式（３−１３）において、Ｒ^６およびＲ^７は独立して、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 8. Item 8. The liquid crystal composition according to any one of items 1 to 7, 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 ⁶ and R ⁷ 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 9. 9. The liquid crystal composition according to item 7 or 8, wherein the proportion of the second component is in the range of 10% by weight to 70% by weight.

式（４）において、環Ｊおよび環Ｐ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Ｋは、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、ナフタレン−１，２−ジイル、ナフタレン−１，３−ジイル、ナフタレン−１，４−ジイル、ナフタレン−１，５−ジイル、ナフタレン−１，６−ジイル、ナフタレン−１，７−ジイル、ナフタレン−１，８−ジイル、ナフタレン−２，３−ジイル、ナフタレン−２，６−ジイル、ナフタレン−２，７−ジイル、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、またはピリジン−２，５−ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；Ｚ^７およびＺ^８は独立して、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、そして少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ_３）−、または−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｐ^１、Ｐ^２、およびＰ^３は、重合性基であり；Ｓｐ^２、Ｓｐ^３、およびＳｐ^４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、そして少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ｑは０、１、または２であり；ｊ、ｋ、およびｐは独立して、０、１、２、３、または４であり、そしてｊ、ｋ、およびｐの和は、１以上である。Item 10. 10. The liquid crystal composition according to any one of items 1 to 9, containing at least one compound selected from the group of polymerizable compounds represented by formula (4) as a second additive.

In the formula (4), ring J and ring P 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 substituted by alkyl having 1 to 12 carbon atoms; ring K 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 ⁷ and Z ⁸ independently is a single bond or alkylene having 1 to 10 carbon atoms, in the alkylene, at least one of _-CH 2 -, -O -, - CO -, - OO-, or it may be replaced by -OCO-, and at least one _-CH 2 CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, or _{-C (CH 3) = C (} CH 3) - may be replaced by, in these groups, at least one hydrogen may be replaced by fluorine or ^chlorine; P ^{1, P} 2, And P ³ is a polymerizable group; Sp ² , Sp ³ and Sp ⁴ are independently a single bond or alkylene having 1 to 10 carbons, and in this alkylene, at least one —CH ₂ — is , -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -is replaced by -CH = CH- or -C≡C- Even In these groups, at least one hydrogen may be replaced by fluorine or chlorine; q is 0, 1 or 2; j, k and p are independently 0, 1, 2 , 3 or 4 and the sum of j, k and p 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 11. 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) 10. The liquid crystal composition according to 10.

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（４−２８）において、Ｐ^１、Ｐ^２、およびＰ^３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^２、Ｓｐ^３、およびＳｐ^４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、そして少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。Item 12. 12. The method according to any one of items 1 to 11, comprising at least one compound selected from the group of polymerizable compounds represented by formula (4-1) to formula (4-28) as a second additive: Liquid crystal composition.

In formulas (4-1) to (4-28), P ¹ , P ² and P ³ independently represent a polymerizable group represented by formulas (P-1) to (P-3) A group selected from the group wherein M ¹ , M ² and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is replaced by fluorine or chlorine C 1 -C 5 alkyl;

Sp ² , Sp ³ and Sp ⁴ 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-, and in these groups, at least 1 One hydrogen may be replaced by fluorine or chlorine.

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

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

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

Item 16. Item 14. A high content containing the liquid crystal composition according to any one of items 1 to 13, wherein the first additive in the liquid crystal composition is polymerized, or the first and second additives are polymerized. Molecular support alignment type liquid crystal display device.

Item 17. Item 14. An alignment comprising the liquid crystal composition according to any one of items 1 to 13, wherein the first additive in the liquid crystal composition is polymerized, or the first additive and the second additive are polymerized. Liquid crystal display device having no film.

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

Item 19. Item 14. Use of the liquid crystal composition according to any one of items 1 to 13 in a polymer supported alignment type liquid crystal display device.

Item 20. Item 14. Use of the liquid crystal composition according to any one of items 1 to 13 in a liquid crystal display device having no alignment film.

