JP6766873B2 - Liquid crystal composition and liquid crystal display element - Google Patents

Description

The present invention relates to a liquid crystal composition having a positive dielectric anisotropy, 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 (or a polymer thereof) having a polymerizable group and capable of achieving vertical orientation of liquid crystal molecules by the action of this compound, and a liquid crystal display element.

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

The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the properties of this composition, an AM device having good properties can be obtained. The relationships in these properties are summarized in Table 1 below. The properties of the composition will be further described based on commercially available AM devices. The temperature range of the nematic phase is related to the temperature range in which the device can be used. The preferred upper limit temperature of the nematic phase is about 70 ° C. or higher, and the preferred lower limit temperature of the nematic phase is about −10 ° C. or lower. The viscosity of the composition is related to the response time of the device. A short response time is preferred for displaying moving images on the device. A shorter response time of even 1 millisecond is desirable. Therefore, a small viscosity in the composition is preferred. Small viscosities at low temperatures are more preferred. The elastic constant of the composition is related to the contrast of the device. In order to increase the contrast in the device, a large elastic constant in the composition is more preferable.

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, an appropriate optical anisotropy is required. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate value of the product depends on the type of operation mode. For devices in modes such as TN, this value is about 0.45 μm. In this case, a composition having a large optical anisotropy is preferable for a device having a small cell gap. The large dielectric anisotropy in the composition contributes to the low threshold voltage, low power consumption and large contrast ratio in the device. Therefore, large dielectric anisotropy is preferred. A large resistivity in the composition contributes to a large voltage retention and a large contrast ratio in the device. Therefore, a composition having a large resistivity in the initial stage is preferable. A composition having a large specific resistance after long-term use is preferable. The stability of the composition against UV light or 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 AM elements used in liquid crystal projectors, liquid crystal televisions, and the like.

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

On the other hand, in a liquid crystal display element having no alignment film, a liquid crystal composition containing a polymer and a polar compound 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 compounds are adsorbed on the surface of the substrate and arranged. The liquid crystal molecules are oriented according to this arrangement. Next, the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of this device. Here, the polymerizable compound polymerizes and stabilizes the orientation of the 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 the image burn-in is improved. Further, in the device having no alignment film, the step of forming the alignment film is unnecessary. Since there is no alignment film, the interaction between the alignment film and the composition does not reduce the electrical resistance of the device. Such effects due to the combination of the polymer and the polar compound can be expected for devices having modes such as TN, ECB, OCB, IPS, VA, FFS and FPA.

In the AM device having the TN mode, a composition having a positive dielectric anisotropy is used. In the AM device having the VA mode, a composition having a 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 the polymer support orientation type AM device, a composition having positive or negative dielectric anisotropy is used. In a device having no alignment film, a composition having positive or negative dielectric anisotropy is used. Compositions having positive dielectric anisotropy are disclosed in the following Patent Documents 1 to 4 and the like. In the present invention, a polar compound having a polymerizable group (or a polymer thereof) is combined with a liquid crystal compound, and this composition is used for a liquid crystal display element having no alignment film.

Special Table 2013-541028 Special Table 2013-543526 Gazette Special Table 2014-513150 International Publication No. 2014-94959

One object of the present invention is to provide a liquid crystal composition containing a polar compound (or a polymer thereof) having a polymerizable group, wherein the polar compound has high compatibility with the liquid crystal compound. .. Another object is to provide a liquid crystal composition capable of achieving vertical orientation of liquid crystal molecules by the action of a polymer generated from this polar compound. Other objectives are high upper temperature limit of nematic phase, lower lower limit temperature of nematic phase, small viscosity, proper optical anisotropy, very large dielectric anisotropy, large specific resistance, high stability to ultraviolet rays, heat resistance. It is to provide a liquid crystal composition that satisfies at least one of the properties such as high stability and large elastic constant. Another object is to provide a liquid crystal composition having an appropriate balance between at least two of these properties. Another object is a liquid crystal display device containing such a composition. Another object is to provide an AM device with characteristics such as short response time, high voltage retention, low threshold voltage, high contrast ratio, long life.

式（１）および式（２）において、Ｒ^１は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルであり；環Ａおよび環Ｂは独立して、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，３−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、ピリミジン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはテトラヒドロピラン−２，５−ジイルであり；環Ｃおよび環Ｅ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、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のアルケニルで置き換えられてもよく；環Ｄは、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、ナフタレン−１，２−ジイル、ナフタレン−１，３−ジイル、ナフタレン−１，４−ジイル、ナフタレン−１，５−ジイル、ナフタレン−１，６−ジイル、ナフタレン−１，７−ジイル、ナフタレン−１，８−ジイル、ナフタレン−２，３−ジイル、ナフタレン−２，６−ジイル、ナフタレン−２，７−ジイル、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、またはピリジン−２，５−ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、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、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ_２Ｏ−、または−ＯＣＦ_２−であり；Ｚ^３およびＺ^４は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、そして少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ_３）−、または−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｘ^１およびＸ^２は独立して、水素またはフッ素であり；Ｙ^１は、フッ素、塩素、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、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２から１２のアルケニルオキシであり；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_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ａは、１、２、３、または４であり；ｂは、０、１、２、または３であり、そしてａおよびｂの和は４以下であり；ｃは、０、１、２、３、または４であり；ｅ、ｆ、およびｇは独立して、０、１、２、３、または４であり、そしてｅ、ｆ、およびｇの和は、２以上であり；Ｐ^１、Ｐ^２、およびＰ^３は独立して、式（Ｐ−Ａ）で表される重合性基であり；

式（Ｐ−Ａ）において、Ｓｐ^４は、単結合または炭素数１から７のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；Ｒ^２は、−ＯＨ、−ＯＲ^０、−ＮＨ_２、−ＮＨＲ^０、または−Ｎ(Ｒ^０)_２で表される基であり、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；Ｍ^４およびＭ^５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。The present invention was selected from the group of at least one compound selected from the group of compounds represented by the formula (1) as the first component, and the group of polar compounds represented by the formula (2) as the first additive. A liquid crystal composition containing at least one compound and having positive dielectric anisotropy, and a liquid crystal display element containing this composition.

In formulas (1) and (2), R ¹ is an alkyl with 1 to 12 carbons, an alkoxy with 1 to 12 carbons, or an alkenyl with 2 to 12 carbons; rings A and B are independent. 1,4-Cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine -2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; rings C and E are independently cyclohexyl, cyclohexenyl, phenyl, 1-. It is naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl, or pyridine-2-yl, and in these rings at least one hydrogen is fluorine. , Chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, alkyl with 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine, or at least 1 One hydrogen may be replaced with an alkenyl having 2 to 12 carbons replaced by fluorine or chlorine; ring D 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 which at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, An alkenyl having 2 to 12 carbon atoms, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine, or an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine. Z ¹ and Z ² may be independently single-bonded, -CH ₂ CH _2- , -CH = CH-, -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CF ₂ O- or -O CF ₂ −; Z ³ and Z ⁴ are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which 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 )-and at least one hydrogen in these groups may be replaced with fluorine or chlorine; X ¹ and X ² Are independently hydrogen or fluorine; Y ¹ is fluorine, chlorine, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, and at least one hydrogen is replaced by fluorine or chlorine. An alkoxy having 1 to 12 carbon atoms, or an alkenyloxy having 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine; Sp ¹ , Sp ² , and Sp ³ are independently single-bonded or It is an alkylene having 1 to 10 carbon atoms, in which at least one -CH _2- may be replaced by -O-, -COO-, -OCO-, or -OCOO-, and at least one. −CH ₂ CH ₂₋ may be replaced by −CH = CH− or −C≡C−, and in these groups at least one hydrogen may be replaced by fluorine or chlorine; 1, 2, 3, or 4; b is 0, 1, 2, or 3, and the sum of a and b is less than or equal to 4; c is 0, 1, 2, 3, or 4 E, f, and g are independently 0, 1, 2, 3, or 4, and the sum of e, f, and g is 2 or greater; P ¹ , P ² , and. P ³ is independently a polymerizable group represented by the formula (PA);

In formula (PA), Sp ⁴ is a single bond or an alkylene with 1 to 7 carbon atoms, in which at least one -CH ₂ − is -O-, -COO-, or -OCO-. At least one −CH ₂ CH ₂ − may be replaced with −CH = CH −, and in these groups at least one hydrogen may be replaced with fluorine; ² is a group represented by -OH, -OR ⁰ , -NH ₂ , -NHR ⁰ , or -N (R ⁰ ) ₂ , where R ⁰ is hydrogen or an alkyl having 1 to 12 carbon atoms. Yes; M ⁴ and M ⁵ are independently hydrogen, fluorine, alkyl with 1 to 5 carbon atoms, or alkyl with 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine.

