JP6729395B2 - Liquid crystal composition and liquid crystal display device - Google Patents

Description

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

In a liquid crystal display device, classification based on the operation mode of liquid crystal molecules is performed by PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), and IPS. The modes include (in-plane switching), VA (vertical alignment), FFS (fringe field switching), and FPA (field-induced photo-reactive alignment). The classification based on the driving method of the element is PM (passive matrix) and AM (active matrix). PM is classified into static and multiplex, and AM is classified into TFT (thin film transistor) and MIM (metal insulator metal). TFTs are classified into amorphous silicon and polycrystal silicon. The latter is classified into a high temperature type and a low temperature type according to the manufacturing process. The light source-based classification is a reflective type that uses natural light, a transmissive type that uses a backlight, and a semi-transmissive type that uses both natural light and a backlight.

The liquid crystal display device contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the characteristics of this composition, an AM device having good characteristics can be obtained. The relationship between the two properties is summarized in Table 1 below. The characteristics of the composition will be further described based on a commercially available AM device. The temperature range of the nematic phase is related to the temperature range in which the device can be used. The preferred maximum temperature of the nematic phase is about 70°C or higher, and the preferred minimum temperature of the nematic phase is about -10°C or lower. The viscosity of the composition is related to the response time of the device. A short response time is preferable for displaying a moving image on the device. Response times as short as 1 millisecond are desirable. Therefore, a low viscosity in the composition is preferred. Small viscosities at low temperatures are even 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 optical anisotropy or a small optical anisotropy, that is, 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 for VA mode devices, and in the range of about 0.20 μm to about 0.30 μm for IPS mode or FFS mode devices. In these cases, a composition having a large optical anisotropy is preferable for a device having a small cell gap. A large dielectric anisotropy in the composition contributes to a low threshold voltage, a small power consumption and a large contrast ratio in the device. Therefore, large dielectric anisotropy is preferable. A large specific resistance in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a large specific resistance not only at room temperature in the initial stage but also at a temperature close to the maximum temperature of the nematic phase is preferable. A composition having a large specific resistance not only at room temperature but also at a temperature close to the maximum temperature of the nematic phase after being used for a long time is preferable. The stability of the composition against ultraviolet rays and heat is related to the life of the device. When this stability is high, the life of the device is long. Such characteristics are preferable for an AM element used in a liquid crystal projector, a liquid crystal television, or the like.

In a general-purpose liquid crystal display device, vertical alignment of liquid crystal molecules is achieved by a specific polyimide alignment film. In a polymer sustained alignment (PSA) type liquid crystal display element, the effect of a polymer is utilized. First, a composition containing a small amount of a polymerizable compound is injected into the device. Next, the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of the device. The polymerizable compound polymerizes to form a polymer network in the composition. In this composition, the orientation of liquid crystal molecules can be controlled by the polymer, so that the response time of the device is shortened and image sticking is improved. Such effects of the polymer can be expected in devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

On the other hand, in a liquid crystal display device having no alignment film, a liquid crystal composition containing a polymer and a polar compound is used. First, a composition containing a small amount of a polymerizable compound and a small amount of a polar compound is injected into the device. Here, the polar compound is adsorbed and arranged on the surface of the substrate. The liquid crystal molecules are aligned according to this arrangement. Next, the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of the device. Here, the polymerizable compound is polymerized to stabilize the alignment of liquid crystal molecules. In this composition, the orientation of the liquid crystal molecules can be controlled by the polymer and the polar compound, so that the response time of the device is shortened and image sticking is improved. Further, in the element having no alignment film, the step of forming the alignment film is unnecessary. Since there is no alignment film, the electrical resistance of the device does not decrease due to the interaction between the alignment film and the composition. Such an effect of the combination of the polymer and the polar compound can be expected in a device having a mode such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

A composition having a positive dielectric anisotropy is used in an AM device having a TN mode. A composition having a negative dielectric anisotropy is used in an AM device having a VA mode. A composition having a positive or 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 orientation type AM device. Examples of liquid crystal compositions having negative dielectric anisotropy are disclosed in Patent Documents 1 to 3 below.

JP, 2003-307720, A JP, 2004-131704, A European Patent Application Publication No. 1889894

One object of the present invention is a liquid crystal composition containing a polymerizable compound (or a polymer thereof) and a polar compound, and capable of achieving vertical alignment of liquid crystal molecules by the action of these compounds. Other objectives are high upper temperature of nematic phase, low lower temperature of nematic phase, small viscosity, suitable optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability to ultraviolet light, high heat resistance. A liquid crystal composition satisfying at least one property in properties such as high stability. Another object is a liquid crystal composition having a suitable balance between at least two properties. Another object is a liquid crystal display device containing such a composition. Another object is an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long life.

式（１）において、環Ａおよび環Ｃ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Ｂは、１，４−シクロへキシレン、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^１およびＺ^２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_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ_３）−、または−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｐ^１、Ｐ^２、およびＰ^３は、重合性基であり；Ｓｐ^１、Ｓｐ^２、およびＳｐ^３は独立して、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_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ａは０、１、または２であり；ｂ、ｃ、およびｄは独立して、０、１、２、３、または４であり；ただし、環Ａおよび環Ｃがフェニルであるとき、ａは１または２であり、そしてａが１であるとき、Ｓｐ^１およびＳｐ^３は単結合である。The present invention contains at least one polymerizable compound selected from the group of compounds represented by formula (1) as a first additive, at least one polar compound as a second additive, and a negative additive. And a liquid crystal display device containing the composition.

In formula (1), ring A and ring C are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidine-. 2-yl or pyridin-2-yl, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen. It may be replaced by alkyl having 1 to 12 carbons which is replaced by fluorine or chlorine; Ring B 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, and 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 may be replaced by an alkyl having 1 to 12 carbons in which fluorine or chlorine is replaced; Z ¹ and Z ² are independently a single bond or an alkylene having 1 to 10 carbons, and this alkylene In, at least one —CH ₂ — may be replaced by —O—, —CO—, —COO—, or —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 are polymerizable groups; Sp ¹ , Sp ² , and Sp ³ are independently a single bond or carbon. An alkylene of the numbers 1 to 10 in which at least one —CH ₂ — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, and at least one —CH ₂ —. CH ₂ -CH ₂ - is - CH=CH- or -C[identical to]C-, in which at least one hydrogen may be replaced by fluorine or chlorine; a is 0, 1, or 2; b , C, and d are independently 0, 1, 2, 3, or 4 provided that when Ring A and Ring C are phenyl, a is 1 or 2 and a is 1. Sometimes Sp ¹ and Sp ³ are single bonds.

One advantage of the present invention is a liquid crystal composition containing a polymerizable compound (or a polymer thereof) and a polar compound, and by these actions, vertical alignment of liquid crystal molecules can be achieved. Another advantage is that the nematic phase has a high upper temperature limit, the nematic phase has a low lower temperature limit, a small viscosity, a suitable optical anisotropy, a large negative dielectric anisotropy, a large specific resistance, a high stability against ultraviolet rays, and a high heat resistance. A liquid crystal composition satisfying at least one property in properties such as high stability. Another advantage is a liquid crystal composition that has a suitable balance between at least two properties. Another advantage is a liquid crystal display device containing such a composition. Another advantage is an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long life.

The usage of terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display device" may be abbreviated as "composition" and "device", respectively. “Liquid crystal display element” is a general 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 a liquid crystal phase, but it is a composition for the purpose of adjusting properties such as temperature range, viscosity and dielectric anisotropy of the nematic phase. It is a general term for the compounds mixed in the product. This compound has a 6-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-like. The “polymerizable compound” is a compound added for the purpose of forming a polymer in the composition.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. If necessary, additives such as an optically active compound, an antioxidant, an ultraviolet 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. It The liquid crystal compound and additives are mixed by 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 containing no additive even when the additive is added. The ratio (addition amount) of the additive is represented by a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive. Weight parts per million (ppm) may be used. The ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.

The “maximum temperature of the nematic phase” may be abbreviated as “maximum temperature”. The "minimum temperature of the nematic phase" may be abbreviated as "minimum temperature". “High specific resistance” means that the composition has a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and after a long time use, it has a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature. Means to have. “High voltage retention” means that the element has a large voltage retention not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and after a long time use, it has a large voltage not only at room temperature but also at a temperature close to the upper limit temperature. Means to have a retention rate. The characteristics of the composition or device may be examined before and after the aging test (including the accelerated deterioration test). The expression “increasing the dielectric anisotropy” means that, in the case of a composition having a positive dielectric anisotropy, that value increases positively, and a composition having a negative dielectric anisotropy. When it is a thing, it means that its value increases negatively.

The compound represented by the 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 the 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's is arbitrary. The expression "at least one'A' may be replaced by'B'" means that when the number of'A' is one, the position of'A' is arbitrary and the number of'A' is two. If there are more than one, those positions can be selected without limitation. This rule also applies to the expression "at least one'A' has been replaced by'B'".

In the chemical formulas of component compounds, the symbol of the terminal group R ¹ is used for a plurality of compounds. In these compounds, the two groups represented by any two R ¹ may be the same or different. For example, there is a case where R ^{1 of} the compound (2-1) is ethyl and R ¹ of the compound (2-2) is ethyl. In some cases, R ^{1 of} compound (2-1) is ethyl and R ¹ of compound (2-2) is propyl. This rule also applies to symbols such as other end groups. In formula (2), when e is 2, two rings D are present. In this compound, the two rings represented by the two rings D may be the same or different. This rule also applies to any two rings D when e is greater than 2. This rule also applies to other symbols. This rule also applies to the case where the compound (1-11) in such a two ^-Sp 2 -P ^2.

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, and represent rings such as six-membered ring and condensed ring. In Formula (1), the diagonal line that crosses this hexagon represents that any hydrogen on the ring may be replaced with a group such as -Sp ¹ -P ¹ . Subscripts such as'b' indicate the number of groups replaced. When the subscript'b' is 0, there is no such replacement. When the subscript'b' is 2 or more, a plurality of -Sp ¹ -P ¹ are present on the ring A. The plurality of groups represented by -Sp ¹ -P ¹ may be the same or different.

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

Expressions such as “at least one —CH ₂ — may be replaced with —O—” are used herein. In this _case, -CH ₂ -CH ₂ -CH ₂ - it is, -CH ₂ nonadjacent - may be converted _-O-CH 2 -O- to by is replaced by -O-. However, adjacent -CH ₂ - is not replaced by -O-. This is because this replacement produces —O—O—CH ₂ — (peroxide). In other words, this representation, and both _{- -} "may be replaced by -O- -CH 2 nonadjacent least two,""one -CH 2 is -O- in may be replaced" with means. This rule applies not only to replacement to -O-, but also to replacement of a divalent group such as -CH=CH- or -COO-. In the formula (5), R ⁵ is alkyl having 4 to 20 carbon atoms, and in this alkyl, at least one —CH ₂ — may be replaced with —CH═CH— or the like. This replacement increases the carbon number of the alkyl. In such a case, the maximum carbon number is 30. This rule also applies to alkylene, cycloalkylene and the like.

The alkyl of the liquid crystal compound is linear or branched and does not include cyclic alkyl. Straight-chain alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. Regarding the configuration of 1,4-cyclohexylene, trans is generally preferred to cis. Halogen means fluorine, chlorine, bromine, iodine. The preferred halogen is fluorine or chlorine. A more preferred halogen is fluorine.

The present invention includes the following items.

式（１）において、環Ａおよび環Ｃ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Ｂは、１，４−シクロへキシレン、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^１およびＺ^２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_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ_３）−、または−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｐ^１、Ｐ^２、およびＰ^３は、重合性基であり；Ｓｐ^１、Ｓｐ^２、およびＳｐ^３は独立して、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_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ａは０、１、または２であり；ｂ、ｃ、およびｄは独立して、０、１、２、３、または４であり；ただし、環Ａおよび環Ｃがフェニルであるとき、ａは１または２であり、そしてａが１であるとき、Ｓｐ^１およびＳｐ^３は単結合である。Item 1. It contains at least one polymerizable compound selected from the group of compounds represented by formula (1) as the first additive, contains at least one polar compound as the second additive, and has a negative dielectric constant difference. A liquid crystal composition having a directionality.

In formula (1), ring A and ring C are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidine-. 2-yl or pyridin-2-yl, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen. It may be replaced by alkyl having 1 to 12 carbons which is replaced by fluorine or chlorine; Ring B 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, and 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 may be replaced by an alkyl having 1 to 12 carbons in which fluorine or chlorine is replaced; Z ¹ and Z ² are independently a single bond or an alkylene having 1 to 10 carbons, and this alkylene In, at least one —CH ₂ — may be replaced by —O—, —CO—, —COO—, or —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 are polymerizable groups; Sp ¹ , Sp ² , and Sp ³ are independently a single bond or carbon. An alkylene of the numbers 1 to 10 in which at least one —CH ₂ — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, and at least one —CH ₂ —. CH ₂ -CH ₂ - is - CH=CH- or -C[identical to]C-, in which at least one hydrogen may be replaced by fluorine or chlorine; a is 0, 1, or 2; b , C, and d are independently 0, 1, 2, 3, or 4 provided that when Ring A and Ring C are phenyl, a is 1 or 2 and a is 1. Sometimes Sp ¹ and Sp ³ are single bonds.

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 2. In the formula (1), P ¹ , P ² , and P ³ are independently a polymerizable group selected from the group of groups represented by formulas (P-1) to (P-5). 1. The liquid crystal composition according to item 1.

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

式（１−１）から式（１−１２）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）で表される基の群から選択された重合性基であり、ここでＭ^１、Ｍ^２、およびＭ^３は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルであり；

Ｓｐ^１、Ｓｐ^２、およびＳｐ^３は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、そして少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。Item 3. Item 3. The liquid crystal composition according to item 1 or 2, wherein the first additive is at least one polymerizable compound selected from the group of compounds represented by formula (1-1) to formula (1-12).