  The present invention also includes the following items. (A) The liquid crystal composition described above is disposed between two substrates, light is irradiated to the composition under voltage application, and the polar compound having a (meth) acrylamide group contained in the composition is The method of manufacturing said liquid crystal display element by superposing | polymerizing. (B) The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy (measured at 25 ° C.) at a wavelength of 589 nm is 0.08 or more, and the dielectric anisotropy (measured at 25 ° C. at a frequency of 1 kHz) The above liquid crystal composition, wherein

  The present invention also includes the following items. (C) Compounds (5) to (7) described in JP-A-2006-199941 are liquid crystal compounds having positive dielectric anisotropy, but at least one selected from the group of these compounds A composition as described above containing one compound. (D) The above composition containing at least two of the above polar compounds. (E) The above composition further comprising a polar compound different from the above polar compound. (F) one, two, or at least three of optically active compounds, antioxidants, ultraviolet light absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, additives such as polar compounds, or the like Composition as described above containing one. This additive may be the same as or different from the first additive or the second additive. (G) AM element containing the above composition. (H) A device containing the composition described above and having a mode of TN, ECB, OCB, IPS, FFS, VA or FPA. (I) A transmission type device containing the above composition. (J) Using the above composition as a composition having a nematic phase. (K) Use as an optically active composition by adding an optically active compound to the above composition.

  The composition of the present invention will be described in the following order. First, the 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 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. The composition of the present invention is classified into composition A and composition B. 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. 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.

  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 properties of the composition 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 between component compounds, the symbol 0 means that the value is zero or close to zero.

  When the component compounds are mixed into the composition, the main effects of the component compounds on the properties of the composition are as follows. The compound (1), which is the first additive, is adsorbed to the substrate surface by the action of a polar group, and controls the alignment of liquid crystal molecules. In order to obtain the desired effect, it is essential that the compound (1) has high compatibility with the liquid crystal compound. The compound (1) has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-like, so it is most suitable for this purpose. The compound (1) gives a polymer by polymerization. The polymer stabilizes the orientation of liquid crystal molecules, thereby reducing the response time of the device and improving the image sticking. The first component, compound (2), raises the dielectric anisotropy and lowers the lower limit temperature. The second component, compound (3), lowers the viscosity, raises the upper limit temperature, or lowers the lower limit temperature. The second additive, compound (4), is added to the composition for the purpose of further adapting to the polymer-supported oriented device. The compound (4) gives 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. From the viewpoint of alignment of liquid crystal molecules, the polymer of the compound (1) is considered to be more effective than the polymer of the compound (4) because it has an interaction with the substrate surface.

  Third, the combination of components in the composition, the preferred ratio of the components and the basis thereof will be described. A preferred combination of the components in the composition is Compound (1) + Compound (2) + Compound (3), or Compound (1) + Compound (2) + Compound (3) + Compound (4).

  The compound (1) is added to the composition for the purpose of controlling the alignment of liquid crystal molecules. The preferred proportion of the compound (1) is about 0.05% 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 7% by weight. An especially desirable ratio is in the range of about 0.5% by weight to about 5% by weight.

  The compound (1) is preferably stable because it is added to the composition. When the compound (1) is added to the composition, it is preferred that the compound does not lower the voltage holding ratio of the device. The compound (1) preferably has low volatility. The preferred molar mass is 130 g / mol or more. A further preferred molar mass is in the range of 150 g / mol to 500 g / mol.

  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 lower the viscosity, to raise the upper limit temperature, or to lower the lower limit temperature, and to increase the dielectric anisotropy by about 70% by weight It is below. A further preferred ratio is in the range of about 15% by weight to about 65% by weight. An especially desirable ratio is in the range of about 20% by weight to about 60% by weight.

  The preferred proportion of the compound (4) is about 0.03% by weight or more to improve the long-term reliability of the device, and about 10% by weight or less to prevent 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% by weight.

Fourth, the preferred embodiments of the component compounds are described. In the formulas (1) and (1-1) to the formulas (1-12), R ¹ is hydrogen, halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, 2 to 12 carbons Alkenyl is alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Desirable R ¹ is alkyl having 1 to 12 carbons because of high compatibility with the liquid crystal compound. R ² and R ³ are independently hydrogen or methyl. Desirable R ² is methyl because of high compatibility with the liquid crystal compound. Desirable R ³ is hydrogen to increase the polymerization rate.

  Ring A and ring B are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1 2,4-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, pyridine-2,5-diyl, fluorene- 2,7-diyl, phenanthrene-2,7-diyl or anthracene-2,6-diyl, wherein in these rings at least one hydrogen is fluorine, chlorine, Alkyl of from prime 1 12, may be replaced by alkyl alkoxy of from 1 to 12 carbons, or at least one hydrogen from a carbon number of 1 which is replaced by fluorine or chlorine, 12. Preferred ring A or ring B is 1,4-cyclohexylene, 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ¹ , Z ² and Z ³ independently represent a single bond, -CH ₂ CH _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, _{-OCF 2 -, - CH 2 O} -, - OCH 2 -, or -CF = CF-. Preferred Z ¹ , Z ² or Z ³ is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO- or -OCO-. Further preferred Z ¹ , Z ² or Z ³ is a single bond.