One advantage of the present invention is to provide a liquid crystal composition containing a polar compound (or a polymer thereof) having a polymerizable group, wherein the polar compound has high compatibility with the liquid crystal compound. .. Another advantage is to provide a liquid crystal composition in which the vertical orientation of the liquid crystal molecules can be achieved by the action of the polymer generated from this polar compound. Other advantages are high upper temperature limit of nematic phase, lower lower limit temperature of nematic phase, small viscosity, proper optical anisotropy, very large dielectric anisotropy, large specific resistance, high stability against ultraviolet rays, heat resistance. It is to provide a liquid crystal composition that satisfies at least one of the properties such as high stability and large elastic constant. Another advantage is to provide a liquid crystal composition having an appropriate balance between at least two of these properties. Another advantage is a liquid crystal display device containing such a composition. Another advantage is to provide AM devices with characteristics such as short response time, high voltage retention, low threshold voltage, high contrast ratio, long life.

The usage of terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "composition" and "element", respectively. "Liquid crystal display element" is a general term for a liquid crystal display panel and a liquid crystal display module. The "liquid crystal compound" is a compound having a liquid crystal phase such as a nematic phase or a smectic phase and a compound having no liquid crystal phase, but is composed for the purpose of adjusting characteristics such as temperature range, viscosity and dielectric anisotropy of the nematic phase. It is a general term for compounds mixed in a product. This compound has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod-like. A "polymerizable compound" is a compound added to form a polymer in a composition. Liquid crystal compounds with alkenyl are not polymerizable in that sense.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are added to the liquid crystal composition as needed. To. The ratio (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 expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive. Parts per million by weight (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 "upper limit temperature of the nematic phase" may be abbreviated as the "upper limit temperature". The "lower limit temperature of the nematic phase" may be abbreviated as the "lower limit temperature". "Large specific resistance" means that the composition has a large specific resistance at an initial stage and has a large specific resistance after long-term use. "Large 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 at the initial stage, and after long-term use, it has a large voltage not only at room temperature but also at a temperature close to the upper limit temperature. It means having a retention rate. The properties of compositions and devices may be evaluated by aging tests (including accelerated aging tests). The expression "increase the dielectric anisotropy" means that when the composition has a positive dielectric anisotropy, its value increases positively, and the composition has 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 the 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'is arbitrary. The expression "at least one'A'may be replaced by'B'" is that when the number of'A's is 1, the position of the'A'is arbitrary and the number of'A's is 2. When there is more than one, their positions can be selected without limitation. This rule also applies to the expression "at least one'A'has been replaced by a'B'".

Expressions such as "at least one -CH _2- may be replaced by -O-" may be used. In this case, −CH ₂ −CH ₂ −CH ₂₋ may be converted to −O−CH ₂₋ O− by replacing the non-adjacent −CH ₂₋ with −O−. However, the adjacent −CH ₂₋ is not replaced by −O−. This replacement produces an unstable -O-O-CH _2- (peroxide). That is, this expression includes both "one -CH _2- may be replaced by -O-" and "at least two non-adjacent-CH _2- may be replaced by -O-". means.

In the chemical formulas of the component compounds, using symbols of terminal groups R ¹ to a plurality of compounds. In these compounds, two groups represented by any two of R ¹ may be may be the same or different. For example, there are cases where R ^{1 of} compound (1-1) is ethyl and R ¹ of compound (1-2) is ethyl. In some cases, R ^{1 of} compound (1-1) is ethyl and R ¹ of compound (1-2) is propyl. This rule also applies to symbols such as other end groups. In equation (1), when the subscript'a'is 2, there are two rings A. In this compound, the two rings represented by the two rings A may be the same or different. This rule also applies to any two rings A when the subscript'a'is greater than 2. This rule also applies to other symbols.

Symbols such as A, B, C, and D surrounded by a hexagon correspond to rings such as ring A, ring B, ring C, and ring D, respectively, and represent rings such as six-membered ring and condensed ring. In formula (2), the diagonal line that crosses one side of the hexagon indicates that any hydrogen on the ring may be replaced by a group such as -Sp ^1- P ¹ . Subscripts such as'e'indicate the number of replaced groups. When the subscript'e'is 0, there is no such replacement. When the subscript'e'is 2 or more, there are a plurality of -Sp ^1- P ¹ on the ring C. -Sp ^{1 The} plurality of groups represented by -P ¹ may be the same or different. In the expression "ring A and ring B are independently X, Y, or Z", "independently" is used because there are a plurality of subjects. In the case of "ring D is X, Y, or Z", "independently" is not used because the subject is singular. When "ring D" is used in a plurality of expressions, the rule "may be the same or different" applies to "ring D". The same applies to other groups.

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

The alkyl of the liquid crystal compound is linear or branched and does not contain cyclic alkyl. Linear alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. For the configuration of 1,4-cyclohexylene, trans is preferable to cis in order to raise the upper limit temperature.

The present invention includes the following items.

式（１）および式（２）において、Ｒ^１は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルであり；環Ａおよび環Ｂは独立して、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，３−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、ピリミジン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはテトラヒドロピラン−２，５−ジイルであり；環Ｃおよび環Ｅ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、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のアルケニルで置き換えられてもよく；環Ｄは、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、ナフタレン−１，２−ジイル、ナフタレン−１，３−ジイル、ナフタレン−１，４−ジイル、ナフタレン−１，５−ジイル、ナフタレン−１，６−ジイル、ナフタレン−１，７−ジイル、ナフタレン−１，８−ジイル、ナフタレン−２，３−ジイル、ナフタレン−２，６−ジイル、ナフタレン−２，７−ジイル、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、またはピリジン−２，５−ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、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、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ_２Ｏ−、または−ＯＣＦ_２−であり；Ｚ^３およびＺ^４は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、そして少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ_３）−、または−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｘ^１およびＸ^２は独立して、水素またはフッ素であり；Ｙ^１は、フッ素、塩素、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、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２から１２のアルケニルオキシであり；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_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ａは、１、２、３、または４であり；ｂは、０、１、２、または３であり、そしてａおよびｂの和は４以下であり；ｃは、０、１、２、３、または４であり；ｅ、ｆ、およびｇは独立して、０、１、２、３、または４であり、そしてｅ、ｆ、およびｇの和は、２以上であり；Ｐ^１、Ｐ^２、およびＰ^３は独立して、式（Ｐ−Ａ）で表される重合性基であり；

式（Ｐ−Ａ）において、Ｓｐ^４は、単結合または炭素数１から７のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；Ｒ^２は、−ＯＨ、−ＯＲ^０、−ＮＨ_２、−ＮＨＲ^０、または−Ｎ(Ｒ^０)_２で表される基であり、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；Ｍ^４およびＭ^５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 1. At least one compound selected from the group of compounds represented by the formula (1) as the first component, and at least one compound selected from the group of polar compounds represented by the formula (2) as the first additive. A liquid crystal composition containing, and having a positive dielectric anisotropy.

In formulas (1) and (2), R ¹ is an alkyl with 1 to 12 carbons, an alkoxy with 1 to 12 carbons, or an alkenyl with 2 to 12 carbons; rings A and B are independent. 1,4-Cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine -2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; rings C and E are independently cyclohexyl, cyclohexenyl, phenyl, 1-. It is naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl, or pyridine-2-yl, and in these rings at least one hydrogen is fluorine. , Chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, alkyl with 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine, or at least 1 One hydrogen may be replaced with an alkenyl having 2 to 12 carbons replaced by fluorine or chlorine; ring D 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 which at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, An alkenyl having 2 to 12 carbon atoms, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine, or an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine. Z ¹ and Z ² may be independently single-bonded, -CH ₂ CH _2- , -CH = CH-, -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CF ₂ O- or -O CF ₂ −; Z ³ and Z ⁴ are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which 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 )-and at least one hydrogen in these groups may be replaced with fluorine or chlorine; X ¹ and X ² Are independently hydrogen or fluorine; Y ¹ is fluorine, chlorine, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, and at least one hydrogen is replaced by fluorine or chlorine. An alkoxy having 1 to 12 carbon atoms, or an alkenyloxy having 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine; Sp ¹ , Sp ² , and Sp ³ are independently single-bonded or It is an alkylene having 1 to 10 carbon atoms, in which at least one -CH _2- may be replaced by -O-, -COO-, -OCO-, or -OCOO-, and at least one. −CH ₂ CH ₂₋ may be replaced by −CH = CH− or −C≡C−, and in these groups at least one hydrogen may be replaced by fluorine or chlorine; 1, 2, 3, or 4; b is 0, 1, 2, or 3, and the sum of a and b is less than or equal to 4; c is 0, 1, 2, 3, or 4 E, f, and g are independently 0, 1, 2, 3, or 4, and the sum of e, f, and g is 2 or greater; P ¹ , P ² , and. P ³ is independently a polymerizable group represented by the formula (PA);

In formula (PA), Sp ⁴ is a single bond or an alkylene with 1 to 7 carbon atoms, in which at least one -CH ₂ − is -O-, -COO-, or -OCO-. At least one −CH ₂ CH ₂ − may be replaced with −CH = CH −, and in these groups at least one hydrogen may be replaced with fluorine; ² is a group represented by -OH, -OR ⁰ , -NH ₂ , -NHR ⁰ , or -N (R ⁰ ) ₂ , where R ⁰ is hydrogen or an alkyl having 1 to 12 carbon atoms. Yes; M ⁴ and M ⁵ are independently hydrogen, fluorine, alkyl with 1 to 5 carbon atoms, or alkyl with 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine.