In formulas (1-1) to (1-12), P ¹ , P ² , and P ³ are independently a group of groups represented by formulas (P-1) to (P-3). A polymerizable group of choice, wherein M ¹ , M ² , and M ³ are independently hydrogen, fluorine, C ¹ -C 5 alkyl, or at least one hydrogen is replaced by fluorine or chlorine. Alkyl having 1 to 5 carbon atoms;

Sp ¹ , Sp ² , and Sp ³ are independently a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO—, —OCO. -, or may be replaced by -OCOO-, and at least one _-CH 2 -CH ₂ - may be replaced by -CH = CH- or -C≡C-, and in the groups, at least One hydrogen may be replaced by fluorine or chlorine.

Item 4. Item 4. The liquid crystal composition according to any one of items 1 to 3, wherein the ratio of the first additive is in the range of 0.03 wt% to 10 wt% based on the weight of the liquid crystal composition.

式（２）において、Ｒ^１およびＲ^２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Ｄおよび環Ｆは独立して、１，４−シクロへキシレン、１，４−シクロへキセニレン、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Ｅは、２，３−ジフルオロ−１，４−フェニレン、２−クロロ−３−フルオロ−１，４−フェニレン、２，３−ジフルオロ−５−メチル−１，４−フェニレン、３，４，５−トリフルオロナフタレン−２，６−ジイル、または７，８−ジフルオロクロマン−２，６−ジイルであり；Ｚ^３およびＺ^４は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、または−ＯＣＯ−であり；ｅは、１、２、または３であり、ｆは０または１であり、そしてｅとｆとの和は３以下である。Item 5. Item 5. The liquid crystal composition according to any one of items 1 to 4, containing at least one compound selected from the group of compounds represented by formula (2) as a first component.

In formula (2), R ¹ and R ² 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. Yes; Ring D and Ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-wherein at least one hydrogen has been replaced by fluorine or chlorine. Phenylene, or tetrahydropyran-2,5-diyl; Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro- 5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl or 7,8-difluorochroman-2,6-diyl; Z ³ and Z ⁴ are independently Te single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or a -OCO-; e is 1, 2, or 3,, f is 0 or 1 and the sum of e and f is 3 or less.

式（２−１）から式（２−２１）において、Ｒ^１およびＲ^２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 6. Item 6. The liquid crystal composition according to any one of items 1 to 5, which contains at least one compound selected from the group of compounds represented by formulas (2-1) to (2-21) as a first component. Stuff.

In formulas (2-1) to (2-21), R ¹ and R ² are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or It is an alkenyloxy having 2 to 12 carbon atoms.

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

式（３）において、Ｒ^３およびＲ^４は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルであり；環Ｇおよび環Ｉは独立して、１，４−シクロへキシレン、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^５は、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、または−ＯＣＯ−であり；ｇは、１、２、または３である。Item 8. Item 8. The liquid crystal composition according to any one of items 1 to 7, containing at least one compound selected from the group of compounds represented by formula (3) as the second component.

In formula (3), R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, at least one hydrogen being replaced by fluorine or chlorine. An alkyl having 1 to 12 carbons, or an alkenyl having 2 to 12 carbons in which at least one hydrogen has been replaced by fluorine or chlorine; ring G and ring I are independently 1,4-cyclohexylene. , 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ⁵ is a single bond, —CH ₂ CH ₂ —, —CH ₂ O. _{-, - OCH 2 -, -} COO-, or a is -OCO-; g is 1, 2 or 3.

式（３−１）から式（３−１３）において、Ｒ^３およびＲ^４は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、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 9. Item 9. The liquid crystal composition according to any one of items 1 to 8, containing at least one compound selected from the group of compounds represented by formulas (3-1) to (3-13) as a second component. Stuff.

In formulas (3-1) to (3-13), R ³ and R ⁴ are independently at least alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least Alkyl having 1 to 12 carbons in which 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.

Item 10. Item 10. The liquid crystal composition according to item 8 or 9, wherein the ratio of the second component is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition.

Item 11. Item 11. The liquid crystal composition according to any one of items 1 to 10, wherein the second additive is a polar compound having a polar group having a hetero atom selected from nitrogen, oxygen, sulfur, and phosphorus.

式（４）において、ＭＥＳは、少なくとも１つの環を有するメソゲン基であり；式（５）において、Ｒ^５は炭素数４から２０のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＨ−、−ＣＨ＝ＣＦ−、−Ｃ≡Ｃ−、または炭素数３から８のシクロアルキレン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；式（４）および式（５）において、Ｒ^６は、ＯＨ構造の酸素原子、ＳＨ構造の硫黄原子、および第一級、第二級、または第三級のアミン構造の窒素原子の少なくとも１つを有する極性基であり；ｈは、１または２である。Item 12. Item 12. The liquid crystal composition according to any one of items 1 to 11, containing at least one polar compound selected from the group of compounds represented by formula (4) and formula (5) as the second additive.

In the formula (4), MES is a mesogenic group having at least one ring; in the formula (5), R ⁵ is alkyl having 4 to 20 carbons, and in this alkyl, at least one —CH ₂ —. May be replaced with -CH=CH-, -CF=CH-, -CH=CF-, -C[identical to]C-, or cycloalkylene having 3 to 8 carbon atoms, and in these groups, at least one Hydrogen may be replaced by fluorine or chlorine; in the formulas (4) and (5), R ⁶ is an oxygen atom of an OH structure, a sulfur atom of a SH structure, and a primary, secondary, or A polar group having at least one nitrogen atom of a tertiary amine structure; h is 1 or 2.

式（４−１）において、環Ｊおよび環Ｋは独立して、炭素数６から２５の芳香族基、炭素数５から２５の複素芳香族基、炭素数３から２５の脂環式基、または炭素数４から２５の複素脂環式基であり、これらの基は縮合環であってもよく、これらの基において、少なくとも１つの水素は基Ｔで置き換えられてもよく、ここで基Ｔは、−ＯＨ、−（ＣＨ_２）_ｊ−ＯＨ、ハロゲン、−ＣＮ、−ＮＯ_２、−ＮＣＯ、−ＮＣＳ、−ＯＣＮ、−ＳＣＮ、−Ｃ（＝Ｏ）Ｎ（Ｒ^０）_２、−Ｃ（＝Ｏ）Ｒ^０、−Ｎ（Ｒ^０）_２、−（ＣＨ_２）_ｊ−Ｎ（Ｒ^０）_２、炭素数６から２０のアリール、炭素数６から２０のヘテロアリール、炭素数１から２５のアルキル、炭素数１から２５のアルコキシ、炭素数２から２５のアルキルカルボニル、炭素数２から２５のアルコキシカルボニル、炭素２から２５のアルキルカルボニルオキシ、または炭素数２から２５のアルコキシカルボニルオキシであり、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく、ここでＲ^０は、水素または炭素数１から１２のアルキルであり、ｊは、１、２、３、または４であり；Ｚ^６は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−ＯＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＳＣＨ_２−、−ＣＨ_２Ｓ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＦ_２Ｓ−、−ＳＣＦ_２−、−（ＣＨ_２）_ｊ−、−ＣＦ_２ＣＨ_２−、−ＣＨ_２ＣＦ_２−、−（ＣＦ_２）_ｊ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−Ｃ（Ｒ^０）_２、または単結合であり、ここでＲ^０は、水素または炭素数１から１２のアルキルであり、ｊは、１、２、３、または４であり；Ｒ^６は、炭素数１から２５のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は、−ＮＲ^０−、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、または炭素数３から８のシクロアルキレンで置き換えられてもよく、ここでＲ^０は、水素または炭素数１から１２のアルキルであり、少なくとも１つの第三級炭素（＞ＣＨ−）は、窒素（＞Ｎ−）で置き換えられてもよく、そして少なくとも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、ただしＲ^６は、少なくとも１つの、ＯＨ構造の酸素原子、ＳＨ構造の硫黄原子、または第一級、第二級、または第三級のアミン構造の窒素原子を有し；Ｒ^７は、水素、ハロゲン、炭素数１から２５のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は、−ＮＲ^０−、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、または炭素数３から８のシクロアルキレンで置き換えられてもよく、そして少なくとも１つの第三級炭素（＞ＣＨ−）は、窒素（＞Ｎ−）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、ここでＲ^０は、水素または炭素数１から１２のアルキルであり；ｉは、０、１、２、３、４、または５である。Item 13. Item 13. The liquid crystal composition according to any one of items 1 to 12, containing at least one compound selected from the group of compounds represented by formula (4-1) as a second additive.

In formula (4-1), ring J and ring K are independently an aromatic group having 6 to 25 carbon atoms, a heteroaromatic group having 5 to 25 carbon atoms, an alicyclic group having 3 to 25 carbon atoms, Or a heteroalicyclic group having 4 to 25 carbon atoms, which may be a condensed ring, in which at least one hydrogen may be replaced by a group T, wherein the group T _{is, -OH, - (CH 2)} j -OH, _{halogen, -CN, -NO 2, -NCO,} -NCS, -OCN, -SCN, -C (= O) N (R 0) 2, -C _{^{(= O) R 0, -N}} (R 0) 2, - (CH 2) j -N (R 0) 2, aryl having 6 to 20 carbon atoms, heteroaryl of from 6 to 20 carbon atoms, having a carbon number of 1 25 alkyl, 1 to 25 alkoxy, 2 to 25 alkylcarbonyl, 2 to 25 alkoxycarbonyl, 2 to 25 alkylcarbonyloxy, or 2 to 25 alkoxycarbonyloxy. And in these groups, at least one hydrogen may be replaced by fluorine or chlorine, wherein R ⁰ is hydrogen or alkyl having 1 to 12 carbons and j is 1, 2, 3, or it is a ^4; Z 6 is, -O -, - S -, - CO -, - CO-O -, - OCO -, - OCO-O -, - OCH 2 -, - CH 2 O-, _{-SCH 2 -, - CH 2 S} -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - (CH 2) j -, - CF 2 CH 2 -, - CH _{2 CF 2 -, - (CF} 2) j -, - CH = CH -, - CF = CF -, - C≡C -, - CH = CH-COO -, - OCO-CH = CH -, - C ( R ⁰ ) ₂ or a single bond, wherein R ⁰ is hydrogen or alkyl having 1 to 12 carbons, j is 1, 2, 3, or 4; R ⁶ is 1 carbon from alkyl of 25, and in the alkyl, at least one of _-CH 2 ^-, -NR 0 -, - O - , - S -, - CO -, - COO -, - OCO -, - OCOO-, or It may be replaced by cycloalkylene having 3 to 8 carbons, wherein R ⁰ is hydrogen or alkyl having 1 to 12 carbons, and at least one tertiary carbon (>CH-) is nitrogen (>). N-), and at least one hydrogen is replaced by fluorine or chlorine. R ⁶ may have at least one oxygen atom of OH structure, sulfur atom of SH structure, or nitrogen atom of primary, secondary, or tertiary amine structure. R ⁷ is hydrogen, halogen, alkyl having 1 to 25 carbon atoms, and in this alkyl, at least one —CH ₂ — is —NR ⁰ —, —O—, —S—, —CO—, —. CO-O-, -O-CO-, -O-CO-O-, or cycloalkylene having 3 to 8 carbon atoms, and at least one tertiary carbon (>CH-) is It may be replaced by nitrogen (>N-), in which at least one hydrogen may be replaced by fluorine or chlorine, wherein R ⁰ is hydrogen or alkyl having 1 to 12 carbons. Yes; i is 0, 1, 2, 3, 4, or 5.

式（５−１）において、Ｒ^５は、炭素数４から２０のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＨ−、−ＣＨ＝ＣＦ−、−Ｃ≡Ｃ−、または炭素数３から８のシクロアルキレンで置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｒ^６は、炭素数１から２５のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は、−ＮＲ^０−、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、または炭素数３から８のシクロアルキレンで置き換えられてもよく、ここでＲ^０は、水素または炭素数１から１２のアルキルであり、少なくとも１つの第三級炭素（＞ＣＨ−）は、窒素（＞Ｎ−）で置き換えられてもよく、そして少なくとも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、ただしＲ^６は、少なくとも１つの、ＯＨ構造の酸素原子、ＳＨ構造の硫黄原子、または第一級、第二級、または第三級のアミン構造の窒素原子を有する。Item 14. Item 13. The liquid crystal composition according to any one of items 1 to 12, containing at least one polar compound selected from the group of compounds represented by formula (5-1) as a second additive.

In Formula (5-1), R ⁵ is alkyl having 4 to 20 carbon atoms, and in this alkyl, at least one —CH ₂ — is —CH═CH—, —CF═CH—, —CH═. CF-, -C≡C-, or C3-C8 cycloalkylene may be substituted, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine; R ⁶ is alkyl of 1 to 25 carbon atoms, in the alkyl, at least one of _-CH 2 ^-, -NR 0 -, - O - , - S -, - CO -, - COO -, - OCO -, - OCOO Or may be replaced by cycloalkylene having 3 to 8 carbons, wherein R ⁰ is hydrogen or alkyl having 1 to 12 carbons, and at least one tertiary carbon (>CH-) is It may be replaced by nitrogen (>N-) and at least one hydrogen may be replaced by fluorine or chlorine, provided that R ⁶ is at least one oxygen atom of OH structure, sulfur atom of SH structure. Or having a nitrogen atom of a primary, secondary, or tertiary amine structure.