Sp ¹ is a single bond or an alkylene having 1 to 7 carbon atoms, and in this alkylene, at least one —CH ₂ — may be replaced by —O—, —COO—, or —OCO—, at least One —CH ₂ CH ₂ — may be replaced by —CH = CH—, and in these groups, at least one hydrogen may be replaced by fluorine. Preferred Sp ¹ is a single bond.

  a is 0, 1, 2, 3 or 4; Preferred a is 1, 2 or 3.

L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ , L ⁸ , L ⁹ , L ¹⁰ , L ¹¹ , L ¹² , L ¹³ and L ¹⁴ independently represent hydrogen or fluorine , Methyl or ethyl. Preferred L ¹ to L ¹⁴ are hydrogen, fluorine or methyl. Further preferred L ¹ to L ¹⁴ is hydrogen or fluorine.

In the formulas (2) and (3), R ⁴ and R ⁵ 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 ⁴ or R ⁵ 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 ⁶ and R ⁷ independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 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 ⁶ or R ⁷ 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 in R ¹ , R ⁴ , R ⁵ and R ⁶ , preferred alkoxy, preferred alkenyl, preferred alkenyloxy, alkyl in which at least one hydrogen is replaced by fluorine or chlorine, and at least one hydrogen is replaced by fluorine or chlorine The described alkenyl is described.

  Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More preferred alkyl is ethyl, propyl, butyl, pentyl or heptyl 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 or chlorine are: 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro -4-pentenyl or 6,6-difluoro-5-hexenyl. Further preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl for decreasing the viscosity.

または

であり、好ましくは

である。Ring C and ring E are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, or Tetrahydropyran-2,5-diyl. Preferred examples of “1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine” are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, or 2-chloro -3-fluoro-1,4-phenylene. Preferred ring C or ring E 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. The configuration of 1,4-cyclohexylene is preferably trans rather than cis in order to increase the maximum temperature. Tetrahydropyran-2,5-diyl is

Or

And preferably

It is.

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

  Ring F and ring G are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene. Preferred ring F or ring G is 1,4-cyclohexylene to lower the viscosity or to raise the upper limit temperature, and to increase the optical anisotropy or to lower the lower limit temperature. It is phenylene. The configuration of 1,4-cyclohexylene is preferably trans rather than cis in order to increase the maximum temperature.

Z ⁴ and ^{Z 5} are independently a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or -OCO-. Desirable Z ⁴ or Z ⁵ is a single bond to lower the viscosity, -CH ₂ CH _2- to lower the lower limit temperature, and -CH ₂ O- or -OCH to increase the dielectric anisotropy. _2- . Z ⁶ represents a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or -OCO-. Preferred ^{Z 6} is a single bond for decreasing the viscosity, _-CH 2 CH ₂ for decreasing the minimum temperature - and for increasing the maximum temperature -COO- or -OCO-.

  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 group selected from the group of polymerizable groups represented by Formula (P-1) to Formula (P-5). Further preferable P ¹ , P ² or P ³ is a group represented by formula (P-1), formula (P-2) or formula (P-3). Particularly preferred P ¹ , P ² or P ³ is a group represented by formula (P-1) or formula (P-2). Most preferable P ¹ , P ² or P ³ is a group represented by formula (P-1). Preferred groups represented by the formula (P-1) is, -OCO-CH = CH ₂ or _{-OCO-C (CH} 3) a = CH _2. The wavy lines in Formula (P-1) to Formula (P-5) indicate the binding site.

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 Preferred M ¹ , M ² or M ³ is hydrogen or methyl to increase the reactivity. Further preferred M ¹ is hydrogen or methyl, and further preferred M ² or M ³ is hydrogen.

Sp ² , Sp ³ and Sp ⁴ 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-, and in these groups, at least 1 One hydrogen may be replaced by fluorine or chlorine. Preferred Sp ² , Sp ³ or Sp ⁴ 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 ² , Sp ³ or Sp ⁴ is a single bond.

  Ring J and ring P 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 J or ring P is phenyl. Ring K is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene 1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2 , 7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl in these rings, At least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is fluorine or chlorine. From the obtained 1 carbon atoms may be replaced by alkyl of 12. Preferred ring K is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁷ and Z ⁸ are independently a single bond or alkylene having 1 to 10 carbons, and in this alkylene, at least one —CH ₂ — is —O—, —CO—, —COO—, or — It may be replaced by OCO-, and at least one _-CH 2 CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, or -C (CH ₃ ) = C (CH ₃ ) — 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, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO- or -OCO-. Further preferred Z ⁷ or Z ⁸ is a single bond.

  q is 0, 1 or 2; Preferred q is 0 or 1. j, k and p are independently 0, 1, 2, 3 or 4 and the sum of j, k and p is 1 or more. Preferred j, k or p is 1 or 2.