Item 2. In the formula (2) described in Item 1, the rings C and E are independently cyclohexyl, phenyl, 1-naphthyl, or 2-naphthyl, and in these rings, at least one hydrogen is fluorine, chlorine. , Alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, alkyl with 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine, or at least one hydrogen May be replaced with an alkenyl having 2 to 12 carbon atoms in which is replaced with fluorine or chlorine; ring D is 1,4-cyclohexylene, 1,4-phenylene, naphthalene-1,2-diyl, or naphthalene-. It is 2,6-diyl, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, at least one. Hydrogen may be replaced with an alkyl having 1 to 12 carbon atoms in which hydrogen is replaced by fluorine or chlorine, or at least one hydrogen may be replaced by an alkenyl having 2 to 12 carbon atoms in which the hydrogen is replaced by fluorine or chlorine; c is 0 or 1. Item 2. The liquid crystal composition according to Item 1.

式（１−１）から式（１−１４）において、Ｒ^１は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルであり；Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５、Ｘ^６、Ｘ^７、Ｘ^８、Ｘ^９、Ｘ^１０、Ｘ^１１、Ｘ^１２、Ｘ^１３、およびＸ^１４は独立して、水素またはフッ素であり；Ｙ^１は、フッ素、塩素、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、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２から１２のアルケニルオキシである。Item 3. Item 2. The liquid crystal composition according to Item 1 or 2, which contains at least one compound selected from the group of compounds represented by formulas (1-1) to (1-14) as a first component.

In formulas (1-1) to (1-14), R ¹ is an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, or an alkenyl having 2 to 12 carbon atoms; X ¹ , X. ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , and X ¹⁴ are independently hydrogen or fluorine; Y ¹ is fluorine, chlorine, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine, an alkoxy having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine, or at least 1 One hydrogen is an alkenyloxy having 2 to 12 carbon atoms in which fluorine or chlorine is replaced.

式（２−１）から式（２−１３）において、Ｒ^２は、−ＯＨ、−ＯＲ^０、−ＮＨ_２、−ＮＨＲ^０、または−Ｎ(Ｒ^０)_２で表される基であり、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；Ｒ^３は、水素、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、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルであり；Ｚ^３およびＺ^４は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、そして少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ_３）−、または−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｓｐ^１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_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｓｐ^４は、単結合または炭素数１から７のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；Ｌ^１、Ｌ^２、Ｌ^３、Ｌ^４、Ｌ^５、およびＬ^６は独立して、水素、フッ素、メチル、またはエチルである。Item 4. Item 2. The liquid crystal according to any one of Items 1 to 3, wherein the first additive is at least one compound selected from the group of polar compounds represented by the formulas (2-1) to (2-13). Composition.

In formulas (2-1) to (2-13), R ² is a group represented by -OH, -OR ⁰ , -NH ₂ , -NHR ⁰ , or -N (R ⁰ ) ₂ . Here, R ⁰ is hydrogen or an alkyl having 1 to 12 carbon atoms; R ³ is hydrogen, fluorine, chlorine, an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, and 2 to 12 carbon atoms. An alkenyl, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine, or an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen has been replaced by fluorine or chlorine; Z ³ and Z ⁴ independently is a single bond or alkylene having 1 to 10 carbon atoms, in the alkylene, at least one of _-CH 2 -, -O -, - CO -, - COO-, or replaced by -OCO- at best, and at least one _-CH 2 CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, or -C _(CH 3) = It may be replaced with C (CH ₃ )-and at least one hydrogen in these groups may be replaced with fluorine or chlorine; Sp ¹ and Sp ³ are independently single-bonded or 1 carbon. To 10 alkylenes, in which at least one -CH ₂ − may be replaced by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ − may be replaced by −CH = CH − or −C≡C−, in these groups at least one hydrogen may be replaced by fluorine or chlorine; Sp ⁴ is a single bond. Alternatively, it is an alkylene having 1 to 7 carbon atoms, in which at least one -CH ₂ − may be replaced by -O-, -COO-, or -OCO-, and at least one -CH ₂ CH. ₂ − may be replaced by −CH = CH−, and in these groups at least one hydrogen may be replaced by fluorine; L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁵ , and L ⁶ are each independently hydrogen, fluorine, methyl or ethyl.

Item 5. Item 1 in which the proportion of the first component is in the range of 5% by weight to 55% by weight and the proportion of the first additive is in the range of 0.05% by weight to 10% by weight based on the weight of the liquid crystal composition. 4. The liquid crystal composition according to any one of 4.

式（３）において、Ｒ^４およびＲ^５は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルであり；環Ｆおよび環Ｇは独立して、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、または２，５−ジフルオロ−１，４−フェニレンであり；Ｚ^５は、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、または−ＯＣＯ−であり；ｈは、１、２、または３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 the formula (3) as a second component.

In formula (3), R ⁴ and R ⁵ are independent of an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, or at least one hydrogen being fluorine or chlorine. It is an alkenyl having 2 to 12 carbon atoms replaced; ring F and ring G are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5. -Difluoro-1,4-phenylene; Z ⁵ is single-bonded, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-; h is 1, 2, or 3.

式（３−１）から式（３−１３）において、Ｒ^４およびＲ^５は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、または少なくとも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 7. Item 6. The liquid crystal composition according to any one of Items 1 to 6, which contains at least one compound selected from the group of compounds represented by the formulas (3-1) to (3-13) as the second component. object.

In the formula (3-13) from equation (3-1), independently of ^{R 4} and ^{R 5,} alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, from 2 to 12 carbons, alkenyl or, An alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine.

Item 8. Item 6. The liquid crystal composition according to Item 6 or 7, wherein the proportion 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.

式（４）において、Ｒ^６は炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルであり；環Ｉは、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，３−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、ピリミジン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはテトラヒドロピラン−２，５−ジイルであり；Ｚ^６は、単結合、−ＣＨ_２ＣＨ_２−、−ＣＯＯ−、または−ＯＣＯ−であり；Ｘ^１５およびＸ^１６は独立して、水素またはフッ素であり；Ｙ^２は、フッ素、塩素、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、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２から１２のアルケニルオキシであり；ｉは、１、２、３、または４である。Item 9. Item 6. The liquid crystal composition according to any one of Items 1 to 8, which contains at least one compound selected from the group of compounds represented by the formula (4) as a third component.

In formula (4), R ⁶ is an alkyl with 1 to 12 carbons, an alkoxy with 1 to 12 carbons, or an alkenyl with 2 to 12 carbons; ring I is 1,4-cyclohexylene, 1,4. -Phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane -2,5-diyl, or tetrahydropyran-2,5-diyl; Z ⁶ is single bond, -CH ₂ CH _2- , -COO-, or -OCO-; X ¹⁵ and X ¹⁶ are Independently, hydrogen or fluorine; Y ² is fluorine, chlorine, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, and at least one hydrogen is replaced by fluorine or chlorine. An alkoxy having 1 to 12 carbon atoms, or an alkenyloxy having 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine; i is 1, 2, 3, or 4.

式（４−１）から式（４−１６）において、Ｒ^６は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルである。Item 10. Item 2. The liquid crystal composition according to any one of Items 1 to 9, which contains at least one compound selected from the group of compounds represented by the formulas (4-1) to (4-16) as the third component. object.

In formulas (4-1) to (4-16), R ⁶ is an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, or an alkenyl having 2 to 12 carbon atoms.

Item 11. Item 9. The liquid crystal composition according to Item 9 or 10, wherein the proportion of the third component is in the range of 5% by weight to 50% by weight based on the weight of the liquid crystal composition.