式（Ａ１）から式（Ａ４）において、Ｓｐ^４、Ｓｐ^６、およびＳｐ^７は独立して、単結合または基（−Ｓｐ’’−Ｘ’’−）であり、ここで、Ｓｐ’’は、炭素数１から２０のアルキレンであり、このアルキレンにおいて少なくとも１つの−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＮＨ−、−Ｎ（Ｒ^０）−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ、−Ｏ−ＣＯ−Ｏ−、−Ｓ−ＣＯ−、−ＣＯ−Ｓ−、−Ｎ（Ｒ^０）−ＣＯ−Ｏ−、−Ｏ−ＣＯ−Ｎ（Ｒ^０）−、−Ｎ（Ｒ^０）−ＣＯ−Ｎ（Ｒ^０）−、−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、塩素、または−ＣＮで置き換えられてもよく、そしてＸ’’は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−Ｎ（Ｒ^０）−、−Ｎ（Ｒ^０）−ＣＯ−、−Ｎ（Ｒ^０）−ＣＯ−Ｎ（Ｒ^０）−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＳＣＨ_２−、−ＣＨ_２Ｓ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＦ_２Ｓ−、−ＳＣＦ_２−、−ＣＦ_２ＣＨ_２−、−ＣＨ_２ＣＦ_２−、−ＣＦ_２ＣＦ_２−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝ＣＲ^０−、−ＣＹ^２＝ＣＹ^３−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＣＨ＝ＣＨ−、または単結合であり、ここでＲ^０は、水素または炭素数１から１２のアルキルであり、Ｙ^２およびＹ^３は独立して、水素、フッ素、塩素、または−ＣＮであり；Ｓｐ^５は、＞ＣＨ−、＞ＣＲ^１１−、＞Ｎ−、または＞Ｃ＜であり；Ｘ^１は、−ＯＨ、−ＯＲ^１１、−ＣＯＯＨ、−ＮＨ_２、−ＮＨＲ^１１、−Ｎ（Ｒ^１１）_２、−ＳＨ、−ＳＲ^１１、

であり、ここでＲ^０は、水素または炭素数１から１２のアルキルであり；Ｘ^２は、−Ｏ−、−ＣＯ−、−ＮＨ−、−ＮＲ^１１−、−Ｓ−、または単結合であり；Ｚ^７は、炭素数１から１５のアルキレン、炭素数５または６の脂環式基、またはこれらの組み合わせであり、これらの基において、少なくとも１つの水素は、−ＯＨ、−ＯＲ^１１、−ＣＯＯＨ、−ＮＨ_２、−ＮＨＲ^１１、−Ｎ（Ｒ^１１）_２、フッ素、または塩素で置き換えられてもよく；Ｒ^１１は、炭素数１から１５のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、または−Ｏ−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；環Ｌは、炭素数６から２５の芳香族基または炭素数３から２５の脂環式基であり、これらの基は縮合環であってもよく、これらの基において、１つから３つの水素はＲ^Ｌで置き換えられてもよく；Ｒ^Ｌは、−ＯＨ、−（ＣＨ_２）_ｊ−ＯＨ、フッ素、塩素、−ＣＮ、−ＮＯ_２、−ＮＣＯ、−ＮＣＳ、−ＯＣＮ、−ＳＣＮ、−Ｃ（＝Ｏ）Ｎ（Ｒ^０）_２、−Ｃ（＝Ｏ）Ｒ^０、−Ｎ（Ｒ^０）_２、−（ＣＨ_２）_ｊ−Ｎ（Ｒ^０）_２、−ＳＨ、−ＳＲ^０、炭素数６から２０のアリール、炭素数６から２０のへテロアリール、炭素数１から２５のアルキル、炭素数１から２５のアルコキシ、炭素数２から２５のアルキルカルボニル、炭素数２から２５のアルコキシカルボニル、炭素数２から２５のアルキルカルボニルオキシ、または炭素数２から２５のアルコキシカルボニルオキシであり、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく、ここでＲ^０は、水素または炭素数１から１２のアルキルであり、ｊは、１、２、３、または４であり；ｋは、０、１、２、または３であり；ｍは、２、３、４、または５である。Item 15. In the formula (4) and the formula (5) according to the item 12, any one of the items 12 to 14, wherein R ⁶ is a group represented by any one of the formula (A1) to the formula (A4). The liquid crystal composition according to item 1.

In formulas (A1) to (A4), Sp ⁴ , Sp ⁶ , and Sp ⁷ are independently a single bond or a group (—Sp″—X″—), where Sp″ is , C 1-20 alkylene, and in this alkylene, at least one —CH ₂ — is —O—, —S—, —NH—, —N(R ⁰ )—, —CO—, —CO—. O-, -O-CO, -O-CO-O-, -S-CO-, -CO-S-, -N( ^R0 )-CO-O-, -O-CO-N( ^R0 ). -, -N( ^R0 )-CO-N( ^R0 )-, -CH=CH-, or -C[identical to]C-, in which at least one hydrogen is fluorine, Chlorine, or -CN may be substituted, and X'' is -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, ^{-CO-N (R 0) -} , - N (R 0) -CO -, - N (R 0) -CO-N (R 0) -, - OCH 2 -, - CH 2 O -, - SCH 2 _{-, - CH 2 S -,} - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 - , -CH = N -, - N = CH -, - N = N -, - CH = CR 0 -, - CY 2 = CY 3 -, - C≡C -, - CH = CH-CO-O-, -O-CO-CH=CH-, or a single bond, wherein R ⁰ is hydrogen or alkyl having 1 to 12 carbons, Y ² and Y ³ are independently hydrogen, fluorine, chlorine, or be -CN; Sp ^{5 is,> CH -,> CR 11} -,> N-, or> is C ^<; X 1 _{^{is, -OH, -OR 11, -COOH,}} -NH 2, -NHR _{^{11, -N (R 11) 2}} , -SH, -SR 11,

Wherein R ⁰ is hydrogen or alkyl having 1 to 12 carbons; X ² is —O—, —CO—, —NH—, —NR ¹¹ —, —S—, or a single bond. Yes; Z ⁷ is alkylene having 1 to 15 carbons, an alicyclic group having 5 or 6 carbons, or a combination thereof, and in these groups, at least one hydrogen is —OH, —OR ¹¹ , or ^{_{-COOH, -NH 2, -NHR 11,}} -N (R 11) 2, fluorine or may be replaced by ^{chlorine,; R 11} is alkyl of 1 to 15 carbon atoms, in the alkyl, at least one One —CH ₂ — may be replaced by —C≡C—, —CH═CH—, —COO—, —OCO—, —CO—, or —O—, and in these groups, at least one Hydrogen may be replaced by fluorine or chlorine; ring L is an aromatic group having 6 to 25 carbon atoms or an alicyclic group having 3 to 25 carbon atoms, and these groups may be condensed rings. well, and in the groups, one to three hydrogen may be replaced by ^{R L; R} L _{is, -OH, - (CH 2)} j -OH, fluorine, chlorine, -CN, _-NO 2, ^{-NCO, -NCS, -OCN, -SCN,} -C (= O) N (R 0) 2, -C (= O) R 0, -N (R 0) 2, - (CH 2) j -N (R ⁰ ) ₂ , —SH, —SR ⁰ , aryl having 6 to 20 carbon atoms, heteroaryl having 6 to 20 carbon atoms, alkyl having 1 to 25 carbon atoms, alkoxy having 1 to 25 carbon atoms, and having 2 carbon atoms 25 alkylcarbonyl, C2 to C25 alkoxycarbonyl, C2 to C25 alkylcarbonyloxy, or C2 to C25 alkoxycarbonyloxy, in which at least one hydrogen is fluorine or It may be replaced by chlorine, wherein R ⁰ is hydrogen or alkyl having 1 to 12 carbons, j is 1, 2, 3, or 4; k is 0, 1, 2, or 3; m is 2, 3, 4, or 5.

式（４−１−１）から式（４−１−４）において、環Ｊおよび環Ｋは独立して、１，４−シクロへキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２−フルオロ−１，３−フェニレン、２−エチル−１，４−フェニレン、２，６−ジエチル−１，４−フェニレン、２−トリフルオロメチル−１，４−フェニレン、２，３−ジフルオロ−１，４−フェニレン、２，５−ジフルオロ−１，４−フェニレン、２，６−ジフルオロ−１，４−フェニレン、または、２，３，５，６−テトラフルオロ−１，４−フェニレンであり；環Ｌは、シクロヘキシルまたはフェニルであり；Ｚ^６は、単結合、エチレン、またはカルボニルオキシであり；Ｚ^７は、単結合、炭素数１から１５のアルキレン、炭素数５または６の脂環式基、またはこれらの組み合わせであり、これらの基において、少なくとも１つの水素は、−ＯＨ、−ＯＲ^１１、−ＣＯＯＨ、−ＮＨ_２、−ＮＨＲ^１１、−Ｎ（Ｒ^１１）_２、またはハロゲンで置き換えられてもよく、Ｒ^１１は、炭素数１から１５のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−Ｏ−、または−ＮＨ−で置き換えられてもよく；Ｓｐ^４は、単結合、エチレン、プロピレン、またはメチレンオキシであり；Ｓｐ^７は、単結合、または炭素数１から５のアルキレンであり、このアルキレンにおいて−ＣＨ_２−は−Ｏ−または−ＮＨ−で置き換えられてもよく；Ｒ^７は、炭素数１から８のアルキルまたはフッ素であり；ｉは、０、１、２、３、４、または５であり；Ｘ^１は−ＯＨ、−ＣＯＯＨ、−ＳＨ、−ＯＣＨ_３、または−ＮＨ_２であり；Ｘ^２は単結合または−Ｏ−である。 Item 16. Item 14. The liquid crystal composition according to item 13, wherein the second additive is at least one compound selected from the group of compounds represented by formula (4-1-1) to formula (4-1-4).

In formulas (4-1-1) to (4-1-4), ring J and ring K are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4. -Phenylene, 2-fluoro-1,3-phenylene, 2-ethyl-1,4-phenylene, 2,6-diethyl-1,4-phenylene, 2-trifluoromethyl-1,4-phenylene, 2,3 -Difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, or 2,3,5,6-tetrafluoro-1,4- Phenylene; ring L is cyclohexyl or phenyl; Z ⁶ is a single bond, ethylene, or carbonyloxy; Z ⁷ is a single bond, alkylene having 1 to 15 carbons, C 5 or 6 cycloaliphatic radical, or a combination thereof, in these groups, at least one of _{^{hydrogen, -OH, -OR 11, -COOH,}} -NH 2, -NHR 11, -N (R 11) 2 , or, R ¹¹ may be substituted with halogen, and R ¹¹ is alkyl having 1 to 15 carbons, and in this alkyl, at least one —CH ₂ — is —C≡C—, —CH═CH—, —COO—. , -OCO -, - CO -, - O-, or -NH- with may be substituted; Sp ⁴ is a single bond, ethylene, propylene or methyleneoxy,; Sp ⁷ is a single bond, or carbon from Equation 1 is an alkylene of 5, -CH ₂ in the alkylene - is -O- or -NH- with may be substituted; ^{R 7} is alkyl or fluorine having a carbon number of 1 to 8; i is 0,1,2,3,4, or a ^5; X 1 is -OH, -COOH, -SH, it is -OCH ₃ or -NH _2,; ^{X 2} is a single bond or -O-.

式（５−１−１）から式（５−１−２９）において、Ｒ^５は、炭素数４から２０のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＨ−、−ＣＨ＝ＣＦ−、−Ｃ≡Ｃ−、または炭素数３から８のシクロアルキレンで置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。Item 17. Item 15. The liquid crystal composition according to item 14, wherein the second additive is at least one compound selected from the group of compounds represented by formulas (5-1-1) to (5-1-29).

In formulas (5-1-1) to (5-1-29), R ⁵ is alkyl having 4 to 20 carbon atoms, and in this alkyl, at least one —CH ₂ — is —CH═CH. -, -CF=CH-, -CH=CF-, -C≡C-, or cycloalkylene having 3 to 8 carbon atoms, in which at least one hydrogen is fluorine or chlorine. May be replaced with.

Item 18. Item 18. The liquid crystal composition according to any one of items 1 to 17, wherein the proportion of the second additive is less than 10% by weight based on the weight of the liquid crystal composition.

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

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

Item 21. Item 19. A polymer-supported alignment type liquid crystal display device, comprising the liquid crystal composition according to any one of items 1 to 18, wherein the polymerizable compound in the liquid crystal composition is polymerized.

Item 22. Item 19. A liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 18, wherein the polymerizable compound in the liquid crystal composition is polymerized, and which has no alignment film.

Item 23. Item 18. Use of the liquid crystal composition according to any one of items 1 to 18 in a liquid crystal display device.

Item 24. Item 18. Use of the liquid crystal composition according to any one of items 1 to 18 in a polymer-supported alignment type liquid crystal display device.

Item 25. Item 18. Use of the liquid crystal composition according to any one of items 1 to 18 in a liquid crystal display device having no alignment film.

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

The present invention also includes the following items. (C) Compounds (5) to (7) described in JP-A-2006-199941 are liquid crystal compounds having a positive dielectric anisotropy, but at least selected from the group of these compounds. A composition as described above containing one compound. (D) The above composition containing at least two polymerizable compounds (1). (E) The above composition further containing a polymerizable compound different from the above polymerizable compound (1). (F) One, two or at least three additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor and a polar compound. The above composition containing. (G) An AM device containing the above composition. (H) A device containing the above composition and having a mode of TN, ECB, OCB, IPS, FFS, VA, or FPA. (I) A transmissive element 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 will be explained. Third, the combination of components in the composition, the preferable ratio of the components and the basis thereof will be described. Fourthly, a preferred form of the component compounds will be described. Fifth, preferable component compounds are shown. Sixth, the additives that may be added to the composition will be described. Seventh, the method of synthesizing the component compounds will be explained. Finally, the use of the composition will be explained.

First, the composition of the composition will be described. The composition of the present invention is classified into composition A and composition B. The composition A may further contain other liquid crystal compounds, additives and the like in addition to the liquid crystal compounds selected from the compound (2) and the compound (3). 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. Additives are optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like.

The composition B consists essentially of a liquid crystal compound selected from the compound (2) and the compound (3). “Substantially” means that the composition may contain an additive, but contains no other liquid crystal compound. Composition B has fewer components than composition A. From the viewpoint of cost reduction, the composition B is preferable to the composition A. The composition A is preferable to the composition B from the viewpoint that the characteristics can be further adjusted by mixing with other liquid crystal compounds.

Secondly, the main properties of the component compounds and the main effects of the compounds on the properties of the composition will be explained. The main characteristics of the component compounds are summarized in Table 2 based on the effects of the present invention. In the symbols in Table 2, L means large or high, M means medium, and S means small or low. The symbols L, M, S are classifications based on qualitative comparisons among the component compounds, and the symbol 0 means that the value is zero or close to zero.