  Fifth, preferred component compounds are shown. The preferable compound (1) is the compound (1-1) described in item 2 to the compound (1-12). It is preferable that at least two of the first additives be a combination of the compound (1-1) and the compound (1-2), or the compound (1-1) and the compound (1-4).

  The preferable compound (2) is a compound (2-1) to a compound (2-22) described in item 5. In these compounds, at least one of the first components is a compound (2-1), a compound (2-3), a compound (2-4), a compound (2-6), a compound (2-8), or a compound It is preferable that it is (2-10). At least two of the first components are compound (2-1) and compound (2-6), compound (2-1) and compound (2-10), compound (2-3) and compound (2-6), It is preferable that it is a combination of a compound (2-3) and a compound (2-10), a compound (2-4) and a compound (2-6), or a compound (2-4) and a compound (2-8).

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

  The preferred compound (4) is a compound (4-1) to a compound (4-28) described in Item 12. In these compounds, at least one of the second additives is a compound (4-1), a compound (4-2), a compound (4-24), a compound (4-25), a compound (4-26), or It is preferable that it is a compound (4-27). At least two of the second additives are the compound (4-1) and the compound (4-2), the compound (4-1) and the compound (4-18), the compound (4-2) and the compound (4-24) A compound (4-2) and a compound (4-25), a compound (4-2) and a compound (4-26), a compound (4-25) and a compound (4-26), or a compound (4-18) It is preferable that it is a combination of and a compound (4-24).

  Sixth, additives that may be added to the composition will be described. Such additives include optically active compounds, antioxidants, ultraviolet light absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules to give a twist angle. Examples of such compounds are compounds (5-1) to (5-5). The preferred proportion of the optically active compound is about 5% by 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 (1) and compound (4) are suitable for this purpose. Along with the compound (1) and the compound (4), other polymerizable compounds different from the compound (1) and the compound (4) may be added to the composition. Preferred examples of other polymerizable compounds are compounds such as acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes), vinyl ketones and the like. Further preferred examples are acrylates or methacrylates. The preferred proportion of compound (1) and compound (4) is about 10% by weight or more based on the total weight of the polymerizable compound. A further preferred ratio is about 50% by weight or more. An especially desirable ratio is about 80% by weight or more. An especially desirable ratio is also 100% by weight. Reactivity of the polymerizable compound or liquid crystal molecule by changing the type of the compound (1) and the compound (4) or by combining the compound (1) and the compound (4) with other polymerizable compounds in an appropriate ratio The pretilt angle of can be adjusted. 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 a suitable initiator such as a photoinitiator. Appropriate conditions for polymerization, appropriate types of initiators, and appropriate amounts 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 total weight of the polymerizable compound. A further preferred ratio is in the range of about 1% by weight to about 3% by weight.

  When the polymerizable compound is stored, 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.

  Seventh, the synthesis methods of the component compounds will be described. These compounds can be synthesized by known methods. The synthesis method is illustrated. The synthesis method of compound (1) is described in the section of Examples. The compound (2-1) is synthesized by the method described in JP-A-2-503441. The compounds (3-5) are synthesized by the method described in JP-A-57-165328. The compound (4-18) is synthesized by the method described in JP-A-7-101900. Some of the compounds (6) are commercially available. Compounds of formula (6) wherein n is 1 are available from Aldrich (Sigma-Aldrich Corporation). Compounds (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 an AM device having a TN, OCB, IPS mode or FFS mode is particularly preferred. In an AM element having an IPS mode or an FFS mode, when no voltage is applied, the alignment of liquid crystal molecules may be parallel or perpendicular to the glass substrate. 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 a method for producing a conventional 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.

  When the compound (1), that is, a polar compound having a (meth) acrylamide group is used as the polymerizable compound, an alignment film is not necessary on the substrate of the device. An element without an alignment film is manufactured from a substrate without an alignment film according to the procedure described in the two preceding paragraphs.

  In this procedure, compound (1) is arranged on the substrate as the polar groups interact with the substrate surface. The liquid crystal molecules are oriented according to this arrangement. When a voltage is applied, the alignment of liquid crystal molecules is further promoted. In this state, the polymerizable group is polymerized by ultraviolet light, so that a polymer maintaining this orientation is formed. The effect of the polymer additionally stabilizes the orientation of the liquid crystal molecules and 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.

  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 composition M1 and composition M2. The present invention also includes a mixture of at least two of the compositions of the 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 following methods.

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 proportion of the liquid crystal compound. When the capillary column described above is used, the correction coefficient of each liquid crystal compound may be regarded as 1. Therefore, the ratio (% 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 and the device, 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. The sample was injected into 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 by the method described in the measurement (6).