式（５）において、Ｒ^７およびＲ^８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Ｊおよび環Ｌは独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレン、またはテトラヒドロピラン−２，５−ジイルであり；環Ｋ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^７およびＺ^８は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、または−ＯＣＯ−であり；ｊは、１、２、または３であり、ｋは０または１であり、そしてｊとｋとの和は３以下である。Item 12. Item 6. The liquid crystal composition according to any one of Items 1 to 11, which contains at least one compound selected from the group of compounds represented by the formula (5) as the fourth component.

In formula (5), R ⁷ and R ⁸ are independently composed of an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, or an alkenyloxy having 2 to 12 carbon atoms. Yes; Ring J and Ring L are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine. , Or tetrahydropyran-2,5-diyl; ring K is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5. - methyl-1,4-phenylene, it is a 3,4,5-trifluoro-2,6-diyl or 7,8-difluoro-chroman-2,6-diyl,; ^{Z 7} and ^{Z 8} are independently a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or a -OCO-; j is 1, 2 or 3,, k is 0 or 1 And the sum of j and k is less than or equal to 3.

式（５−１）から式（５−２２）において、Ｒ^７およびＲ^８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 13. Item 2. The liquid crystal composition according to any one of Items 1 to 12, which contains at least one compound selected from the group of compounds represented by the formulas (5-1) to (5-22) as the fourth component. object.

In formulas (5-1) to (5-22), R ⁷ and R ⁸ are independently alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or It is an alkoxyoxy having 2 to 12 carbon atoms.

Item 14. Item 12. The liquid crystal composition according to Item 12 or 13, wherein the proportion of the fourth component is in the range of 3% by weight to 40% by weight based on the weight of the liquid crystal composition.

式（６）において、環Ｔおよび環Ｖ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Ｕは、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、ナフタレン−１，２−ジイル、ナフタレン−１，３−ジイル、ナフタレン−１，４−ジイル、ナフタレン−１，５−ジイル、ナフタレン−１，６−ジイル、ナフタレン−１，７−ジイル、ナフタレン−１，８−ジイル、ナフタレン−２，３−ジイル、ナフタレン−２，６−ジイル、ナフタレン−２，７−ジイル、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、またはピリジン−２，５−ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；Ｚ^１１およびＺ^１２は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、そして少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ_３）−、または−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｐ^４、Ｐ^５、およびＰ^６は、項１に記載の式（Ｐ−Ａ）で表される重合性基とは異なる重合性基であり；Ｓｐ^１０、Ｓｐ^１１、およびＳｐ^１２は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、そして少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ｔは０、１、または２であり；ｕ、ｖ、およびｗは独立して、０、１、２、３、または４であり、そしてｕ、ｖ、およびｗの和は、１以上である。Item 15. Item 6. The liquid crystal composition according to any one of Items 1 to 14, which contains at least one compound selected from the group of polymerizable compounds represented by the formula (6) as the second additive.

In formula (6), rings T and V are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-. 2-Il or pyridine-2-yl, in these rings at least one hydrogen may be fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least one hydrogen. It may be replaced with an alkyl having 1 to 12 carbon atoms replaced with fluorine or chlorine; ring U 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 which at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least 1 One hydrogen may be replaced with an alkyl having 1 to 12 carbon atoms replaced with fluorine or chlorine; Z ¹¹ and Z ¹² are independently single-bonded or alkylenes having 1 to 10 carbon atoms, and in this alkylene. , 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 at least one in these groups. hydrogen may be replaced by fluorine or chlorine; P ^{4, P 5,} and P ⁶ is located at a different polymerizable group is a polymerizable group represented by the formula (P-a) according to claim 1 Sp ¹⁰ , Sp ¹¹ , and Sp ¹² are independently single-bonded or 1 to 10 carbon alkylenes, in which at least one -CH ₂ − is -O-, -COO-,-. Even if it is replaced by OCO- or -OCOO- Well, and at least one -CH ₂ CH _2- may be replaced by -CH = CH- or -C≡C-, in these groups at least one hydrogen is replaced by fluorine or chlorine. Often; t is 0, 1, or 2; u, v, and w are independently 0, 1, 2, 3, or 4, and the sum of u, v, and w is 1. That is all.

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 16. In the formula (6) described in Item 15, P ⁴ , P ⁵ , and P ⁶ were independently selected from the group of polymerizable groups represented by the formulas (P-1) to (P-5). Item 2. The liquid crystal composition according to Item 15, which is a group.

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

式（６−１）から式（６−２８）において、Ｐ^４、Ｐ^５、およびＰ^６は独立して、式（Ｐ−１）から式（Ｐ−３）で表される重合性基の群から選択された基であり、

ここでＭ^１、Ｍ^２、およびＭ^３は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルであり；Ｓｐ^１０、Ｓｐ^１１、およびＳｐ^１２は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、そして少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。Item 17. Item 6. The item according to any one of Items 1 to 16, which contains at least one compound selected from the group of polymerizable compounds represented by the formulas (6-1) to (6-28) as the second additive. Liquid crystal composition.

In the formula (6-28) from equation ^(6-1), P 4, ^{P 5,} and ^{P 6} are each independently of the polymerizable group represented by the formula (P-1) by the formula (P-3) A group selected from the group

Here, M ¹ , M ² , and M ³ are independently hydrogen, fluorine, an alkyl having 1 to 5 carbon atoms, or an alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. Sp ¹⁰ , Sp ¹¹ , and Sp ¹² are independently single-bonded or alkylenes with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -COO-,-. It may be replaced by OCO-, or -OCOO-, and at least one -CH ₂ CH _2- may be replaced by -CH = CH- or -C≡C-, at least in these groups. One hydrogen may be replaced with fluorine or chlorine.

Item 18. Item 2. The liquid crystal composition according to any one of Items 15 to 17, wherein the ratio of the second additive is in the range of 0.03% by weight to 10% by weight based on the weight of the liquid crystal composition.

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

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

Item 21. A polymer-supported orientation type liquid crystal display device containing the liquid crystal composition according to any one of Items 1 to 14 and polymerized with the first additive contained in the liquid crystal composition.

Item 22. A polymer-supported oriented liquid crystal display device containing the liquid crystal composition according to any one of Items 15 to 18, wherein the first additive and the second additive contained in the liquid crystal composition are polymerized. ..

Item 23. A liquid crystal display device having no alignment film, which contains the liquid crystal composition according to any one of Items 1 to 14, and is polymerized with the first additive contained in the liquid crystal composition.

Item 24. A liquid crystal display element having no alignment film, which contains the liquid crystal composition according to any one of Items 15 to 18, wherein the first additive and the second additive contained in the liquid crystal composition are polymerized.

Item 25. Use of the liquid crystal composition according to any one of Items 1 to 18 in a liquid crystal display element.

Item 26. Use of the liquid crystal composition according to any one of Items 1 to 18 in a polymer-supported oriented liquid crystal display device.

Item 27. 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 sections. (A) The above liquid crystal composition is placed between two substrates, and light is applied to the composition while a voltage is applied to polymerize the polar compound having a polymerizable group contained in the composition. The method for manufacturing the above-mentioned liquid crystal display element. (B) The upper limit 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 more, the above liquid crystal composition.

The present invention also includes the following sections. (C) The above composition containing at least two compounds selected from the above polar compounds (2). (D) The above composition further containing a polar compound different from the above polar compound (2). (E) One, two or at least three additives such as optically active compounds, antioxidants, UV absorbers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds. The above composition containing. (F) AM device containing the above composition. (G) A device containing the above composition and having a mode of TN, ECB, OCB, IPS, FFS, VA, or FPA. (H) A transmissive device containing the above composition. (I) The above composition is used as a composition having a nematic phase. (J) A composition prepared by adding an optically active compound to the above composition is used as an optically active composition.

The composition of the present invention will be described in the following order. First, the composition of the composition will be described. Secondly, the main properties of the constituent compounds and the main effects of this compound on the composition will be described. Third, the combination of ingredients in the composition, the preferred proportions of the ingredients and the rationale thereof will be described. Fourth, preferred forms of the component compounds will be described. Fifth, preferred component compounds are shown. Sixth, additives that may be added to the composition will be described. Seventh, a method for synthesizing a component compound will be described. Finally, the use of the composition will be described.

First, the composition of the composition will be described. The compositions of the present invention are classified into composition A and composition B. The composition A further contains other liquid crystal compounds, additives and the like in addition to the liquid crystal compound selected from the compound (1), the compound (3), the compound (4) and the compound (5). May be good. The "other liquid crystal compound" is a liquid crystal compound different from the compound (1), the compound (3), the compound (4), and the compound (5). Such compounds are mixed into the composition for the purpose of further adjusting the properties. Additives include optically active compounds, antioxidants, UV absorbers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like.