The main effects of the component compounds on the properties of the composition when the component compounds are mixed with the composition are as follows. The compound (1) gives a polymer by polymerization. This polymer stabilizes the alignment of the liquid crystal molecules, thus shortening the response time of the device and improving the image sticking. The compound (2) increases the dielectric anisotropy and lowers the minimum temperature. The compound (3) reduces the viscosity. The compound (4) and the compound (5) are adsorbed on the substrate surface by the action of the polar group, and control the alignment of the liquid crystal molecules. From the viewpoint of alignment of liquid crystal molecules, the polymer of compound (1) is effective. Compound (4) or compound (5) is also effective. The compound (1) and the compound (4), or the combination of the compound (1) and the compound (5) is more effective. A synergistic effect can be expected by this combination. This combination can be expected to have better long-term stability than compound (4) alone or compound (5) alone.

Third, the combination of components in the composition, the preferable ratio of the components and the basis thereof will be described. A preferred combination of components in the composition is compound (1)+compound (2)+compound (3)+compound (4), compound (1)+compound (2)+compound (3)+compound (5), or Compound (1)+Compound (2)+Compound (3)+Compound (4)+Compound (5). A more preferable combination is Compound (1)+Compound (2)+Compound (3)+Compound (4).

The compound (1) is added to the composition for the purpose of adapting to a polymer-supported orientation type device. The preferable ratio of the compound (1) is about 0.03% by weight or more for improving the long-term reliability of the device, and about 10% by weight or less for preventing display failure of the device. A more desirable ratio is in the range of approximately 0.1% by weight to approximately 2% by weight. A particularly desirable ratio is in the range of approximately 0.2% by weight to approximately 1.0% by weight.

A desirable ratio of the compound (2) is about 10% by weight or more for increasing the dielectric anisotropy, and about 90% by weight or less for decreasing the minimum temperature. A more desirable ratio is in the range of approximately 20% by weight to approximately 85% by weight. A particularly desirable ratio is in the range of approximately 30% by weight to approximately 85% by weight.

A desirable ratio of the compound (3) is about 10% by weight or more for increasing the maximum temperature or decreasing the minimum temperature, and about 90% by weight or less for increasing the dielectric anisotropy. A more desirable ratio is in the range of approximately 15% by weight to approximately 75% by weight. A particularly desirable ratio is in the range of approximately 15% by weight to approximately 60% by weight.

The compound (4) or the compound (5) is added to the composition for the purpose of controlling the alignment of liquid crystal molecules. A desirable ratio of the compound (4) or the compound (5) is about 0.05% by weight or more for orienting liquid crystal molecules, and about 10% by weight or less for preventing display failure of the device. A more desirable ratio is in the range of approximately 0.1% by weight to approximately 7% by weight. A particularly desirable ratio is in the range of approximately 0.5% by weight to approximately 5% by weight.

Fourthly, a preferred form of the component compounds will be described. In Formula (1), P ¹ , P ² , and P ³ are independently a polymerizable group. Preferred P ¹ , P ² or P ³ is a polymerizable group selected from the group of groups represented by formula (P-1) to formula (P-5). More desirable 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 preferred 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 line in the formulas (P-1) to (P-5) indicates the binding site.

In formulas (P-1) to (P-5), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is fluorine or chlorine. Is an alkyl having 1 to 5 carbon atoms replaced by. Preferred M ¹ , M ² or M ³ is hydrogen or methyl for increasing the reactivity. More preferred M ¹ is hydrogen or methyl, and more preferred M ² or M ³ is hydrogen.

Sp ¹ , Sp ² , and Sp ³ are independently a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO—, —OCO. -, or may be replaced by -OCOO-, and at least one _-CH 2 -CH ₂ - may be replaced by -CH = CH- or -C≡C-, and in the groups, at least One hydrogen may be replaced by fluorine or chlorine. Preferred ^Sp 1, Sp ² or Sp ^3, is a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CO-CH = CH-, or -CH=CH-CO-. More desirable Sp ¹ , Sp ² or Sp ³ is a single bond. However, when Ring A and Ring C are phenyl, Sp ¹ and Sp ³ are single bonds.

Ring A and ring C are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-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. It may be replaced with an alkyl having 1 to 12 carbons. Preferred ring A or ring C is phenyl. Ring B 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 replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine May be. Preferred ring B is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ¹ and Z ² are independently a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —CO—, —COO—, or —. may be replaced by OCO-, 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 1} or ^{Z 2} is a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or -OCO-. More desirable Z ¹ or Z ² is a single bond.

a is 0, 1, or 2. Preferred a is 0 or 1. b, c, and d are independently 0, 1, 2, 3, or 4, and the sum of b, c, and d is 1 or more. Preferred b, c, and d are 1 or 2. Provided that when Ring A and Ring C are phenyl, a is 1 or 2. Therefore, polymerizable compounds having a biphenyl skeleton are excluded.

In the formulas (2) and (3), R ¹ and R ² are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 to 12 is alkenyloxy. Desirable R ¹ or R ² is alkyl having 1 to 12 carbons for increasing the stability against ultraviolet rays or heat, and alkoxy having 1 to 12 carbons for increasing the dielectric anisotropy. R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and 1 to carbons in which at least one hydrogen is replaced by fluorine or chlorine. 12 alkyl or alkenyl having 2 to 12 carbons in which at least one hydrogen has been replaced by fluorine or chlorine. Preferred R ³ or R ⁴ is alkenyl having 2 to 12 carbons for decreasing the viscosity and alkyl having 1 to 12 carbons for increasing the stability against ultraviolet rays and heat. The alkyl of the liquid crystal compound is linear or branched and does not include cyclic alkyl. Straight-chain alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl.

Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More desirable alkyl is ethyl, propyl, butyl, pentyl, or heptyl for decreasing 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, It is 3-hexenyl, 4-hexenyl, or 5-hexenyl. More desirable alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for decreasing the viscosity. The preferred configuration of -CH=CH- in these alkenyls depends on the position of the double bond. Trans is preferable in the alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity. 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 desirable alkenyloxy is allyloxy or 3-butenyloxy for decreasing the viscosity.

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

Preferred examples of alkenyl in which at least one hydrogen has been 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. A more preferred example is 2,2-difluorovinyl or 4,4-difluoro-3-butenyl for decreasing the viscosity.

Ring D and ring F are 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 it is tetrahydropyran-2,5-diyl. Preferred examples of "1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine" include 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, or 2-chloro. It is -3-fluoro-1,4-phenylene. Preferred ring D or ring F is 1,4-cyclohexylene for decreasing the viscosity, tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and for increasing the optical anisotropy. It is 1,4-phenylene. Regarding the configuration of 1,4-cyclohexylene, trans is preferable to cis for increasing the maximum temperature. Tetrahydropyran-2,5-diyl is

Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4. It is 5-trifluoronaphthalene-2,6-diyl or 7,8-difluorochroman-2,6-diyl. Preferred ring E is 2,3-difluoro-1,4-phenylene for decreasing the viscosity, 2-chloro-3-fluoro-1,4-phenylene for decreasing the optical anisotropy, and the dielectric constant. It is 7,8-difluorochroman-2,6-diyl for increasing anisotropy.

Ring G and ring I are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. Preferred ring G or ring I is 1,4-cyclohexylene for decreasing the viscosity or increasing the maximum temperature, and 1,4-phenylene for decreasing the minimum temperature. Regarding the configuration of 1,4-cyclohexylene, trans is preferable to cis for increasing the maximum temperature.

Z ^{3, Z 4,} and ^{Z 5} are independently a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or -OCO-. Desirable Z ³ or Z ⁴ is a single bond for decreasing the viscosity, —CH ₂ CH ₂ — for decreasing the minimum temperature, and —CH ₂ O— or —OCH for increasing the dielectric anisotropy. _2- . Preferred Z ⁵ is a single bond for decreasing the viscosity, —CH ₂ CH ₂ — for decreasing the minimum temperature, and —COO— or —OCO— for increasing the maximum temperature.

e is 1, 2, or 3, f is 0 or 1, and the sum of e and f is 3 or less. Preferred e is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature. Preferred f is 0 for decreasing the viscosity and 1 for decreasing the minimum temperature. g is 1, 2, or 3. Preferred g is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.

In Formula (4) and Formula (5), R ⁶ is a polar group. The polar compound having a polar group is preferably stable because it is added to the composition. When a polar compound is added to the composition, it is preferred that this compound does not reduce the voltage holding ratio of the device. The polar compound preferably has low volatility. A preferable molar mass is 130 g/mol or more. A more preferred molar mass is in the range of 150 g/mol to 500 g/mol. Preferred polar compounds are acryloyloxy _{(-OCO-CH = CH 2)} , not having a polymerizable group such as a methacryloyloxy _{(-OCO- (CH 3) C =} CH 2).

The polar group has a non-covalent interaction with the surface of the glass substrate or the metal oxide film. Preferred polar groups have heteroatoms selected from the group of nitrogen, oxygen, sulfur and phosphorus. Preferred polar groups have at least one, or at least two of these heteroatoms. More preferred polar groups are hydrogens from compounds selected from the group of alcohols, primary, secondary and tertiary amines, ketones, carboxylic acids, thiols, esters, ethers, thioethers, and combinations thereof. It is a monovalent group derived by elimination. The structure of these groups may be linear, branched, cyclic, or a combination thereof. Particularly preferred polar groups have at least one OH-structure oxygen atom or a primary, secondary, or tertiary amine-structure nitrogen atom. The most preferred polar group is the hydroxy group (carbon-OH).

Examples of the polar group R ⁶ are groups represented by formula (A1) to formula (A4).

In formulas (A1) to (A4), Sp ⁴ , Sp ⁶ , and Sp ⁷ are independently a single bond or a group (—Sp″—X″—), and X″ is MES. Attached to a group or R ⁵ . Sp″ is alkylene having 1 to 20 carbon atoms, preferably alkylene having 1 to 12 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —S—, —NH—. , -N( ^R0 )-, -CO-, -CO-O-, -O-CO, -O-CO-O-, -S-CO-, -CO-S-, -N( ^R0 ). -CO-O-, -O-CO-N( ^R0 )-, -N( ^R0 )-CO-N( ^R0 )-, -CH=CH-, or -C≡C-. Alternatively, in these groups, at least one hydrogen may be replaced by fluorine, chlorine, or —CN, and X″ is —O—, —S—, —CO—, —CO—O—. , -O-CO-, -O-CO-O-, -CO-N( ^R0 )-, -N( ^R0 )-CO-, -N( ^R0 )-CO-N( ^R0 )-. _{, -OCH 2 -, - CH 2} O -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CF 2 CH 2 _{-, - CH 2 CF 2 -} , - CF 2 CF 2 -, - CH = N -, - N = CH -, - N = N -, - CH = CR 0 -, - CY 2 = CY 3 -, - C≡C-, -CH=CH-CO-O-, -O-CO-CH=CH-, or a single bond, wherein R ⁰ is hydrogen or alkyl having 1 to 12 carbons, and Y ² and Y ³ are independently hydrogen, fluorine, chlorine, or —CN. Preferred X '' is, -O -, - S -, - CO -, - COO -, - OCO -, - O-COO -, - CO-NR 0 -, - NR 0 -CO -, - NR 0 - CO-NR ⁰ -or a single bond. Sp ^{5 is,> CH -,> CR 11} -,> N-, or> is C <. That is, Sp ⁵ in formula (A2) is >CH—, >CR ¹¹ −, or >N—, and Sp ⁵ in formula (A3) is >C<.

Preferred Sp '' _{is, - (CH 2) p1 -} , - (CH 2 CH 2 O) q1 -CH 2 CH 2 -, - CH 2 CH 2 -S-CH 2 CH 2 -, or _-CH 2 CH ₂ -NHCH ₂ CH ₂ - and is, where p1 is an integer of 1 to 12, q1 is an integer from 1 to 3. Preferred groups (-Sp '' - X '' -) _{is, - (CH 2) p1 -} , - (CH 2) p1 -O -, - (CH 2) p1 -O-CO -, - (CH 2) _p1- O-CO-O-, where p1 and q1 have the meanings given above. More preferable group Sp'' is ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methylimino. Ethylene, 1-methylalkylene, ethenylene, propenylene, and butenylene.

であり、ここでＲ^１１は、炭素数１から１５のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、または−Ｏ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく、Ｒ^０は、水素または炭素数１から１２のアルキルである。X ^{1 _{is, -NH 2, -NHR 11, -N}} (R 11) 2, -OR 11, -OH, -COOH, -SH, -SR 11,

Wherein R ¹¹ is alkyl having 1 to 15 carbons, and in this alkyl, at least one —CH ₂ — is —C≡C—, —CH═CH—, —COO—, —OCO. -, -CO-, or -O- may be substituted, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine, and R ⁰ is hydrogen or C ^1-12 . It is alkyl.

X ² is —O—, —CO—, —NH—, —NR ¹¹ —, —S—, or a single bond, and Z ⁷ is an alkylene having 1 to 15 carbons, an aliphatic having 5 to 6 carbons. cyclic group, or represents a combination of at least one ring and alkylene, in these groups, at least one of _{^{hydrogen, -OH, -OR 11, -COOH,}} -NH 2, -NHR 11, -N ( It may be replaced by R ¹¹ ) ₂ , fluorine, or chlorine, where R ¹¹ has the meaning given above. k is 0, 1, 2, or 3.

Particularly preferred nitrogen-containing group ^{R 6} _{is, -NH 2, -NH- (CH 2} ) n3 H, - (CH 2) n -NH 2, - (CH 2) n -NH- (CH 2) n3 H, - _{NH- (CH 2) n -NH 2} , -NH- (CH 2) n -NH- (CH 2) n3 H, - (CH 2) n1 -NH- (CH 2) n2 -NH 2, - (CH _{2) n1 -NH- (CH 2)} n2 -NH- (CH 2) n3 H, -O- (CH 2) n -NH 2, - (CH 2) n1 -O- (CH 2) n -NH 2 _{, - (CH 2) n1 -NH-} (CH 2) n2 -OH, -O- (CH 2) n1 -NH- (CH 2) n2 -NH 2, -O- (CH 2) n1 -NH- ( CH _{2) n2} -OH, or _{- (CH 2) n1 -NH- (} CH 2) a _{n2 -NH- (CH 2) n3 H} , wherein n, n1, n2, and n3 are independently 1 Is an integer from 1 to 12, preferably 1, 2, 3, or 4.