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

(6) Dielectric anisotropy (Δε; measured at 25 ° C.): The value of dielectric anisotropy was calculated from the equation of Δε = εΔ−ε⊥. The dielectric constants (ε‖ and ε⊥) were measured as follows.
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 injected into 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 injecting the sample. 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 VA element in which the distance between two glass substrates (cell gap) was 3.5 μm and no alignment film was provided. The device was sealed with a UV curable adhesive. The device was irradiated with ultraviolet light of 78 mW / cm ² (405 nm) for 449 seconds (35 J) while applying a voltage of 30 V. For irradiation with ultraviolet light, a multi-metal lamp M04-L41 for ultraviolet curing was used, manufactured by Eye Graphics Co., Ltd. A rectangular wave (120 Hz) 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 maximum voltage of the square wave was set so that the transmittance was 90%. The lowest voltage of the rectangular wave was set to 2.5 V at which the transmittance was 0%. The response time is represented by the time (rise time; milliseconds) taken to change from 10% transmittance to 90% transmittance.

(13) Elastic constant (K11: splay elastic constant, K33: bend elastic constant; measured at 25 ° C .; pN): To measure, EC-type 1 elastic constant measuring instrument manufactured by Toyo Corporation. Using. The sample was injected into a vertical alignment device in which the distance between two glass substrates (cell gap) was 20 μm. A charge of 20 volts to 0 volts was applied to the device, and the capacitance and the applied voltage were measured. Fitting the measured capacitance (C) and applied voltage (V) values using the formula (2.98) and formula (2.101) on page 75 of “Liquid Crystal Device Handbook” (Nippon Kogyo Shimbun Ltd.) And the value of the elastic constant was obtained from equation (2.100).

(14) Specific resistance (ρ; measured at 25 ° C .; Ω cm): 1.0 mL of a sample was placed in 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)}. (Formula 1)

(15) Pretilt angle (degree): A spectral ellipsometer M-2000U (manufactured by JA Woollam Co., Inc.) was used for measurement of the pretilt angle.

(16) Alignment stability (liquid crystal alignment axis stability): Changes in the liquid crystal alignment axis on the electrode side of the liquid crystal display element were evaluated. Measure the liquid crystal orientation angle φ (before) on the electrode side before applying stress, then apply a rectangular wave 4.5 V, 60 Hz for 20 minutes to the device, then short for 1 second, and after 1 second and 5 minutes again The liquid crystal alignment angle φ (after) of the side was measured. From these values, the change Δφ (deg.) Of the liquid crystal alignment angle after 1 second and 5 minutes was calculated using the following equation.
Δφ (deg.) = Φ (after) −φ (before) (Expression 2)
These measurements were made with reference to J. Hilfiker, B. Johs, C. Herzinger, JF Elman, E. Montbach, D. Bryant, and PJ Bos, Thin Solid Films, 455-456, (2004) 596-600. . The smaller the Δφ, the smaller the change rate of the liquid crystal alignment axis, and the better the stability of the liquid crystal alignment axis.

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

Step 1 Compound (T-1) (25.0 g), triethylamine (16.65 ml), and THF (300 ml) were charged into a reactor and cooled to 0 ° C. The acrylic chloride (9.7 ml) was dripped slowly there, and it stirred for 6 hours, returning to room temperature. After filtering off insolubles, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layers were washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 9: 1) to obtain compound (T-2) (16.4 g; 54%).

Step 2 Sodium hydride (2.57 g) was charged to the reactor with THF (300 ml) and cooled to 0 ° C. The THF solution (100 ml) solution of compound (T-2) (16.4 g) was dripped slowly there, and it stirred for 1 hour. The methyl iodide (3.7 ml) was dripped slowly there, and it stirred for 3 hours, returning to room temperature. After filtering off insolubles, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layers were washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 4: 1). The residue was further purified by recrystallization from heptane to give compound (1-1) (14.2 g; 83%).

Compound (1-1)
¹ H-NMR: chemical shift δ (ppm; CDCl ₃ ): 6.56 (m, 1 H), 6.27 (t, 1 H), 5.65 (t, 1 H), 4.45 (m, 1 H) , 2.90 (s, 3 H), 1.83-1.52 (m, 8 H), 1.43-1.20 (m, 8 H), 1.18-0.92 (m, 9 H), 0 .89-0.80 (m, 5 H).

  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 parentheses 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.

Device Example 1. The composition which added the polar compound which has a (meth) acrylamide group represented by Formula (1) was inject | poured into the element which does not have a raw material alignment film. After irradiation with ultraviolet light, the vertical alignment of liquid crystal molecules in this device was examined. I will explain the ingredients first. The raw materials are composition (M1) to (M18), polar compound (PC-1) having a (meth) acrylamide group to (PC-13), and polymerizable compound (RM-1) to (RM-8). It selected from. The composition is as follows.