The composition B is substantially composed of only a liquid crystal compound selected from the compound (1), the compound (3), the compound (4), and the compound (5). "Substantially" means that composition B may contain additives but does not contain other liquid crystal compounds. The composition B has a smaller number of components than the composition A. The composition B is preferable to the composition A from the viewpoint of reducing the cost. Composition A is preferable to composition B from the viewpoint that the properties can be further adjusted by mixing other liquid crystal compounds.

Secondly, the main properties of the constituent compounds and the main effects of this compound on the properties of the composition will be described. The main properties of the constituent 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 and S are classifications based on qualitative comparisons between the constituent compounds, and the symbol 0 means that the value is or is close to zero.

When the component compound is mixed with the composition, the main effects of the component compound on the properties of the composition are as follows. Compound (1) increases the dielectric anisotropy. Compound (3) raises the upper temperature limit or lowers the viscosity. Compound (4) increases the dielectric anisotropy and lowers the lower limit temperature. Compound (5) increases the dielectric constant in the minor axis direction. Compound (5) is added for the purpose of adjusting the elastic constant of the composition and adjusting the voltage-transmittance curve of the device.

Compound (2) is adsorbed on the substrate surface by the action of polar groups to control the orientation of liquid crystal molecules. In order to obtain the desired effect, it is essential that the compound (2) has high compatibility with the liquid crystal compound. Compound (2) has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-shaped, which is most suitable for this purpose. Compound (6) is added for the purpose of further adapting to a polymer support oriented device. Compound (2) or compound (6) gives a polymer by polymerization. This polymer stabilizes the orientation of the liquid crystal molecules, thus reducing the response time of the device and improving image burn-in. From the viewpoint of the orientation of the liquid crystal molecules, the polymer of compound (2) is effective. The polymer of compound (6) is also effective. The combination of compound (2) and compound (6) is even more effective. A synergistic effect can be expected from this combination. With this combination, better long-term stability can be expected than with compound (2) alone.

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

The preferable ratio of the compound (1) is about 5% by weight or more in order to increase the dielectric anisotropy, and about 55% by weight or less in order to lower the lower limit temperature or lower the viscosity. A more preferred proportion is in the range of about 5% by weight to about 45% by weight. A particularly preferred proportion is in the range of about 10% by weight to about 35% by weight.

The preferable ratio of the compound (2) is about 0.05% by weight or more for aligning the liquid crystal molecules, and about 10% by weight or less for preventing display defects of the device. A more preferred ratio is in the range of about 0.1% by weight to about 7% by weight. A particularly preferred ratio is in the range of about 0.5% by weight to about 5% by weight.

The preferred proportion of compound (3) is about 10% by weight or more to raise the upper temperature limit or lower the viscosity, and about 90% by weight or less to raise the dielectric anisotropy. A more preferred proportion is in the range of about 15% to about 85% by weight. A particularly preferred proportion is in the range of about 20% by weight to about 80% by weight.

The preferable ratio of the compound (4) is about 5% by weight or more in order to increase the dielectric anisotropy, and about 50% by weight or less in order to lower the lower limit temperature. A more preferred ratio is in the range of about 5% by weight to about 40% by weight. A particularly preferred proportion is in the range of about 5% by weight to about 30% by weight.

The preferable ratio of the compound (5) is about 3% by weight or more in order to increase the dielectric constant in the minor axis direction, and about 40% by weight or less in order to lower the lower limit temperature. A more preferred proportion is in the range of about 5% by weight to about 35% by weight. A particularly preferred proportion is in the range of about 10% by weight to about 35% by weight.

The preferable ratio of the compound (6) is about 0.03% by weight or more in order to improve the long-term reliability of the device, and about 10% by weight or less in order to prevent display defects of the device. A more preferred ratio is in the range of about 0.1% by weight to about 2% by weight. A particularly preferred ratio is in the range of about 0.2% by weight to about 1.0% by weight.

Fourth, preferred forms of the component compounds will be described. In formulas (1), (3), (4), and (5), R ¹ is an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, or an alkenyl having 2 to 12 carbon atoms. Is. Preferred R ¹ is an alkyl having 1 to 12 carbon atoms for increased stability to UV light or heat. R ⁴ and R ⁵ are independently alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, or 2 carbons in which at least one hydrogen is replaced with fluorine or chlorine. To 12 alkenyl. Preferred R ⁴ or R ⁵ is an alkyl having 1 to 12 carbon atoms to increase stability against UV light or heat, and an alkenyl having 2 to 12 carbon atoms to lower the lower temperature limit or to lower the viscosity. ..

R ⁶ is an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, or an alkenyl having 2 to 12 carbon atoms. Preferred R ⁶ is an alkyl having 1 to 12 carbon atoms for increased stability to UV light or heat. R ⁷ and R ⁸ are independently alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or alkenyloxy with 2 to 12 carbon atoms. Preferred R ⁷ or R ⁸ is an alkyl having 1 to 12 carbon atoms to increase stability to ultraviolet light or heat, and an alkoxy having 1 to 12 carbon atoms to increase dielectric anisotropy.

Preferred alkyls are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. More preferred alkyls are ethyl, propyl, butyl, pentyl, or heptyl to reduce viscosity.

Preferred alkoxys are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. More preferred alkoxys for reducing viscosity are methoxy or ethoxy.

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

Preferred alkenyloxys are vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. More preferred alkenyloxy to reduce viscosity are allyloxy or 3-butenyloxy.

Preferred examples of alkyl in which at least one hydrogen has been replaced with fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl. , Or 8-fluorooctyl. More preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl to increase the dielectric anisotropy.

Preferred examples of alkenyl in which at least one hydrogen is replaced with 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. More preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl to reduce the viscosity.

Ring A and Ring B are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro. It is -1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl. Preferred ring A or ring B is 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,6-difluoro-1,4-phenylene to increase optical anisotropy. Rings F and G are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. Preferred ring F or ring G is 1,4-cyclohexylene to reduce viscosity and 1,4-phenylene to increase optical anisotropy. Ring I is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene. , Pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl. The preferred ring I is 1,4-phenylene or 2-fluoro-1,4-phenylene to increase the optical anisotropy.

または

であり、好ましくは

である。Ring J and Ring L are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine, or Tetrahydropyran-2,5-diyl. Preferred ring J or ring L is 1,4-cyclohexylene to reduce viscosity, tetrahydropyran-2,5-diyl to increase dielectric anisotropy, and to increase optical anisotropy. It is 1,4-phenylene. Ring K 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. The preferred ring K is 2,3-difluoro-1,4-phenylene to increase the dielectric anisotropy. Tetrahydropyran-2,5-diyl is

Or

And preferably

Is.

Z ¹ and Z ² are independently single-bonded, -CH ₂ CH _2- , -CH = CH-, -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CF ₂ O- , Or −OCF _2- . Preferred Z ¹ or Z ² is a single bond to reduce viscosity. Z ⁵ represents a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or -OCO-. Preferred Z ⁵ is a single bond to reduce viscosity. Z ⁶ is a single bond, -CH ₂ CH _2- , -COO-, or -OCO-. Preferred Z ⁶ is a single bond to reduce viscosity. Z ⁷ and Z ⁸ are independently single-bonded, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. Preferred Z ⁷ or Z ⁸ is a single bond to reduce the viscosity and −CH ₂ O− or −OCH ₂ − to increase the dielectric anisotropy.

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ , and X ¹⁶ are independent. And then hydrogen or fluorine. Preferred X ¹ to X ¹⁵ or X ¹⁶ are fluorine to increase the dielectric anisotropy.

Y ¹ and Y ² are independently from fluorine, chlorine, alkyl with 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine, and 1 carbon number in which at least one hydrogen is replaced with fluorine or chlorine. Twelve alkoxys, or alkenyloxys having 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine. Preferred Y ¹ or Y ² is fluorine to lower the lower limit temperature. A preferred example of an alkyl in which at least one hydrogen has been replaced with fluorine or chlorine is trifluoromethyl. A preferred example of an alkoxy in which at least one hydrogen has been replaced with fluorine or chlorine is trifluoromethoxy. A preferred example of alkenyloxy in which at least one hydrogen has been replaced with fluorine or chlorine is trifluorovinyloxy.

a is 1, 2, 3, or 4, b is 0, 1, 2, or 3, and the sum of a and b is 4 or less. Preferred a is 2 or 3 in order to increase the dielectric anisotropy. Preferred b is 0 or 1 to lower the lower limit temperature. h is 1, 2, or 3. The preferred h is 1 for lowering the viscosity and 2 for lowering the lower limit temperature. i is 1, 2, 3, or 4. Preferred i is 2 or 3 to increase the dielectric anisotropy. j is 1, 2, or 3, k is 0 or 1, and the sum of j and k is 3 or less. The preferred j is 1 for lowering the viscosity and 2 or 3 for raising the upper temperature limit. The preferred k is 0 to lower the viscosity and 1 to lower the lower limit temperature.