Particularly preferred nitrogen-containing group ^R 6 _{is, -OH, - (CH 2)} n -OH, -O- (CH 2) n -OH, - [O- (CH 2) n1 -] n2 -OH, -COOH _{, - (CH 2) n -COOH} , -O- (CH 2) n -COOH _{or, - [O- (CH 2)} n1 -] is n2 -COOH, wherein n, n1, and n2 are independently Is an integer of 1 to 12, and preferably 1, 2, 3, or 4.

From the viewpoint of high solubility in the liquid crystal composition, R ⁶ is particularly preferably —OH or —NH ₂ . -OH is preferable to -O-, -CO-, or -COO- because it has a high anchoring force. Groups having multiple heteroatoms (nitrogen, oxygen) are particularly preferred. The compound having such a polar group is effective even at a low concentration.

In the formula (4), MES is a mesogenic group having at least one ring. Mesogenic groups are well known to those of ordinary skill in the art. The mesogen group means a part that contributes to the formation of a liquid crystal phase when the compound has a liquid crystal phase (mesophase). A preferable example of the compound (4) is the compound (4-1).

In formula (4-1), ring J and ring K are independently an aromatic group having 6 to 25 carbon atoms, a heteroaromatic group having 5 to 25 carbon atoms, an alicyclic group having 3 to 25 carbon atoms, Or a heteroalicyclic group having 4 to 25 carbon atoms, which group may be a condensed ring, and in these groups, at least one hydrogen may be replaced by a group T. The preferred carbon number is from 4 to 25, these groups may be fused rings, in which at least one hydrogen may be replaced by a group T. The meaning of the group T is given at the end of this paragraph. Preferred ring J or ring K is 1,4-phenylene, naphthalene-1,4-diyl, or naphthalene-2,6-diyl (at least one tertiary carbon (>CH-) in these three groups is nitrogen (> N-) may be replaced by), 1,4-cyclohexylene (in this group, at least one -CH ₂ - may be replaced by -O- or -S-), 3 , 3′-bicyclobutylidene, 1,4-cyclohexenylene, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[ 3.3] Heptane-2,6-diyl, piperidine-1,4-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indane-2 ,5-diyl, octahydro-4,7-methanoindane-2,5-diyl, or perhydrocyclopenta[a]phenanthrene-3,17-diyl (especially gonane-3,17-diyl), in the group, may be at least one hydrogen is replaced by a group T, wherein the group T _{is, -OH, - (CH 2)} j -OH, _halogen, -CN, -NO 2, -NCO, -NCS, ^{_{-OCN, -SCN, -C (= O}} ) N (R 0) 2, -C (= O) R 0, -N (R 0) 2, - (CH 2) j -N (R 0) 2, Aryl or heteroaryl having 6 to 20 carbon atoms, alkyl, alkoxy having 1 to 25 carbon atoms, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy having 2 to 25 carbon atoms, and in these groups, at least One hydrogen may be replaced by fluorine or chlorine, wherein R ⁰ is hydrogen or alkyl having 1 to 12 carbons, and j is 1, 2, 3, or 4.

Z ⁶ represents a single bond, -O -, - S -, - CO -, - CO-O -, - OCO -, - OCO-O -, - OCH 2 -, - CH 2 O -, - SCH _{2 -, - CH 2 S -} , - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - (CH 2) j -, - CF 2 CH 2 -, - CH 2 CF _{2 -, - (CF 2)} j -, - CH = CH -, - CF = CF -, - C≡C -, - CH = CH-COO -, - OCO-CH = CH-, or -C (R ⁰ ) ₂₋ . R ⁰ is hydrogen or alkyl having 1 to 12 carbons, and j is 1, 2, 3, or 4. Preferred Z ⁶ is a single bond.

R ⁶ is alkyl having 1 to 25 carbon atoms, and in this alkyl, at least one —CH ₂ — is —NR ⁰ —, —O—, —S—, —CO—, —COO—, —OCO. -, -OCOO-, or cycloalkylene having 3 to 8 carbon atoms, wherein R ⁰ is hydrogen or alkyl having 1 to 12 carbon atoms, and at least one tertiary carbon (>CH). -) may be replaced by nitrogen (>N-), and at least one hydrogen may be replaced by fluorine or chlorine, provided that R ⁶ is an oxygen atom of OH structure, a sulfur atom of SH structure. , And at least one of the nitrogen atoms of the primary, secondary, or tertiary amine structure. Preferred ^{R 6} has at least one> NH, -OH or -SH,. R ⁷ is hydrogen, halogen, alkyl having 1 to 25 carbons, and in this alkyl, at least one —CH ₂ — is —NR ⁰ —, —O—, —S—, —CO—, —CO. -O-, -O-CO-, -O-CO-O-, or cycloalkylene having 3 to 8 carbon atoms, and at least one tertiary carbon (>CH-) is nitrogen. (>N-), in which at least one hydrogen may be replaced by fluorine or chlorine, wherein R ⁰ is hydrogen or alkyl having 1 to 12 carbons. .. Preferred R ⁷ is alkyl.

Aromatic group refers to aryl or substituted aryl. Heteroaromatic groups refer to heteroaryl or substituted heteroaryl. Heteroaryl represents an aromatic radical having at least one heteroatom. Aryl and heteroaryl may be either monocyclic or polycyclic. That is, these groups have at least one ring, which rings may be fused (eg, naphthyl), two rings may be covalently linked (eg, biphenyl), or fused rings and linked It may have a combination of rings. Preferred heteroaryls have at least one heteroatom selected from the group of nitrogen, oxygen, sulfur and phosphorus.

Preferred aryl or heteroaryl has 6 to 25 carbon atoms and may be a 5-membered ring, 6-membered ring or 7-membered ring. Preferred aryl or heteroaryl may be monocyclic, bicyclic or tricyclic. These groups may be condensed rings or may be substituted.

Preferred aryls are benzene, biphenyl, terphenyl, [1,1′:3′,1″]terphenyl, naphthalene, anthracene, binaphthyl, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene. , Indene, indenofluorene, and spirobifluorene are monovalent groups derived by removing one hydrogen.

Preferred heteroaryls are pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole. 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1 5-membered ring compounds such as 2,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, or pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2, One from six-membered ring compounds such as 4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine It is a monovalent group derived by removing hydrogen.

Preferred heteroaryls are indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphtheimidazole, phenanthrimidazole, pyridimidazole, pyrazineimidazole, quinoxalineimidazole, benzoxazole, naphthoxazole, anthroxax. Sol, phenanthrazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, Benzisoquinoline, acridine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthridine, phenanthroline, thieno[2,3b]thiophene, thieno[3,2b]thiophene, It is also a monovalent group derived by removing one hydrogen from a condensed ring compound such as dithienothiophene, isobenzothiophene, dibenzothiophene, and benzothiadiazothiophene. The preferred heteroaryl is also a monovalent group derived by removing one hydrogen from a ring obtained by combining two groups selected from these five-membered ring, six-membered ring and condensed ring. These heteroaryls may be substituted with alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl, aryl, or heteroaryl.

The alicyclic group and the heteroalicyclic group may be saturated or unsaturated. That is, these groups may have only a single bond or a combination of a single bond and a multiple bond. Saturated rings are preferred over unsaturated rings. Preferred heteroalicyclic groups have at least one heteroatom selected from nitrogen, oxygen, sulfur and phosphorus.

The alicyclic group and the heteroalicyclic group may be one ring or plural rings. Preferred examples of these groups are monocyclic, bicyclic or tricyclic having 3 to 25 carbon atoms, and these groups may be condensed rings or may be substituted. Preferred examples of these groups are five-membered, six-membered, seven-membered or eight-membered rings, in which at least one carbon may be replaced by silicon and at least one >CH - it is> may be replaced by N-, and at least one -CH ₂ - may be replaced by -O- or -S-.

Preferred alicyclic groups and heteroalicyclic groups are five-membered rings such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran and pyrrolidine, cyclohexane, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane and 1,3- Six-membered rings such as dithiane and piperidine, seven-membered rings such as cycloheptane, tetrahydronaphthalene, decahydronaphthalene, indane, bicyclo[1.1.1]pentane, bicyclo[2.2.2]octane, spiro[3. 3] A divalent group derived by removing two hydrogens from a condensed ring such as heptane and octahydro-4,7-methanoindane.

i is 0, 1, 2, 3, 4, or 5.

In the formula (5), R ⁵ is alkyl having 4 to 20 carbon atoms, and in this alkyl, at least one —CH ₂ — is —CH═CH—, —CF═CH—, —CH═CF—, It may be replaced by —C≡C— or cycloalkylene having 3 to 8 carbon atoms, and at least one hydrogen may be replaced by fluorine or chlorine. h is 1 or 2, and preferably 1.

Preferred R ⁵ is alkyl having 4 to 20 carbons. More desirable R ⁵ is alkyl having 6 to 18 carbons. At least one of -CH ₂ -, -CH = CH -, - CF = CH -, - CH = CF -, - C≡C-, or -O- in may be replaced, and at least one hydrogen It may be replaced by fluorine or chlorine.

Particularly preferred compound (4-1) is selected from the following compounds.

式（４−１−１−１）から式（４−１−４−４）において、Ｒ^７は、炭素数１から８のアルキルまたはフッ素である。

In formulas (4-1-1-1) to (4-1-4-4), R ⁷ is alkyl having 1 to 8 carbons or fluorine.

Particularly preferred compound (5-1) is selected from the following compound (5-1-1-1) to compound (5-1-29-1).

Fifth, preferable component compounds are shown. Preferred compound (1) includes compounds (1-1) to (1-12) according to item 3. In these compounds, at least one of the first additives is preferably compound (1-7), compound (1-8), compound (1-9), or compound (1-10). At least two of the first additives are preferably a combination of compound (1-8) and compound (1-9), or compound (1-2) and compound (1-7).

Preferred compound (2) includes compound (2-1) to compound (2-21) according to item 6. In these compounds, at least one of the first components is compound (2-1), compound (2-4), compound (2-5), compound (2-7), compound (2-10), or compound. It is preferably (2-15). At least two of the first components are compound (2-1) and compound (2-7), compound (2-1) and compound (2-15), compound (2-4) and compound (2-7), The compound (2-4) and the compound (2-15), or the combination of the compound (2-5) and the compound (2-10) is preferable.

Preferred compound (3) includes compound (3-1) to compound (3-13) according to item 9. In these compounds, at least one of the second components is compound (3-1), compound (3-3), compound (3-5), compound (3-6), compound (3-7), or compound. It is preferably (3-8). At least two of the second components are the compound (3-1) and the compound (3-3), the compound (3-1) and the compound (3-5), or the compound (3-1) and the compound (3-6). It is preferably a combination.

Preferred compound (4) is compound (4-1) according to item 13. More desirable compound (4) are the compounds (4-1-1) to (4-1-4) according to item 16. Preferred compound (5) is compound (5-1) according to item 14. More desirable compound (5) are the compounds (5-1-1) to (5-1-29) according to item 17. Compound (4) is generally preferred over compound (5).

Sixth, the additives that may be added to the composition will be described. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules to give a twist angle. Examples of such compounds are compound (6-1) to compound (6-5). A desirable ratio of the optically active compound is about 5% by weight or less. A more desirable ratio is in the range of approximately 0.01% by weight to approximately 2% by weight.

In order to prevent the decrease of the specific resistance due to heating in the atmosphere, or to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after using the element for a long time, an antioxidant composition is used. Is added to the product. Preferred examples of the antioxidant include compound (7) in which n is an integer of 1 to 9.

In compound (7), preferred n is 1, 3, 5, 7, or 9. More desirable n is 7. Since the compound (7) in which n is 7 has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after the device is used for a long time. A preferable ratio of the antioxidant is about 50 ppm or more to obtain the effect, and about 600 ppm or less so as not to lower the upper limit temperature or to raise the lower limit temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 300 ppm.

Preferred examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as sterically hindered amines are also preferred. A desirable ratio of these absorbers and stabilizers is about 50 ppm or more for obtaining the effect, and about 10,000 ppm or less for not lowering the upper limit temperature or for not raising the lower limit temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 10,000 ppm.

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

Polymerizable compounds are used to adapt to polymer-supported orientation (PSA) type devices. Compound (1) is suitable for this purpose. Along with the compound (1), another polymerizable compound different from the compound (1) 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), and vinyl ketones. A more preferred example is acrylate or methacrylate. A desirable ratio of the compound (1) is about 10% by weight or more based on the total weight of the polymerizable compound. A more desirable ratio is about 50% by weight or more. A particularly desirable ratio is about 80% by weight or more. A particularly desirable ratio is also 100% by weight. The reactivity of the polymerizable compound and the pretilt angle of liquid crystal molecules can be adjusted by changing the type of the compound (1) or by combining the compound (1) with another polymerizable compound in an appropriate ratio. By optimizing the pretilt angle, a short response time of the device can be achieved. Since the alignment of the liquid crystal molecules is stabilized, a large contrast ratio and a long life can be achieved.

A polymerizable compound such as the compound (1) is polymerized by irradiation with ultraviolet rays. The polymerization may be carried out in the presence of a suitable initiator such as a photopolymerization initiator. Suitable conditions for the polymerization, suitable types of initiators and suitable amounts are known to the person skilled in the art and are described in the literature. For example, the photoinitiators Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF) are suitable for radical polymerization. A preferred ratio of the photopolymerization initiator 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 more desirable ratio is in the range of approximately 1% by weight to approximately 3% by weight.

When storing a polymerizable compound such as the compound (1), 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 the polymerization inhibitor are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine and the like.

Seventh, the method of synthesizing the component compounds will be explained. These compounds can be synthesized by known methods. A synthetic method is illustrated. The compound (1-2) is synthesized by the method described in JP-A-7-101900. The compound (2-1) is synthesized by the method described in JP-A-2-503441. The compound (3-5) is synthesized by the method described in JP-A-57-165328. Compound (4-1) is synthesized by the method described in International Publication No. 2012-038026. A part of the compound (5) is commercially available. Compounds of formula (7) where n is 1 are available from Aldrich (Sigma-Aldrich Corporation). The compound (7) in which n is 7 and the like are synthesized by the method described in US Pat. No. 3,660,505.