[Composition M1]
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%
NI = 73.2 ° C .; Tc <−20 ° C .; Δn = 0.113; Δε = −4.0; Vth = 2.18 V;

[Composition M2]
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%
Tc <−30 ° C .; Δn = 0.118; Δε = −4.4; Vth = 2.13 V; = 2 = 22.5 mPa · s.

[Composition M3]
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%
Tc <−30 ° C .; Δn = 0.107; Δε = −3.2; Vth = 2.02 V; 3.2 = 15.9 mPa · s.

[Composition M4]
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%
Tc <−30 ° C .; Δn = 0.108; Δε = −3.8; Vth = 2.25 V; = 2 = 24.6 mPa · s; VHR−1 = 99.1%; VHR -2 = 98.2%; VHR-3 = 97.8%.

[Composition M5]
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%
Tc <−30 ° C .; Δn = 0.119; Δε = −4.5; Vth = 1.69 V; = 3 = 31.4 mPa · s.

[Composition M6]
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%
NI = 98.8 ° C .; Tc <−30 ° C .; Δn = 0.111; Δε = −3.2; Vth = 2.47 V;. = 23.9 mPa · s.

[Composition M7]
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%
Tc <−30 ° C .; Δn = 0.084; Δε = −2.6; Vth = 2.43 V; = 2 = 22.8 mPa · s.

[Composition M8]
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%
Tc <−20 ° C .; Δn = 0.129; Δε = −4.3; Vth = 1.69 V; = 2 = 27.0 mPa · s.

[Composition M9]
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%
Tc <−30 ° C .; Δn = 0.123; Δε = −4.0; Vth = 2.27 V; = 2 = 29.6 mPa · s.

[Composition M10]
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%
Tc <−30 ° C .; Δn = 0.126; Δε = −4.5; Vth = 2.21 V; = 2 = 25.3 mPa · s.

[Composition M11]
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%
NI = 93.0 ° C .; Tc <−20 ° C .; Δn = 0.124; Δε = −4.5; Vth = 2.22 V; = 2 = 25.0 mPa · s.

[Composition M12]
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%
Tc <−30 ° C .; Δn = 0.104; Δε = −3.2; Vth = 2.06 V; = 1 = 15.6 mPa · s.

[Composition M13]
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%
NI = 78.3 ° C .; Tc <−20 ° C .; Δn = 0.103; Δε = −3.2; Vth = 2.17 V; = 1 = 17.7 mPa · s.

[Composition M14]
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%
Tc <−20 ° C .; Δn = 0.107; Δε = −3.2; Vth = 2.11 V; = 1 = 15.5 mPa · s.

[Composition M15]
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%
Tc <−30 ° C .; Δn = 0.115; Δε = −1.9; Vth = 2.82 V; Vth = 17.3 mPa · s.

[Composition M16]
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%
Tc <-20 ° C; Δn = 0.122; Δε = -4.2; Vth = 2.16 V; = 2 = 23.4 mPa · s.

[Composition M17]
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%
Tc <−20 ° C .; Δn = 0.101; Δε = −3.0; Vth = 2.04 V; = 1 = 13.9 mPa · s.

[Composition M18]
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%
Tc <-20 ° C; Δn = 0.114; Δε = -3.9; Vth = 2.20 V; = 2 = 24.7 mPa · s.

The first additive is a polar compound (PC-1) having a (meth) acrylamide group to (PC-13). In addition, in order to clarify the structure of the (meth) acrylamide group, notation of NH is carried out in the structural formula only when there is hydrogen which is directly bonded to nitrogen, that is, when R ² in the formula (1) is hydrogen.

The second additive is a polymerizable compound (RM-1) to (RM-8).

2. Vertical alignment of liquid crystal molecules Example 1
The polar compound (PC-1) which has a (meth) acrylamide group was added to the composition M1 in the ratio of 5 weight%. This mixture was injected on a hot stage at 100 ° C. into an element having no alignment film, in which the distance between two glass substrates (cell gap) was 4.0 μm. The polar compound (PC-1) having a (meth) acrylamide group was polymerized by irradiating the device with ultraviolet light (28 J) using an ultrahigh pressure mercury lamp USH-250-BY (manufactured by Ushio Inc.). This element was set in a polarization microscope in which a polarizer and an analyzer were disposed at right angles, light was irradiated to the element from below, and the presence or absence of light leakage was observed. When liquid crystal molecules were sufficiently aligned and light did not pass through the device, the vertical alignment was judged as "good". When the light which passed the element was observed, it was judged as "defect."