In the polymerizable group represented by the formula (PA) in the formula (2), R ² is represented by −OH, −OR ⁰ , −NH ₂ , −NHR ⁰ , or −N (R ⁰ ) ₂ . The group represented, where R ⁰ is hydrogen or an alkyl having 1 to 12 carbon atoms. From the viewpoint of high compatibility with the liquid crystal composition, it is particularly preferable that R ² is −OH or −NH ₂ . -OH is preferable to -O-, -CO-, or -COO- because it has a high anchoring force. Groups with multiple heteroatoms (nitrogen, oxygen) are particularly preferred. Compounds with such polar groups are effective even at low concentrations. Compound (2) is preferably stable against ultraviolet rays and heat. When the compound (2) is added to the composition, it is preferable that the compound does not lower the voltage holding ratio of the device. Compound (2) preferably has low volatility. The preferred 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.

Rings C and E 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 with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, at least one hydrogen. May be replaced with an alkyl having 1 to 12 carbon atoms replaced with fluorine or chlorine, or at least one hydrogen with an alkenyl having 2 to 12 carbon atoms replaced with fluorine or chlorine. Preferred ring C or ring E is cyclohexyl or phenyl.

Ring D 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, pyrimidin-2,5-diyl, or pyridine-2,5-diyl, in these rings. At least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, from 1 carbon number in which at least one hydrogen is replaced with fluorine or chlorine. Twelve alkyls, or at least one hydrogen, may be replaced with an alkenyl having 2 to 12 carbon atoms in which fluorine or chlorine has been replaced. The preferred ring D is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ³ and Z ⁴ are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, or-. It may be replaced by OCO-, and at least one _-CH 2 CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, or -C It may be replaced by (CH ₃ ) = C (CH ₃ ) −, and in these groups at least one hydrogen may be replaced by fluorine or chlorine. Preferred Z ³ or Z ⁴ are single bonds, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. A more preferred Z ³ or Z ⁴ is a single bond.

Sp ¹ , Sp ² , and Sp ³ are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH ₂ − is -O-, -COO-, -OCO. -Or -OCOO- may be replaced, and at least one -CH ₂ CH _2- may be replaced with -CH = CH- or -C≡C-, at least 1 in these groups. One hydrogen may be replaced with fluorine or chlorine. Preferred Sp ¹ or Sp ² are alkylenes having 1 to 10 carbon atoms with a single bond and at least one −CH ₂ − replaced with −O−. Sp ⁴ is a single bond or an alkylene having 1 to 7 carbon atoms, in which at least one -CH ₂ − may be replaced with -O-, -COO-, or -OCO-, at least. One −CH ₂ CH ₂₋ may be replaced by −CH = CH−, and at least one hydrogen in these groups may be replaced by fluorine.

c is 0, 1, 2, 3, or 4. Preferred c is 0, 1, or 2. e, f, and g are independently 0, 1, 2, 3, or 4, and the sum of e, f, and g is 2 or greater.

P ¹ , P ² , and P ³ are independently polymerizable groups represented by the formula (PA).

M ⁴ and M ⁵ are independently hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. Preferred M ⁴ or M ⁵ is hydrogen or methyl to increase reactivity. A more preferred M ⁴ or M ⁵ is hydrogen.

In formulas (2-1) to (2-13), R ³ is hydrogen, fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or at least. An alkyl having 1 to 12 carbon atoms in which one hydrogen has been replaced with fluorine or chlorine, or an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine. Preferred ^{R 3} is alkyl of 1 to 12 carbons.

L ¹ , L ² , L ³ , L ⁴ , L ⁵ , and L ⁶ are independently hydrogen, fluorine, methyl, or ethyl. ^{L 6} from the preferred ^{L 1} is hydrogen, fluorine or methyl. More preferred L ¹ to L ⁶ are hydrogen or fluorine.

In the formula ^{(6), P 4, P} 5, and ^{P 6} are each independently a different polymerizable group and a polymerizable group represented by the formula (P-A). This polymerizable group does not have a polar group such as -OH, -OR ⁰ , -NH ₂ , -NHR ⁰ , or -N (R ⁰ ) ₂ . Here, R ⁰ is hydrogen or an alkyl having 1 to 12 carbon atoms. Preferred ^P 4, ^{P 5} or ^{P 6,} is selected based on the group of the polymerizable group represented by the formula (P-1) by the formula (P-5). Further preferred ^P 4, ^{P 5} or ^{P 6,} has the formula (P-1), formula (P-2), or a group represented by the formula (P-3). Particularly preferred P ⁴ , P ⁵ , or P ⁶ is a group represented by the formula (P-1) or the formula (P-2). The most preferred ^P 4, ^{P 5} or ^{P 6,} is a group represented by the formula (P-1). The preferred group represented by the formula (P-1) is acryloyloxy (-OCO-CH = CH ₂ ) or methacryloyloxy (-OCO-C (CH ₃ ) = CH ₂ ). The wavy lines of the formulas (P-1) to (P-5) indicate the sites to be combined.

In formulas (P-1) to (P-5), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine. It is an alkyl having 1 to 5 carbon atoms replaced with. Preferred M ¹ , M ² , or M ³ is hydrogen or methyl to increase reactivity. The more preferred M ¹ is hydrogen or methyl, and the more preferred M ² or M ³ is hydrogen.

In formula (6), Sp ¹⁰ , Sp ¹¹ , and Sp ¹² are independently single bonds or alkylenes having 1 to 10 carbon atoms. In this alkylene, at least one −CH ₂ − may be replaced by −O −, −COO−, −OCO−, or −OCOO−, and at least one −CH ₂ CH ₂₋ is −CH. = CH- or -C≡C- may be replaced, and in these groups at least one hydrogen may be replaced with fluorine or chlorine. Preferred Sp ¹⁰ , Sp ¹¹ , or Sp ¹² are single bonds, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CO-CH = CH-, or. -CH = CH-CO-. More preferred Sp ¹⁰ , Sp ¹¹ , or Sp ¹² are single bonds.

In formula (6), rings T and V are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-. In these rings, 2-yl or pyridin-2-yl, at least one hydrogen can be fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least one hydrogen. It may be replaced with an alkyl having 1 to 12 carbon atoms replaced with fluorine or chlorine. The preferred ring T or ring V is phenyl.

Ring U 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 with fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, or alkyl with 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. May be good. The preferred ring U is 1,4-phenylene or 2-fluoro-1,4-phenylene.

In formula (6), Z ¹¹ and Z ¹² are independently single-bonded or alkylenes having 1 to 10 carbon atoms, in which 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 at least one hydrogen in these groups may be replaced with fluorine or chlorine. Preferred Z ¹¹ or Z ¹² are single bonds, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. A more preferred Z ¹¹ or Z ¹² is a single bond.

In formula (6), t is 0, 1, or 2. Preferred t is 0 or 1. u, v, and w are independently 0, 1, 2, 3, or 4, and the sum of u, v, and w is greater than or equal to 1. Preferred u, v, or w is 1 or 2.

Fifth, preferred component compounds are shown. Preferred compounds (1) are compounds (1-1) to compounds (1-14) according to Item 3. In these compounds, at least one of the first components is compound (1-3), compound (1-4), compound (1-7), compound (1-9), compound (1-10), or compound. It is preferably (1-12). At least two of the first components are compound (1-3) and compound (1-4), compound (1-3) and compound (1-7), compound (1-3) and compound (1-10), It is preferably a combination of compound (1-7) and compound (1-10), or compound (1-9) and compound (1-10).

Preferred compounds (2) are compounds (2-1) to compounds (2-13) according to Item 4. In these compounds, at least one of the first additives is compound (2-1), compound (2-3), compound (2-5), compound (2-6), compound (2-7), compound. It is preferably (2-9), compound (2-10), or compound (2-11). At least two of the first additives are compound (2-1) and compound (2-5), compound (2-3) and compound (2-5), or compound (2-10) and compound (2-11). ) Is preferable.

Preferred compounds (3) are compounds (3-1) to compounds (3-13) according to Item 7. In these compounds, at least one of the second components is compound (3-1), compound (3-3), compound (3-5), compound (4-6), compound (5-8), or compound. (6-13) is preferable. At least two of the second components are compound (3-1) and compound (3-3), compound (3-1) and compound (3-5), compound (3-1) and compound (3-8), Alternatively, it is preferably a combination of compound (3-3) and compound (3-5).

Preferred compounds (4) are compounds (4-1) to compounds (4-16) according to Item 10. In these compounds, at least one of the third components is compound (4-4), compound (4-8), compound (4-9), compound (4-11), compound (4-12), compound ( It is preferably 4-13) or compound (4-16). At least two of the third components are compound (4-9) and compound (4-12), compound (4-11) and compound (4-12), compound (4-12) and compound (4-13), Alternatively, it is preferably a combination of compound (4-12) and compound (4-16).