Compounds for which no synthetic method is described include Organic Syntheses, John Wiley & Sons, Inc., Organic Reactions, John Wiley & Sons, Inc., Comprehensive Organic Synthesis, Comprehensive Organic Synthesis, Pergamon Press), New Experimental Chemistry Course (Maruzen), etc. The composition is prepared from the compounds thus obtained by known methods. For example, the component compounds are mixed and heated to dissolve each other.

Finally, the use of the composition will be explained. Most compositions have a minimum temperature of about −10° C. or lower, a maximum temperature 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 ratio of component compounds or by mixing with other liquid crystal compounds. Furthermore, a composition having an optical anisotropy in the range of about 0.10 to about 0.30 may be prepared by trial and error. A device containing this composition has a large voltage holding ratio. This composition is suitable for an AM device. This composition is particularly suitable for a transmissive AM device. This composition can be used as a composition having a nematic phase, or as an optically active composition by adding an optically active compound.

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

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

In this procedure, when a voltage is applied, the liquid crystal molecules are aligned by the action of the alignment film and the electric field. The molecules of the polymerizable compound are also oriented according to this orientation. In this state, the polymerizable compound is polymerized by ultraviolet rays, so that a polymer maintaining this orientation is produced. The effect of this polymer reduces the response time of the device. Since image sticking is a malfunction of liquid crystal molecules, the effect of this polymer improves the sticking at the same time. It is also possible to polymerize the polymerizable compound in the composition in advance and arrange the composition between the substrates of the liquid crystal display device.

An example of a method of manufacturing an element having no alignment film is as follows. An element having two substrates called an array substrate and a color filter substrate is prepared. This substrate has no alignment film. At least one of the substrates has an electrode layer. A liquid crystal composition is prepared by mixing liquid crystal compounds. A polymerizable compound and a polar compound are added to this composition. You may add an additive further as needed. This composition is injected into the device. Light irradiation is performed with a voltage applied to this element. UV light is preferred. The polymerizable compound is polymerized by irradiation with light. This polymerization forms a layer of the composition including the polymer and the polar compound on the substrate.

In this procedure, polar compounds align on the substrate as the polar groups interact with the substrate surface. The liquid crystal molecules are aligned according to this arrangement. When a voltage is applied, the alignment of liquid crystal molecules is further promoted, and the polymerizable compound is also aligned according to this alignment. In this state, the polymerizable compound is polymerized by ultraviolet rays, so that a polymer maintaining this orientation is produced. The effect of this polymer additionally stabilizes the alignment of the liquid crystal molecules and shortens the response time of the device. Since image sticking is a malfunction of liquid crystal molecules, the effect of this polymer improves the sticking at the same time.

The present invention will be described in more detail 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 mixtures of at least two of the example compositions. The synthesized compound was identified by a method such as NMR analysis. The characteristics of the compounds, compositions and devices were measured by the following methods.

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

Gas chromatographic analysis: A Shimadzu GC-14B type gas chromatograph was used for the 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. A capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm; stationary liquid phase dimethylpolysiloxane; nonpolar) manufactured by Agilent Technologies Inc. was used to separate the component compounds. The column was held 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 a C-R5A type Chromatopac manufactured by Shimadzu Corporation or its equivalent. The obtained gas chromatogram showed the retention time of peaks and the area of peaks corresponding to the component compounds.

As the 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 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies, Rtx-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Restek Corporation, BP-1 manufactured by SGE International Pty. Ltd (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm). 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 compound peaks from overlapping.

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

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

The following mother liquid crystals were used. The ratio of the component compounds is shown by weight.

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

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

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

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

(4) Viscosity (rotational viscosity; γ1; measured at 25° C.; mPa·s): The method is described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). I obeyed. The sample was injected into a VA element in which the distance (cell gap) between two glass substrates was 20 μm. A voltage of 39 V to 50 V was applied to the device in steps of 1 V. After 0.2 seconds of non-application, application was repeated under the conditions of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and the peak time of the transient current generated by this application were measured. These measurements and M. The value of rotational viscosity was obtained from the paper of Imai et al., Formula (8) on page 40. The dielectric anisotropy required for this calculation was measured by the method described in Measurement (6).

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

(6) Dielectric anisotropy (Δε; measured at 25° C.): The value of the dielectric anisotropy was calculated from the formula Δε=ε∥−ε⊥. The dielectric constants (ε ∥ and ε ⊥) were measured as follows.
1) Measurement of dielectric constant (ε|): A well-cleaned glass substrate was coated with a solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL). The glass substrate was rotated with a spinner and then heated at 150° C. for 1 hour. The sample was put in a VA element having a distance (cell gap) between the two glass substrates of 4 μm, and the element was sealed with an adhesive that was cured by ultraviolet rays. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the dielectric constant (ε∥) of the liquid crystal molecule in the major axis direction was measured.
2) Measurement of dielectric constant (ε⊥): A polyimide solution was applied to a well washed glass substrate. After firing this glass substrate, the obtained alignment film was rubbed. The sample was injected into a TN device in which the distance (cell gap) between the two glass substrates was 9 μm and the twist angle was 80 degrees. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the dielectric constant (ε⊥) in the short axis direction of the liquid crystal molecule was measured.

(7) Threshold voltage (Vth; measured at 25° C.; V): LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. A sample was put in a VA device in a normally black mode in which the distance between two glass substrates (cell gap) was 4 μm, and the rubbing direction was antiparallel, and an adhesive agent that cures the device with ultraviolet light was applied. Used to seal. The voltage (60 Hz, rectangular wave) applied to this element was gradually increased from 0 V to 20 V by 0.02 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 in which the transmittance is 100% when the light amount is maximum and the transmittance is 0% when the light amount is minimum was created. The threshold voltage is represented by the voltage when the transmittance becomes 10%.

(8) Voltage holding ratio (VHR-1; measured at 25° C.; %): The TN device used for measurement had a polyimide alignment film, and the distance (cell gap) between two glass substrates was 5 μm. .. This device was sealed with an adhesive which was cured by ultraviolet rays after the sample was injected. 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 obtained. Area B was the area when it was not attenuated. The voltage holding ratio was expressed as a percentage of the area A with respect to the area B.

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

(10) Voltage holding ratio (VHR-3; measured at 25° C.; %): After irradiation with ultraviolet rays, the voltage holding ratio was measured to evaluate stability to ultraviolet rays. The TN device used for the measurement had a polyimide alignment film, and the cell gap was 5 μm. A sample was injected into this 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 voltage that decays for 16.7 milliseconds was measured. A composition having a large VHR-3 has great stability to ultraviolet rays. VHR-3 is preferably 90% or more, more preferably 95% or more.

(11) Voltage holding ratio (VHR-4; measured at 25° C.; %): After heating the TN device injecting the sample in a constant temperature bath at 80° C. for 500 hours, the voltage holding ratio was measured and stability to heat was measured. Was evaluated. In the measurement of VHR-4, the voltage that decays for 16.7 milliseconds was measured. Compositions with large VHR-4 have great stability to heat.

(12) Response time (τ; measured at 25° C.; ms): Measurement was carried out with LCD Evaluation System Model LCD-5100 made by Otsuka Electronics Co., Ltd. The light source was a halogen lamp. The low-pass filter (Low-pass filter) was set to 5 kHz. The sample was put in a VA element in which the distance (cell gap) between the two glass substrates was 3.5 μm and which did not have an alignment film. The device was sealed with an ultraviolet curing adhesive. This device was irradiated with UV light of 78 mW/cm ² (405 nm) for 449 seconds (35 J) while applying a voltage of 30V. For the irradiation of ultraviolet rays, a multi-metal lamp M04-L41 for UV curing manufactured by Eye Graphics Co., Ltd. was used. 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 rectangular wave was set so that the transmittance was 90%. The minimum voltage of the rectangular wave was set to 2.5 V, which gives 0% transmittance. The response time was represented by the time required to change the transmittance from 10% to 90% (rise time; rise time; millisecond).

(13) Elastic constant (K11: spread elastic constant, K33: bend elastic constant; measured at 25° C.; pN): EC-1 type elastic constant measuring instrument manufactured by Toyo Technica Co., Ltd. for measurement Using. The sample was injected into a vertical alignment device in which the distance (cell gap) between two glass substrates was 20 μm. A charge of 20 V to 0 V was applied to this device, and the electrostatic capacity 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" (Nikkan Kogyo Shimbun). Then, the value of the elastic constant was obtained from the formula (2.100).

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

(15) Pretilt angle (degree): A spectroscopic ellipsometer M-2000U (manufactured by J.A. Woollam Co., Inc.) was used for measuring 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. The liquid crystal orientation angle φ (before) on the electrode side before stress application was measured, and then a rectangular wave of 4.5 V and 60 Hz was applied to the device for 20 minutes, followed by shorting for 1 second and electrode again after 1 second and 5 minutes. The liquid crystal orientation angle φ (after) on the side was measured. From these values, the change Δφ (deg.) in the liquid crystal orientation angle after 1 second and 5 minutes was calculated using the following formula.
Δφ(deg.)=φ(after)−φ(before) (Equation 2)
These measurements were performed with reference to J. Hilfiker, B. Johs, C. Herzinger, JF Elman, E. Montbach, D. Bryant, and PJ Bos, Thin Solid Films, 455-456, (2004) 596-600. .. It can be said that the smaller the Δφ, the smaller the rate of change of the liquid crystal alignment axis and the better the stability of the liquid crystal alignment axis.

Examples of compositions are given below. The component compounds are represented by symbols based on the definitions in Table 3 below. In Table 3, the configuration of 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 compound. The ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition. Finally, the characteristic values of the composition are summarized.

Example of device 1. A device having no alignment film was prepared, and the vertical alignment of liquid crystal molecules, the conversion rate of the polymerizable compound, and the response time were examined. First, the raw materials will be explained. The raw materials are liquid crystal compositions (M1) to (M15), polymerizable compounds (RM-1) to (RM-8), and polar compounds (PC-1) to (PC-33), which are listed in this order. ..

[Composition M1]
3-HB(2F,3F)-O2 (2-1) 10%
5-HB(2F,3F)-O2 (2-1) 7%
2-BB(2F,3F)-O2 (2-5) 7%
3-BB(2F,3F)-O2 (2-5) 7%
3-B(2F,3F)B(2F,3F)-O2 (2-6) 3%
2-HHB(2F,3F)-O2 (2-7) 5%
3-HHB(2F,3F)-O2 (2-7) 10%
2-HBB(2F,3F)-O2 (2-15) 8%
3-HBB(2F,3F)-O2 (2-15) 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=2.18V; η=22.6 mPa·s.

[Composition M2]
3-HB(2F,3F)-O4 (2-1) 6%
3-H2B(2F,3F)-O2 (2-3) 8%
3-H1OB(2F,3F)-O2 (2-4) 4%
3-BB(2F,3F)-O2 (2-5) 7%
2-HHB(2F,3F)-O2 (2-7) 7%
3-HHB(2F,3F)-O2 (2-7) 7%
3-HH2B(2F,3F)-O2 (2-9) 7%
5-HH2B(2F,3F)-O2 (2-9) 4%
2-HBB(2F,3F)-O2 (2-15) 5%
3-HBB(2F,3F)-O2 (2-15) 5%
4-HBB(2F,3F)-O2 (2-15) 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%
NI=82.8° C.; Tc<−30° C.; Δn=0.118; Δε=−4.4; Vth=2.13V; η=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 (2-5) 8%
3-HHB(2F,3F)-O2 (2-7) 5%
5-HHB(2F,3F)-O2 (2-7) 4%
3-HH1OB(2F,3F)-O2 (2-10) 4%
2-BB (2F, 3F) B-3 (2-11) 5%
2-HBB(2F,3F)-O2 (2-15) 3%
3-HBB(2F,3F)-O2 (2-15) 8%
4-HBB(2F,3F)-O2 (2-15) 5%
5-HBB(2F,3F)-O2 (2-15) 8%
3-HH-V (3-1) 27%
3-HH-V1 (3-1) 6%
V-HHB-1 (3-5) 3%
NI=78.1° C.; Tc<−30° C.; Δn=0.107; Δε=−3.2; Vth=2.02V; η=15.9 mPa·s.

[Composition M4]
3-HB(2F,3F)-O2 (2-1) 10%
5-HB(2F,3F)-O2 (2-1) 10%
3-H2B(2F,3F)-O2 (2-3) 8%
5-H2B(2F,3F)-O2 (2-3) 8%
3-HDhB(2F,3F)-O2 (2-13) 5%
2-HBB(2F,3F)-O2 (2-15) 6%
3-HBB(2F,3F)-O2 (2-15) 8%
4-HBB(2F,3F)-O2 (2-15) 7%
5-HBB(2F,3F)-O2 (2-15) 7%
3-HH-4 (3-1) 14%
V-HHB-1 (3-5) 10%
3-HBB-2 (3-6) 7%
NI=88.5° C.; Tc<−30° C.; Δn=0.108; Δε=−3.8; Vth=2.25V; η=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-H2B(2F,3F)-O2 (2-3) 8%
3-BB(2F,3F)-O2 (2-5) 10%
2-HHB(2F,3F)-O2 (2-7) 4%
3-HHB(2F,3F)-O2 (2-7) 7%
3-HHB(2F,3F)-1 (2-7) 6%
3-HDhB(2F,3F)-O2 (2-13) 5%
2-HBB(2F,3F)-O2 (2-15) 6%
3-HBB(2F,3F)-O2 (2-15) 6%
4-HBB(2F,3F)-O2 (2-15) 5%
5-HBB(2F,3F)-O2 (2-15) 4%
3-HEB(2F,3F)B(2F,3F)-O2
(2-17) 3%
3-H1OCro(7F,8F)-5 (2-20) 3%
3-HH-O1 (3-1) 5%
1-BB-5 (3-3) 4%
V-HHB-1 (3-5) 4%
5-HBBH-3 (3-11) 5%
NI=81.5° C.; Tc<−30° C.; Δn=0.119; Δε=−4.5; Vth=1.70V; η=31.8 mPa·s.