Examples 2 to 19 and Comparative Example 1
In Examples 2 to 19, a device having no alignment film was manufactured using a mixture prepared by adding a polar compound having a (meth) acrylamide group to the composition. The presence or absence of light leakage was observed in the same manner as in Example 1. The results are summarized in Table 4. In Example 19, a polymerizable compound (RM-1) was also added in a proportion of 0.5% by weight. In Comparative Example 1, the following polar compound (PC-14) was selected for comparison. This compound is different from the compound (1) because it does not have a polymerizable group.

As can be seen from Table 4, in Examples 1 to 18, the type of the composition and the polar compound having a (meth) acrylamide group was changed, but no light leakage was observed. This result indicates that the vertical alignment is good even if the element does not have an alignment film, and the liquid crystal molecules are stably aligned. In Example 19, the polymerizable compound (RM-1) was further added, but similar results were obtained. On the other hand, in Comparative Example 1, light leakage was observed. This result indicates that the vertical alignment was not good. Therefore, it is understood that the polymer produced from the polar compound having a (meth) acrylamide group plays an important role in the vertical alignment of liquid crystal molecules.

3. Miscibility of Polar Compound and Liquid Crystal Composition Example 20
The polar compound (PC-1) which has a (meth) acrylamide group was added to the composition M1 in the ratio of 5 weight%. It was heated to 100 ° C., changed to an isotropic liquid, and allowed to cool to 25 ° C. After one day at room temperature, the presence or absence of a precipitate was confirmed. When a precipitate was confirmed, it was judged as "no precipitation" when no "precipitation" deposit was confirmed.

Examples 21 to 22 and Comparative Examples 2 to 4
In Examples 21 and 22, the compatibility between the polar compound and the liquid crystal composition was evaluated in the same manner as in Example 20. The results are summarized in Table 5. In Comparative Examples 2 to 4, the following polar compounds (PC-15 to PC-17) were selected for comparison. These compounds are different from the compound (1) because they do not have a polymerizable group.

As can be seen from Table 5, in Examples 20 to 22, no precipitate was observed. On the other hand, the precipitate was confirmed in Comparative Examples 2 and 3. This result indicates that the polar compound having a (meth) acrylamide group has better compatibility with the liquid crystal composition than the polar compound having a hydroxyl group.

  The liquid crystal composition of the present invention can control the alignment of liquid crystal molecules in an element having no alignment film. The liquid crystal display element containing this composition has characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, long life, etc., so it can be used for liquid crystal projectors, liquid crystal televisions, etc. .

Claims (20)

A liquid crystal composition containing at least one compound selected from the group of polar compounds having a (meth) acrylamide group represented by the formula (1) as a first additive and having negative dielectric anisotropy.

In formula (1), R ¹ is hydrogen, halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, 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 A and ring B are independently 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, naphtha Lene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7 -Diyl, phenanthrene-2,7-diyl or anthracene-2,6-diyl, in which ring at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, 1 to 12 carbons Or an alkyl of 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine; Z ¹ is a single bond, -CH ₂ CH _2- , -CH = CH-, _{-C≡C -, - COO -, -} OCO -, - CF 2 O -, - OCF 2 -, - CH 2 O -, - OCH 2 - or a -CF = CF-,; Sp ¹ is A bond or alkylene of 1 to 7 carbon atoms, in the alkylene, at least one of _-CH 2 -, -O -, - COO-, or it may be replaced by -OCO-, at least one -CH ₂ CH ₂ -may be replaced by -CH = CH-, and in these groups at least one hydrogen may be replaced by fluorine; a is by 0, 1, 2, 3, or 4 R ² and R ³ are independently hydrogen or methyl. The composition according to claim 1, which contains at least one compound selected from the group of polar compounds having a (meth) acrylamide group represented by Formula (1-1) to Formula (1-12) as a first additive. Liquid crystal composition.

In formulas (1-1) to (1-12), R ¹ represents hydrogen, halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, at least one of C 1 to C 12 alkyl in which hydrogen is replaced by fluorine or chlorine, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; Z ¹ , Z ² and Z ³ are independently represent a single _{bond, -CH 2 CH 2 -, -} CH = CH -, - C≡C -, - COO -, - OCO -, - CF 2 O -, - OCF 2 -, - CH 2 O- , -OCH _2- , or -CF = CF-; Sp ¹ is a single bond or an alkylene having 1 to 7 carbon atoms, and in this alkylene, at least one -CH ₂ -is -O-,- COO , Or may be replaced by -OCO-, at least one _-CH 2 CH ₂ - may be replaced by -CH = CH-, in these groups, at least one hydrogen is replaced by fluorine L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ , L ⁸ , L ⁹ , L ¹⁰ , L ¹¹ , L ¹² , L ¹³ , and L ¹⁴ are independently , Hydrogen, fluorine, methyl or ethyl; R ² and R ³ are independently hydrogen or methyl.   The liquid crystal composition according to claim 1 or 2, wherein the proportion of the first additive is in the range of 0.05% by weight to 10% by weight. The liquid crystal composition according to any one of claims 1 to 3, containing at least one compound selected from the group of compounds represented by formula (2) as a first component.