Preferred compounds (5) are compounds (5-1) to compounds (5-22) according to Item 13. In these compounds, at least one of the fourth components is compound (5-1), compound (5-3), compound (5-4), compound (5-6), compound (5-8), or compound. (5-10) is preferable. At least two of the fourth components are compound (5-1) and compound (5-6), compound (5-1) and compound (5-10), compound (5-3) and compound (5-8), It is preferably a combination of compound (5-4) and compound (5-6), compound (5-4) and compound (5-8), or compound (5-4) and compound (5-10).

Preferred compounds (6) are compounds (6-1) to compounds (6-28) according to Item 17. More preferred compounds (6) are compound (6-1), compound (6-2), compound (6-3), compound (6-4), compound (6-5), compound (6-6), With compound (6-7), compound (6-18), compound (6-20), compound (6-23), compound (6-24), compound (6-25), and compound (6-26). is there. Particularly preferred compounds (6) are compound (6-2), compound (6-3), compound (6-4), and compound (6-18).

Sixth, additives that may be added to the composition will be described. Such additives include optically active compounds, antioxidants, UV 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 (7-1) to compound (7-5). The preferred proportion of the optically active compound is about 5% by weight or less. A more preferred ratio is in the range of about 0.01% by weight to about 2% by weight.

An antioxidant is composed to prevent a decrease in resistivity due to heating in the atmosphere, or to maintain a large voltage retention not only at room temperature but also at temperatures close to the upper limit temperature after long-term use of the device. It is added to the thing. A preferred example of the antioxidant is compound (8) in which n is an integer of 1 to 9.

In compound (8), preferred n is 1, 3, 5, 7, or 9. A more preferable n is 7. Since the compound (8) having n of 7 has low volatility, it is effective in 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 has been used for a long time. The preferable ratio of the antioxidant is about 50 ppm or more in order to obtain the effect, and is about 600 ppm or less so as not to lower the upper limit temperature or raise the lower limit temperature. A more preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferred examples of the UV absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as sterically hindered amines are also preferred. The preferable ratio of these absorbents and stabilizers is about 50 ppm or more in order to obtain the effect, and about 10,000 ppm or less so as not to lower the upper limit temperature or raise the lower limit temperature. A more preferred ratio is in the range of about 100 ppm to about 10000 ppm.

Dichroic dyes such as azo dyes, anthraquinone dyes, etc. are added to the composition to accommodate devices in GH (guest host) mode. The preferred proportion of dye is in the range of about 0.01% by weight to about 10% by weight. To prevent foaming, a defoaming agent such as dimethyl silicone oil or methyl phenyl silicone oil is added to the composition. The preferable ratio of the defoaming agent is about 1 ppm or more in order to obtain the effect, and about 1000 ppm or less in order to prevent display defects. A more preferred ratio is in the range of about 1 ppm to about 500 ppm.

Polymerizable compounds are used to adapt to polymer-supported orientation (PSA) type devices. Compound (2) and compound (6) are suitable for this purpose. Along with the compound (2) and the compound (6), a polymerizable compound different from the compound (2) and the compound (6) may be added to the composition. Preferred examples of such polymerizable compounds are compounds such as acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxylane, oxetane), vinyl ketones and the like. More preferred examples are acrylates or methacrylates. The preferred proportion of compound (2) and compound (6) is about 10% by weight or more based on the total weight of the polymerizable compound. A more preferable ratio is about 50% by weight or more. A particularly preferable ratio is about 80% by weight or more. A particularly preferable ratio is also 100% by weight. Reactivity of polymerizable compounds and liquid crystal molecules by changing the types of compound (2) and compound (6), or by combining compound (2) and compound (6) with other polymerizable compounds in an appropriate ratio. The pre-tilt angle of can be adjusted. By optimizing the pre-tilt angle, a short response time of the device can be achieved. Since the orientation of the liquid crystal molecules is stabilized, a large contrast ratio and a long life can be achieved.

This polymerizable compound is polymerized by irradiation with ultraviolet rays. Polymerization may be carried out in the presence of a suitable initiator, such as a photopolymerization initiator. Appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those of skill in the art and are described in the literature. For example, the photopolymerization initiators Irgacure651®, Irgacure184® (registered trademark; BASF), or Darocur1173® are suitable for radical polymerization. The preferred proportion of 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 preferred ratio is in the range of about 1% by weight to about 3% by weight.

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

A polar compound is an organic compound having polarity. Compounds having an ionic bond are not included here. Atoms such as oxygen, sulfur, and nitrogen are more electrically negative and tend to have partial negative charges. Carbon and hydrogen tend to be neutral or have a partially positive charge. Polarity arises from the uneven distribution of partial charges between different atoms in a compound. For example, polar compounds have at least one of the partial structures such as -OH, -COOH, -SH, -NH ₂ ,>NH,> N-.

Seventh, a method for synthesizing a component compound will be described. These compounds can be synthesized by known methods. An example of the synthesis method. Compound (1-4) and compound (1-10) are synthesized by the method described in JP-A-10-251186. The method for synthesizing compound (2) is described in the section of Examples. Compound (3-1) is synthesized by the method described in JP-A-59-176221. Compound (4-4) and compound (4-8) are synthesized by the method described in JP-A-2-233626. Compound (5-1) and compound (5-6) are synthesized by the method described in JP-A-2-503441. Compound (6-18) is synthesized by the method described in JP-A-7-101900. The compound of formula (8) where n is 1 is available from Sigma-Aldrich Corporation. Compound (8) and the like having n of 7 are synthesized by the method described in US Pat. No. 3,660,505.

Compounds for which synthetic methods were not described are Organic Syntheses, John Wiley & Sons, Inc., Organic Reactions, John Wiley & Sons, Inc., and Comprehensive Organic Syntheses ( Comprehensive Organic Synthesis, Pergamon Press), New Experimental Chemistry Course (Maruzen), etc. can be synthesized by the methods described in the books. The composition is prepared from the compound thus obtained by a known method. For example, the constituent compounds are mixed and dissolved by heating.

Finally, the use of the composition will be described. Most compositions have a lower limit temperature of about −10 ° C. or lower, an upper limit temperature of about 70 ° C. or higher, and optical anisotropy in the range of about 0.07 to about 0.20. Compositions with optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the proportions of the constituent compounds or by mixing 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. The element containing this composition has a large voltage holding ratio. This composition is suitable for AM devices. This composition is particularly suitable for transmissive AM devices. This composition can be used as a composition having a nematic phase, or can be used as an optically active composition by adding an optically active compound.

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

An example of a 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 prepared. This substrate has an alignment film. At least one of the substrates has an electrode layer. Liquid crystal compounds are mixed to prepare a liquid crystal composition. A polymerizable compound is added to this composition. Additional additives may be added as needed. This composition is injected into the device. Light is irradiated while a voltage is applied to this element. Ultraviolet rays are preferred. The polymerizable compound is polymerized by light irradiation. By this polymerization, a composition containing a polymer is produced. The polymer-supported orientation type device is manufactured by such a procedure.

In this procedure, when a voltage is applied, the liquid crystal molecules are oriented by the action of the alignment film and the electric field. The molecules of the polymerizable compound are also oriented according to this orientation. Since the polymerizable compound is polymerized by ultraviolet rays in this state, a polymer that maintains this orientation is produced. Due to the effect of this polymer, the response time of the device is shortened. Since the burn-in of the image is a malfunction of the liquid crystal molecules, the burn-in is also improved at the same time by the effect of this polymer. It is also possible to prepolymerize the polymerizable compound in the composition and arrange the composition between the substrates of the liquid crystal display element.

When a polar compound having a polymerizable group such as compound (2) is used as the polymerizable compound, an alignment film is not required on the substrate of the element. Devices without an alignment film are manufactured from a substrate without an alignment film according to the procedure described in the previous paragraph.

In this procedure, compound (2) is arranged on the substrate because the polar groups interact with the surface of the substrate. Liquid crystal molecules are oriented according to this arrangement. When a voltage is applied, the orientation of the liquid crystal molecules is further promoted. Since the polymerizable group is polymerized by ultraviolet rays in this state, a polymer that maintains this orientation is produced. Due to the effect of this polymer, the orientation of the liquid crystal molecules is additionally stabilized, and the response time of the device is shortened. Since the burn-in of the image is a malfunction of the liquid crystal molecules, the burn-in is also improved at the same time by the effect of this polymer.