[Composition M6]
3-HB(2F,3F)-O4 (2-1) 15%
3-chB(2F,3F)-O2 (2-2) 7%
2-HchB(2F,3F)-O2 (2-8) 8%
3-HBB(2F,3F)-O2 (2-15) 8%
4-HBB(2F,3F)-O2 (2-15) 5%
5-HBB(2F,3F)-O2 (2-15) 7%
3-dhBB(2F,3F)-O2 (2-16) 5%
5-HH-V (3-1) 18%
7-HB-1 (3-2) 5%
V-HHB-1 (3-5) 7%
V2-HHB-1 (3-5) 7%
3-HBB(F)B-3 (3-13) 8%
NI=98.8° C.; Tc<−30° C.; Δn=0.111; Δε=−3.2; Vth=2.47V; η=23.9 mPa·s.

[Composition M7]
3-H2B(2F,3F)-O2 (2-3) 18%
5-H2B(2F,3F)-O2 (2-3) 17%
3-DhHB(2F,3F)-O2 (2-12) 5%
3-HHB(2F,3CL)-O2 (2-18) 5%
3-HBB(2F,3CL)-O2 (2-19) 8%
5-HBB(2F,3CL)-O2 (2-19) 7%
3-HH-V (3-1) 11%
3-HH-VFF (3-1) 7%
F3-HH-V (3-1) 10%
3-HHEH-3 (3-4) 4%
3-HHEBH-3 (3-9) 4%
3-HB(F)HH-2 (3-10) 4%
NI=77.5° C.; Tc<−30° C.; Δn=0.084; Δε=−2.6; Vth=2.43V; η=22.8 mPa·s.

[Composition M8]
3-HB(2F,3F)-O2 (2-1) 8%
3-H2B(2F,3F)-O2 (2-3) 10%
3-BB(2F,3F)-O2 (2-5) 10%
2O-BB(2F,3F)-O2 (2-5) 3%
2-HHB(2F,3F)-O2 (2-7) 4%
3-HHB(2F,3F)-O2 (2-7) 7%
2-HHB(2F,3F)-1 (2-7) 5%
2-BB (2F, 3F) B-3 (2-11) 6%
2-BB (2F, 3F) B-4 (2-11) 6%
3-HDhB(2F,3F)-O2 (2-13) 6%
2-HBB(2F,3F)-O2 (2-15) 4%
3-HBB(2F,3F)-O2 (2-15) 7%
3-dhBB(2F,3F)-O2 (2-16) 4%
3-HH1OCro(7F,8F)-5 (2-21) 4%
3-HH-V (3-1) 11%
1-BB-5 (3-3) 5%
NI=70.6° C.; Tc<−20° C.; Δn=0.129; Δε=−4.3; Vth=1.69V; η=27.0 mPa·s.

[Composition M9]
3-HB(2F,3F)-O4 (2-1) 14%
3-H1OB(2F,3F)-O2 (2-4) 3%
3-BB(2F,3F)-O2 (2-5) 10%
2-HHB(2F,3F)-O2 (2-7) 7%
3-HHB(2F,3F)-O2 (2-7) 7%
3-HH1OB(2F,3F)-O2 (2-10) 6%
2-HBB(2F,3F)-O2 (2-15) 4%
3-HBB(2F,3F)-O2 (2-15) 6%
4-HBB(2F,3F)-O2 (2-15) 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%
NI=93.0° C.; Tc<−30° C.; Δn=0.123; Δε=−4.0; Vth=2.27V; η=29.6 mPa·s.

[Composition M10]
3-HB(2F,3F)-O4 (2-1) 6%
3-H2B(2F,3F)-O2 (2-3) 8%
3-H1OB(2F,3F)-O2 (2-4) 5%
3-BB(2F,3F)-O2 (2-5) 10%
2-HHB(2F,3F)-O2 (2-7) 7%
3-HHB(2F,3F)-O2 (2-7) 7%
5-HHB(2F,3F)-O2 (2-7) 7%
2-HBB(2F,3F)-O2 (2-15) 4%
3-HBB(2F,3F)-O2 (2-15) 7%
5-HBB(2F,3F)-O2 (2-15) 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%
NI=87.6° C.; Tc<−30° C.; Δn=0.126; Δε=−4.5; Vth=2.21V; η=25.3 mPa·s.

[Composition M11]
3-HB(2F,3F)-O4 (2-1) 6%
3-H2B(2F,3F)-O2 (2-3) 8%
3-H1OB(2F,3F)-O2 (2-4) 4%
3-BB(2F,3F)-O2 (2-5) 7%
2-HHB(2F,3F)-O2 (2-7) 6%
3-HHB(2F,3F)-O2 (2-7) 10%
5-HHB(2F,3F)-O2 (2-7) 8%
2-HBB(2F,3F)-O2 (2-15) 5%
3-HBB(2F,3F)-O2 (2-15) 7%
5-HBB(2F,3F)-O2 (2-15) 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=2.22V; η=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 (2-5) 8%
3-HHB(2F,3F)-O2 (2-7) 4%
5-HHB(2F,3F)-O2 (2-7) 5%
3-HH1OB(2F,3F)-O2 (2-10) 5%
2-BB (2F, 3F) B-3 (2-11) 4%
2-HBB(2F,3F)-O2 (2-15) 3%
3-HBB(2F,3F)-O2 (2-15) 8%
4-HBB(2F,3F)-O2 (2-15) 5%
5-HBB(2F,3F)-O2 (2-15) 8%
3-HH-V (3-1) 33%
V-HHB-1 (3-5) 3%
NI=76.4° C.; Tc<−30° C.; Δn=0.104; Δε=−3.2; Vth=2.06V; η=15.6 mPa·s.

[Composition M13]
2-H1OB(2F,3F)-O2 (2-4) 6%
3-H1OB(2F,3F)-O2 (2-4) 4%
3-BB(2F,3F)-O2 (2-5) 3%
2-HH1OB(2F,3F)-O2 (2-10) 14%
2-HBB(2F,3F)-O2 (2-15) 7%
3-HBB(2F,3F)-O2 (2-15) 11%
5-HBB(2F,3F)-O2 (2-15) 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=2.17V; η=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 (2-5) 8%
3-HHB(2F,3F)-O2 (2-7) 5%
5-HHB(2F,3F)-O2 (2-7) 4%
3-HH1OB(2F,3F)-O2 (2-10) 5%
2-BB (2F, 3F) B-3 (2-11) 4%
2-HBB(2F,3F)-O2 (2-15) 3%
3-HBB(2F,3F)-O2 (2-15) 9%
4-HBB(2F,3F)-O2 (2-15) 4%
5-HBB(2F,3F)-O2 (2-15) 8%
3-HH-V (3-1) 27%
3-HH-V1 (3-1) 6%
V-HHB-1 (3-5) 5%
NI=81.2° C.; Tc<−20° C.; Δn=0.107; Δε=−3.2; Vth=2.11V; η=15.5 mPa·s.

[Composition M15]
3-H2B(2F,3F)-O2 (2-3) 7%
3-HHB(2F,3F)-O2 (2-7) 8%
2-HchB(2F,3F)-O2 (2-8) 8%
3-HH1OB(2F,3F)-O2 (2-10) 5%
2-BB (2F, 3F) B-3 (2-11) 7%
2-BB (2F, 3F) B-4 (2-11) 7%
3-HDhB(2F,3F)-O2 (2-13) 3%
3-DhH1OB(2F,3F)-O2 (2-14) 4%
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%
NI=88.3° C.; Tc<−30° C.; Δn=0.115; Δε=−2.0; Vth=2.80 V; η=17.8 mPa·s.

The following polymerizable compounds (RM-1) to (RM-8) were used as the first additive.

The following polar compounds (PC-1) to (PC-33) were used as the second additive.

2. Vertical alignment test number 1 for liquid crystal molecules
The polymerizable compound (RM-1) was added to the composition (M1) at a ratio of 0.5% by weight, and the polar compound (PC-1) was added at a ratio of 5% by weight. This mixture was injected onto a device having no alignment film, in which the distance (cell gap) between two glass substrates was 4.0 μm on a hot stage at 100° C. The polymerizable compound was polymerized by irradiating the device with ultraviolet rays (28J) using an ultra-high pressure mercury lamp USH-250-BY (manufactured by Ushio Inc.). This device was set on a polarizing microscope in which a polarizer and an analyzer were arranged orthogonally, and the device was irradiated with light from below to observe the presence or absence of light leakage. When the liquid crystal molecules were sufficiently aligned and light did not pass through the device, the vertical alignment was judged to be “good”. When the light passing through the device was observed, it was indicated as “poor”.

Exam number 2-33
An element having no alignment film was prepared using a mixture of the composition, the polymerizable compound, and the polar compound. The presence or absence of light leakage was observed by the same method as Test No. 1. The results are summarized in Table 4.

3. Conversion Rate of Polymerizable Compound The polymerizable compound was added to the composition together with the polar compound. This polymerizable compound was consumed by the polymerization to give the polymer. It is preferable that the conversion rate of this reaction is large. This is because the remaining amount of the polymerizable compound (the amount of the unreacted polymerizable compound) is preferably smaller from the viewpoint of image sticking. When a polymer-supported alignment type device is produced, ultraviolet rays are generally irradiated in two steps for the purpose of optimizing the pretilt angle of liquid crystal molecules. In the next test, after irradiating the ultraviolet rays of the first stage, the remaining amount of the polymerizable compound was measured and the conversion rate was calculated. The following polymerizable compound (RM-9) was selected for comparison. This compound is excluded from the compound (1) by the definition of symbols.

The polymerization was performed as follows. A device having no alignment film was prepared by the method described in the paragraph “Vertical alignment of liquid crystal molecules”. This device was irradiated with 78 mW/cm ² (405 nm) of ultraviolet rays for 359 seconds (28 J) while applying a voltage of 30V. For the irradiation of ultraviolet rays, a multi-metal lamp M04-L41 for UV curing manufactured by Eye Graphics Co., Ltd. was used. Then, the remaining amount of the polymerizable compound was measured by HPLC and the conversion rate was calculated. The results are summarized in Table 5. The conversions of test numbers 1 to 8 ranged from 34% to 44%. In Comparative Example 1, the polymerizable compound (RM-1) used in Test No. 1 was replaced with the polymerizable compound (RM-9) for polymerization. In this case, the conversion rate was 16%. From this comparison, it can be concluded that the composition of the present invention is also excellent in terms of conversion rate.

4. Response time As described in Table 6, a mixture prepared by combining various compositions, a polymerizable compound, and a polar compound was injected into a device having no alignment film. According to the item (12), the response time of the device was measured after polymerizing the polymerizable compound by irradiating with ultraviolet rays. For comparison, a device was prepared from the composition (M5) or the composition (M9) without adding the polymerizable compound and the polar compound, and the response time was measured by the same method. As can be seen from Table 6, in the test numbers 1 to 33, the response time was in the range of 5.2 milliseconds to 10.4 milliseconds. On the other hand, the response times of Comparative 1 and Comparative 2 were 21.8 milliseconds and 21.7 milliseconds, respectively. That is, when the polymerizable compound and the polar compound were not added, the response time was about double. Therefore, it can be concluded that the combination of the polymer derived from the polymerizable compound (1) and the polar compound (4) or (5) is effective in shortening the response time.

In a liquid crystal display device, a shorter response time is preferable. The response time of the examples shown in Table 6 was in the range of 5.2 msec to 10.4 msec, which was shorter than that of the comparative example. It can be said that this result indicates that the use of the liquid crystal composition containing the polymerizable compound and the polar compound achieves a short response time in the device having no alignment film, despite the difference in the type of each component. This is because the liquid crystal molecules are stably aligned even without the alignment film, which is a special feature of the present invention.

The liquid crystal composition of the present invention can control the alignment of liquid crystal molecules in an element having no alignment film. This composition has properties such as high maximum temperature, low minimum temperature, small viscosity, suitable optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability against ultraviolet rays, and high stability against heat. At, satisfying at least one property, or having an appropriate balance with respect to at least two properties. A liquid crystal display device containing this composition has characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long life, so that it can be used for a liquid crystal projector, a liquid crystal television and the like. ..

Claims (24)

At least one polymerizable compound selected from the group of compounds represented by formula (1) as the first additive, the table with the formula (2) at least one polar compound as the second additive, and as a first component A liquid crystal composition containing at least one compound selected from the group of compounds described above and having a negative dielectric anisotropy.

In formula (1), ring A and ring C are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidine-. 2-yl or pyridin-2-yl, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen. It may be replaced by alkyl having 1 to 12 carbons which is replaced by fluorine or chlorine; Ring B 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, and 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 may be replaced by an alkyl having 1 to 12 carbons in which fluorine or chlorine is replaced; Z ¹ and Z ² are independently a single bond or an alkylene having 1 to 10 carbons, and this alkylene In, at least one —CH ₂ — may be replaced by —O—, —CO—, —COO—, or —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 are polymerizable groups; Sp ¹ , Sp ² , and Sp ³ are independently a single bond or carbon. An alkylene of the numbers 1 to 10 in which at least one —CH ₂ — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, and at least one —CH ₂ —. CH ₂ -CH ₂ - is - CH=CH- or -C[identical to]C-, in which at least one hydrogen may be replaced by fluorine or chlorine; a is 0, 1, or 2; b , C, and d are independently 0, 1, 2, 3, or 4 provided that when Ring A and Ring C are phenyl, a is 1 or 2 and a is 1. When Sp ¹ and Sp ³ are single bonds;
In formula (2), R ¹ and R ² 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. Yes; Ring D and Ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-wherein at least one hydrogen has been replaced by fluorine or chlorine. Phenylene or tetrahydropyran-2,5-diyl; Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro- 5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl; Z ³ and Z ⁴ are independently Te single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or a -OCO-; e is 1, 2, or 3,, f is 0 or 1 and the sum of e and f is 3 or less. In the formula (1), P ¹ , P ² , and P ³ are independently a polymerizable group selected from the group of groups represented by formulas (P-1) to (P-5). Item 2. The liquid crystal composition according to item 1.

In formulas (P-1) to (P-5), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is fluorine or chlorine. Is an alkyl having 1 to 5 carbon atoms replaced by. The liquid crystal composition according to claim 1, wherein the first additive is at least one polymerizable compound selected from the group of compounds represented by formulas (1-1) to (1-12).