In formula (2), R ⁴ and R ⁵ 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 C and ring E are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine Or tetrahydropyran-2,5-diyl; ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5 - methyl-1,4-phenylene, it is a 3,4,5-trifluoro-2,6-diyl or 7,8-difluoro-chroman-2,6-diyl,; ^{Z 4} Oyo Z ⁵ is independently a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or a -OCO-; b is 1, 2 or 3, , 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 1 to 4, containing at least one compound selected from the group of compounds represented by formulas (2-1) to (2-22) as a first component. Composition.

In formulas (2-1) to (2-22), R ⁴ and R ⁵ 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 4 or 5, 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 1 to 6, containing at least one compound selected from the group of compounds represented by formula (3) as a second component.

In formula (3), R ⁶ and R ⁷ 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 to C 12 alkyl or C 2 to C 12 alkenyl in which at least one hydrogen is replaced by fluorine or chlorine; ring F and ring G are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ⁶ represents a single bond, -CH ₂ CH _2- , -CH ₂ O- , -OCH _2- , -COO-, or -OCO-; d is 1, 2 or 3; The liquid crystal according to any one of claims 1 to 7, comprising 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 ⁶ and R ⁷ 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 7 or 8, wherein the proportion of the second component is in the range of 10% by weight to 70% by weight. The liquid crystal composition according to any one of claims 1 to 9, comprising at least one compound selected from the group of polymerizable compounds represented by formula (4) as a second additive.

In the formula (4), ring J and ring P 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 substituted by alkyl having 1 to 12 carbon atoms; ring K 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 ⁷ and Z ⁸ independently is a single bond or alkylene having 1 to 10 carbon atoms, in the alkylene, at least one of _-CH 2 -, -O -, - CO -, - OO-, or it may be replaced by -OCO-, and at least one _-CH 2 CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, or _{-C (CH 3) = C (} CH 3) - may be replaced by, in these groups, at least one hydrogen may be replaced by fluorine or ^chlorine; P ^{1, P} 2, And P ³ is a polymerizable group; Sp ² , Sp ³ and Sp ⁴ are independently a single bond or alkylene having 1 to 10 carbons, and in this alkylene, at least one —CH ₂ — is , -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -is replaced by -CH = CH- or -C≡C- Even In these groups, at least one hydrogen may be replaced by fluorine or chlorine; q is 0, 1 or 2; j, k and p are independently 0, 1, 2 , 3 or 4 and the sum of j, k and p 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 10. The liquid crystal composition according to item 10.

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 second additive according to any one of claims 1 to 11, containing at least one compound selected from the group of polymerizable compounds represented by formulas (4-1) to (4-28). The liquid crystal composition as described.

In formulas (4-1) to (4-28), P ¹ , P ² and P ³ independently represent a polymerizable group represented by formulas (P-1) to (P-3) A group selected from the group wherein M ¹ , M ² and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is replaced by fluorine or chlorine C 1 -C 5 alkyl;

Sp ² , Sp ³ and Sp ⁴ 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-, and in these groups, at least 1 One hydrogen may be replaced by fluorine or chlorine.   The liquid crystal composition according to any one of claims 10 to 12, wherein the proportion of the second additive is in the range of 0.03% by weight to 10% by weight.   A liquid crystal display device comprising the liquid crystal composition according to any one of claims 1 to 13.   The liquid crystal display element according to claim 14, wherein an operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and a driving method of the liquid crystal display element is an active matrix method.   A liquid crystal composition according to any one of claims 1 to 13, wherein the first additive in the liquid crystal composition is polymerized, or the first and second additives are polymerized. Polymer-supported liquid crystal display device.   A liquid crystal composition according to any one of claims 1 to 13, wherein the first additive in the liquid crystal composition is polymerized, or the first and second additives are polymerized. Liquid crystal display device having no alignment film.   Use of the liquid crystal composition according to any one of claims 1 to 13 in a liquid crystal display device.   Use of the liquid crystal composition according to any one of claims 1 to 13 in a polymer supported alignment type liquid crystal display device.   Use of the liquid crystal composition according to any one of claims 1 to 13 in a liquid crystal display device having no alignment film.