In formulas (1-1) to (1-12), P ¹ , P ² , and P ³ are independently a group of groups represented by formulas (P-1) to (P-3). A polymerizable group of choice, wherein M ¹ , M ² , and M ³ are independently hydrogen, fluorine, C ¹ -C 5 alkyl, or at least one hydrogen is replaced by fluorine or chlorine. Alkyl having 1 to 5 carbon atoms;

Sp ¹ , Sp ² , and Sp ³ are independently a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO—, —OCO. -, or may be replaced by -OCOO-, and at least one _-CH 2 -CH ₂ - may be replaced by -CH = CH- or -C≡C-, and in the groups, at least One hydrogen may be replaced by fluorine or chlorine. The liquid crystal composition according to claim 1, wherein the ratio of the first additive is in the range of 0.03% by weight to 10% by weight based on the weight of the liquid crystal composition. The liquid crystal according to any one of claims 1 to 4 , which contains at least one compound selected from the group of compounds represented by formulas (2-1) to (2-21) as a first component. Composition.

In formulas (2-1) to (2-21), R ¹ and R ² are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or It is an alkenyloxy having 2 to 12 carbon atoms. Based on the weight of the liquid crystal composition, the ratio of the first component is from 10 wt% to 90 wt%, the liquid crystal composition according to any one of claims 1 to 5. 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 the second component.

In formula (3), R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, at least one hydrogen being replaced by fluorine or chlorine. An alkyl having 1 to 12 carbons, or an alkenyl having 2 to 12 carbons in which at least one hydrogen has been replaced by fluorine or chlorine; ring G and ring I are independently 1,4-cyclohexylene. , 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ⁵ is a single bond, —CH ₂ CH ₂ —, —CH ₂ O. _{-, - OCH 2 -, -} COO-, or a is -OCO-; g is 1, 2 or 3. The liquid crystal according to any one of claims 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. Composition.

In formulas (3-1) to (3-13), R ³ and R ⁴ are independently at least alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least Alkyl having 1 to 12 carbons in which 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. Based on the weight of the liquid crystal composition, the proportion of the second component is in the range of 10 wt% to 90 wt%, the liquid crystal composition according to claim 7 or 8. The liquid crystal composition according to any one of claims 1 to 9 , wherein the second additive is a polar compound having a polar group having a hetero atom selected from nitrogen, oxygen, sulfur, and phosphorus. The liquid crystal composition according to any one of claims 1 to 10 , containing at least one polar compound selected from the group of compounds represented by formula (4) and formula (5) as the second additive. ..

In the formula (4), MES is a mesogenic group having at least one ring; in the formula (5), R ⁵ is alkyl having 4 to 20 carbons, and in this alkyl, at least one —CH ₂ —. May be replaced with -CH=CH-, -CF=CH-, -CH=CF-, -C[identical to]C-, or cycloalkylene having 3 to 8 carbon atoms, and in these groups, at least one Hydrogen may be replaced by fluorine or chlorine; in the formulas (4) and (5), R ⁶ is an oxygen atom of an OH structure, a sulfur atom of a SH structure, and a primary, secondary, or A polar group having at least one nitrogen atom of a tertiary amine structure; h is 1 or 2. The liquid crystal composition according to any one of claims 1 to 11 , containing at least one compound selected from the group of compounds represented by formula (4-1) as a second additive.

In formula (4-1), ring J and ring K are independently an aromatic group having 6 to 25 carbon atoms, a heteroaromatic group having 5 to 25 carbon atoms, an alicyclic group having 3 to 25 carbon atoms, Or a heteroalicyclic group having 4 to 25 carbon atoms, which may be a condensed ring, in which at least one hydrogen may be replaced by a group T, wherein the group T _{is, -OH, - (CH 2)} j -OH, _{halogen, -CN, -NO 2, -NCO,} -NCS, -OCN, -SCN, -C (= O) N (R 0) 2, -C _{^{(= O) R 0, -N}} (R 0) 2, - (CH 2) j -N (R 0) 2, aryl having 6 to 20 carbon atoms, heteroaryl of from 6 to 20 carbon atoms, having a carbon number of 1 25 alkyl, 1 to 25 alkoxy, 2 to 25 alkylcarbonyl, 2 to 25 alkoxycarbonyl, 2 to 25 alkylcarbonyloxy, or 2 to 25 alkoxycarbonyloxy. And in these groups, at least one hydrogen may be replaced by fluorine or chlorine, wherein R ⁰ is hydrogen or alkyl having 1 to 12 carbons and j is 1, 2, 3, or it is a ^4; Z 6 is, -O -, - S -, - CO -, - CO-O -, - OCO -, - OCO-O -, - OCH 2 -, - CH 2 O-, _{-SCH 2 -, - CH 2 S} -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - (CH 2) j -, - CF 2 CH 2 -, - CH _{2 CF 2 -, - (CF} 2) j -, - CH = CH -, - CF = CF -, - C≡C -, - CH = CH-COO -, - OCO-CH = CH -, - C ( R ⁰ ) ₂ or a single bond, wherein R ⁰ is hydrogen or alkyl having 1 to 12 carbons, j is 1, 2, 3, or 4; R ⁶ is 1 carbon from alkyl of 25, and in the alkyl, at least one of _-CH 2 ^-, -NR 0 -, - O - , - S -, - CO -, - COO -, - OCO -, - OCOO-, or It may be replaced by cycloalkylene having 3 to 8 carbons, wherein R ⁰ is hydrogen or alkyl having 1 to 12 carbons, and at least one tertiary carbon (>CH-) is nitrogen (>). N-), and at least one hydrogen is replaced by fluorine or chlorine. R ⁶ may have at least one oxygen atom of OH structure, sulfur atom of SH structure, or nitrogen atom of primary, secondary, or tertiary amine structure. R ⁷ is hydrogen, halogen, alkyl having 1 to 25 carbon atoms, and in this alkyl, at least one —CH ₂ — is —NR ⁰ —, —O—, —S—, —CO—, —. CO-O-, -O-CO-, -O-CO-O-, or cycloalkylene having 3 to 8 carbon atoms, and at least one tertiary carbon (>CH-) is It may be replaced by nitrogen (>N-), in which at least one hydrogen may be replaced by fluorine or chlorine, wherein R ⁰ is hydrogen or alkyl having 1 to 12 carbons. Yes; i is 0, 1, 2, 3, 4, or 5. The liquid crystal composition according to any one of claims 1 to 11 , containing at least one polar compound selected from the group of compounds represented by formula (5-1) as a second additive.

In Formula (5-1), R ⁵ is alkyl having 4 to 20 carbon atoms, and in this alkyl, at least one —CH ₂ — is —CH═CH—, —CF═CH—, —CH═. CF-, -C≡C-, or C3-C8 cycloalkylene may be substituted, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine; R ⁶ is alkyl of 1 to 25 carbon atoms, in the alkyl, at least one of _-CH 2 ^-, -NR 0 -, - O - , - S -, - CO -, - COO -, - OCO -, - OCOO Or may be replaced by cycloalkylene having 3 to 8 carbons, wherein R ⁰ is hydrogen or alkyl having 1 to 12 carbons, and at least one tertiary carbon (>CH-) is It may be replaced by nitrogen (>N-) and at least one hydrogen may be replaced by fluorine or chlorine, provided that R ⁶ is at least one oxygen atom of OH structure, sulfur atom of SH structure. Or having a nitrogen atom of a primary, secondary, or tertiary amine structure. In the formula (4) and (5) as claimed in claim 11, ^{R 6} is a group represented by any one of formula (A4) from the equation (A1), any of claims 11 13, Item 2. The liquid crystal composition according to item 1.

In formulas (A1) to (A4), Sp ⁴ , Sp ⁶ , and Sp ⁷ are independently a single bond or a group (—Sp″—X″—), where Sp″ is , C 1-20 alkylene, and in this alkylene, at least one —CH ₂ — is —O—, —S—, —NH—, —N(R ⁰ )—, —CO—, —CO—. O-, -O-CO, -O-CO-O-, -S-CO-, -CO-S-, -N( ^R0 )-CO-O-, -O-CO-N( ^R0 ). -, -N( ^R0 )-CO-N( ^R0 )-, -CH=CH-, or -C[identical to]C-, in which at least one hydrogen is fluorine, It may be replaced by chlorine or -CN, and X'' is -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -. ^{CO-N (R 0) -} , - N (R 0) -CO -, - N (R 0) -CO-N (R 0) -, - OCH 2 -, - CH 2 O -, - SCH 2 - _{, -CH 2 S -, - CF} 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 -, -CH = N -, - N = CH -, - N = N -, - CH = CR 0 -, - CY 2 = CY 3 -, - C≡C -, - CH = CH-CO-O -, - O-CO-CH = CH-, or a single bond, wherein ^{R 0} is hydrogen or alkyl having a carbon number of 1 to 12, ^{Y 2} and ^{Y 3} are independently hydrogen, fluorine, chlorine or, be -CN; Sp ^{5 is,> CH -,> CR 11} -,> N-, or> is C ^<; X 1 _{^{is, -OH, -OR 11, -COOH,}} -NH 2, -NHR 11 _{^{, -N (R 11) 2,}} -SH, -SR 11,

Wherein R ⁰ is hydrogen or alkyl having 1 to 12 carbons; X ² is —O—, —CO—, —NH—, —NR ¹¹ —, —S—, or a single bond. Yes; Z ⁷ is alkylene having 1 to 15 carbons, an alicyclic group having 5 or 6 carbons, or a combination thereof, and in these groups, at least one hydrogen is —OH, —OR ¹¹ , or ^{_{-COOH, -NH 2, -NHR 11,}} -N (R 11) 2, fluorine or may be replaced by ^{chlorine,; R 11} is alkyl of 1 to 15 carbon atoms, in the alkyl, at least one One —CH ₂ — may be replaced by —C≡C—, —CH═CH—, —COO—, —OCO—, —CO—, or —O—, and in these groups, at least one Hydrogen may be replaced by fluorine or chlorine; ring L is an aromatic group having 6 to 25 carbon atoms or an alicyclic group having 3 to 25 carbon atoms, and these groups may be condensed rings. well, and in the groups, one to three hydrogen may be replaced by ^{R L; R} L _{is, -OH, - (CH 2)} j -OH, fluorine, chlorine, -CN, _-NO 2, ^{-NCO, -NCS, -OCN, -SCN,} -C (= O) N (R 0) 2, -C (= O) R 0, -N (R 0) 2, - (CH 2) j -N (R ⁰ ) ₂ , —SH, —SR ⁰ , aryl having 6 to 20 carbon atoms, heteroaryl having 6 to 20 carbon atoms, alkyl having 1 to 25 carbon atoms, alkoxy having 1 to 25 carbon atoms, and having 2 carbon atoms 25 alkylcarbonyl, C2 to C25 alkoxycarbonyl, C2 to C25 alkylcarbonyloxy, or C2 to C25 alkoxycarbonyloxy, in which at least one hydrogen is fluorine or It may be replaced by chlorine, wherein R ⁰ is hydrogen or alkyl having 1 to 12 carbons, j is 1, 2, 3, or 4; k is 0, 1, 2, or 3; m is 2, 3, 4, or 5. The liquid crystal composition according to claim 12 , wherein the second additive is at least one compound selected from the group of compounds represented by formulas (4-1-1) to (4-1-4).

In formula (4-1-1) and formula (4-1-4), ring J and ring K are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4. -Phenylene, 2-fluoro-1,3-phenylene, 2-ethyl-1,4-phenylene, 2,6-diethyl-1,4-phenylene, 2-trifluoromethyl-1,4-phenylene, 2,3 -Difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, or 2,3,5,6-tetrafluoro-1,4- Phenylene; ring L is cyclohexyl or phenyl; Z ⁶ is a single bond, ethylene, or carbonyloxy; Z ⁷ is a single bond, alkylene having 1 to 15 carbons, C 5 or 6 An alicyclic group, or a combination thereof, in which at least one hydrogen is replaced with —OH, —OR ¹¹ , —COOH, —NH ₂ , —NHR ¹¹ , —NR ¹¹ ₂ or halogen. R ¹¹ is alkyl having 1 to 15 carbons, and at least one —CH ₂ — in these groups is —C≡C—, —CH═CH—, —COO—, —OCO. -, -CO-, -O-, or -NH- may be substituted; Sp ⁴ is a single bond, ethylene, propylene, or methyleneoxy; Sp ⁷ is a single bond or has 1 to 12 carbon atoms. 5 is alkylene, and in this alkylene, —CH ₂ — may be replaced by —O— or —NH—; R ⁷ is alkyl having 1 to 8 carbons or fluorine; i is 0, 1 , 2,3,4, or a ^5; X 1 is -OH, -COOH, -SH, it is -OCH ₃ or -NH _2,; ^{X 2} is a single bond or -O-. The liquid crystal composition according to claim 13 , wherein the second additive is at least one compound selected from the group of compounds represented by formulas (5-1-1) to (5-1-29).

In formulas (5-1-1) to (5-1-29), R ⁵ is alkyl having 4 to 20 carbon atoms, and in this alkyl, at least one —CH ₂ — is —CH═CH. -, -CF=CH-, -CH=CF-, -C≡C-, or cycloalkylene having 3 to 8 carbon atoms, in which at least one hydrogen is fluorine or chlorine. May be replaced with. The liquid crystal composition according to any one of claims 1 to 16 , wherein the proportion of the second additive is less than 10% by weight based on the weight of the liquid crystal composition. A liquid crystal display device containing the liquid crystal composition according to any one of claims 1 17. 19. The liquid crystal display element according to claim 18 , 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. Containing the liquid crystal composition according to any one of claims 1 17, the polymerizable compound of the liquid crystal composition is polymerized, the liquid crystal display device of a polymer sustained alignment type. Containing the liquid crystal composition according to any one of claims 1 17, the polymerizable compound of the liquid crystal composition is polymerized, the liquid crystal display device having no alignment film. Use of the liquid crystal composition according to any one of claims 1 to 17 in a liquid crystal display device. Use of the liquid crystal composition according to any one of claims 1 to 17 in a polymer-supported alignment type liquid crystal display device. Use of the liquid crystal composition according to any one of claims 1 to 17 in a liquid crystal display device having no alignment film.