The present invention will be described in more detail by way of examples. The present invention is not limited by these examples. The present invention includes a mixture of the composition (M1) and the composition (M2). The present invention also includes a mixture of at least two of the compositions of the Examples. The synthesized compound was identified by a method such as NMR analysis. The properties of the compound, composition and device were measured by the following methods.

NMR analysis: A DRX-500 manufactured by Bruker Biospin was used for the measurement. ^{1 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. ^{19 In the} F-NMR measurement, CFCl ₃ was used as an internal standard, and the number of integrations was 24. In the description of the nuclear magnetic resonance spectrum, s is singlet, d is doublet, t is triplet, q is quartet, quin is quintet, sex is sextet, m is multiplet, and br is broad.

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

A solvent such as chloroform or hexane may be used to dilute the sample. The following capillary columns may be used to separate the constituent compounds. HP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc., 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 overlapping of compound peaks.

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

Measurement sample: When measuring the characteristics of the composition and the device, the composition was used as it was as a sample. When measuring the properties of the compound, a sample for measurement was prepared by mixing this compound (15% by weight) with the mother liquid crystal (85% by weight). From the values obtained by the measurement, the characteristic values of the compound were calculated by the extrapolation method. (Extrapolated value) = {(Measured value of sample) −0.85 × (Measured value of mother liquid crystal)} /0.15. When the smectic phase (or crystal) precipitates at 25 ° C. at this ratio, the ratio of the compound to 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. The values of upper temperature, optical anisotropy, viscosity, and permittivity anisotropy for the compound were determined by this extrapolation method.

The following mother liquid crystal was used. The ratio of the component compounds is shown in% by weight.

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

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

(2) Minimum Temperature of a Nematic Phase _{(T C;} ° C.): A sample having a nematic phase was put in a glass bottle, 0 ℃, -10 ℃, -20 ℃, -30 ℃, and -40 ℃ for 10 days in a freezer After storage, the liquid crystal phase was observed. For example, _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 the measurement.

(4) Viscosity (rotational viscosity; γ1; measured at 25 ° C.; mPa · s): The measurement is carried out according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. I obeyed. The sample was placed in a TN device having a twist angle of 0 ° and a distance (cell gap) between the two glass substrates of 5 μm. A stepwise application was applied to this device in 0.5 V increments in the range of 16 V to 19.5 V. After no application for 0.2 seconds, application was repeated under the conditions of only one square wave (square pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. These measurements and M.I. The value of rotational viscosity was obtained from the paper by Imai et al., Calculation 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 light having a wavelength of 589 nm and using an Abbe refractometer with a polarizing plate attached to the eyepiece. After rubbing the surface of the main prism in one direction, the sample was dropped onto the main prism. The refractive index n‖ was measured when the direction of polarization was parallel to the direction of rubbing. The refractive index n⊥ was measured when the direction of polarization was perpendicular to the direction of rubbing. The value of optical anisotropy was calculated from the equation of Δn = n ‖ −n ⊥.

(6) Dielectric constant anisotropy (Δε; measured at 25 ° C.): The sample was placed in a TN device having a distance (cell gap) between two glass substrates of 9 μm and a twist angle of 80 degrees. A sine wave (10 V, 1 kHz) was applied to this device, and after 2 seconds, the permittivity (ε ‖) of the liquid crystal molecule in the long axis direction was measured. A sine wave (0.5V, 1kHz) was applied to this device, and the dielectric constant (ε⊥) of the liquid crystal molecule in the minor axis direction was measured 2 seconds later. The value of permittivity anisotropy was calculated from the formula Δε ＝ ε‖−ε⊥.

(7) Threshold voltage (Vth; measured at 25 ° C.; V): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The sample was placed in a normally white mode TN element in which the distance (cell gap) between the two glass substrates was 0.45 / Δn (μm) and the twist angle was 80 degrees. The voltage (32 Hz, square wave) applied to this device was gradually increased by 0.02 V from 0 V to 10 V. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the amount of light was maximum and the transmittance was 0% when the amount of light was minimum. The threshold voltage is expressed as the voltage when the transmittance reaches 90%.

(8) Voltage retention rate (VHR-1; measured at 25 ° C.;%): The TN element used for the measurement had a polyimide alignment film, and the distance (cell gap) between the two glass substrates was 5 μm. .. This element was sealed with an adhesive that cures with UV light after injecting the sample. A pulse voltage (60 microseconds at 5 V) was applied to the TN element 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 period was determined. Area B was the area when there was no attenuation. The voltage holding ratio is expressed as a percentage of the area A with respect to the area B.

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

(10) Voltage retention rate (VHR-3; measured at 25 ° C.;%): After irradiation with ultraviolet rays, the voltage retention rate was measured to evaluate the stability against ultraviolet rays. The TN element 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 VHR-3 measurement, the voltage decayed for 16.7 milliseconds was measured. Compositions with large VHR-3 have great stability to UV light. VHR-3 is preferably 90% or more, and more preferably 95% or more.

(11) Voltage retention rate (VHR-4; measured at 25 ° C.;%): After heating the TN element into which the sample was injected in a constant temperature bath at 80 ° C. for 500 hours, the voltage retention rate was measured and stability against heat was measured. Was evaluated. In the measurement of VHR-4, the voltage decayed 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): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The low-pass filter was set to 5 kHz. The sample was placed in an FFS device having a distance (cell gap) between two glass substrates of 3.5 μm and having no alignment film. This device was sealed with an adhesive that cures with UV light. This device was irradiated with ultraviolet rays of 78 mW / cm ² (405 nm) for 359 seconds (28 J) while applying a voltage of 30 V. For the irradiation of ultraviolet rays, a multi-metal lamp M04-L41 for ultraviolet curing manufactured by Eye Graphics Limited was used. A square wave (120 Hz) was applied to this device. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. It was considered that the transmittance was 100% when the amount of light was maximum, and the transmittance was 0% when the amount of light was minimum. The maximum voltage of the square wave was set so that the transmittance was 90%. The minimum voltage of the square wave was set to 2.5 V at which the transmittance was 0%. The response time was expressed as the time required for the transmittance to change from 90% to 10% (fall time; fall time; millisecond).

(13) Elastic constant (K; measured at 25 ° C.; pN): An HP4284A type LCR meter manufactured by Yokogawa Hewlett-Packard Co., Ltd. was used for the measurement. The sample was placed in a horizontally oriented element in which the distance (cell gap) between the two glass substrates was 20 μm. A charge of 0 to 20 volts was applied to this device, and the capacitance and applied voltage were measured. Fit the measured capacitance (C) and applied voltage (V) values using the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), formulas (2.98) and formula (2.11) on page 75. Then, the values of K11 and K33 were obtained from the formula (2.99). Next, K22 was calculated using the values of K11 and K33 obtained earlier in the formula (3.18) on page 171 of the same. The elastic constant K is represented by the average value of K11, K22, and K33 thus obtained.

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

(16) Pretilt angle A spectroscopic ellipsometer M-2000U (manufactured by JA Woollam Co., Inc.) was used for measuring the pretilt angle.

(17) Orientation stability (liquid crystal alignment axis stability)
The change in the liquid crystal alignment axis on the electrode side of the liquid crystal display element was evaluated. The liquid crystal orientation angle φ (before) on the electrode side before applying stress was measured, and then a square wave of 4.5 V, 60 Hz was applied to the element for 20 minutes, short-circuited for 1 second, and 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.) Of the liquid crystal orientation angle after 1 second and 5 minutes was calculated using the following formula.
Δφ (deg.) = φ (after) −φ (before)
These measurements were made with reference to J. Hilfiker, B. Johs, C. Herzinger, JF Elman, E. Montbach, D. Bryant, and PJ Bos, Thin Solid Films, 455-456, (2004) 596-600. .. It can be said that the smaller Δφ, the smaller the rate of change of the liquid crystal alignment axis, and the better the stability of the liquid crystal alignment axis.

Synthesis example 1
[Synthesis Example 1]
Synthesis of compound (2-7) First, the synthesis of compound (T-4) will be described.

Step 1 Paraformaldehyde (60.0 g), 1,4-diazabicyclo [2.2.2] octane (DABCO; 56.0 g), and water (200 ml) were placed in the reactor and stirred at room temperature for 15 minutes. .. A solution of compound (T-1) (50.0 g) in THF (400 ml) was added dropwise, and the mixture was stirred at room temperature for 72 hours. The reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 2: 1) to give compound (T-2) (44.1 g; 68%).

Second Step Compound (T-2) (44.1 g), imidazole (25.0 g) and dichloromethane (400 ml) were placed in a reactor and cooled to 0 ° C. A dichloromethane solution (200 ml) of t-butyldimethylchlorosilane (TBSCl; 53 g) was added dropwise, and the mixture was stirred for 4 hours while raising the temperature to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate = 9: 1) to give compound (T-3) (105 g; 84%).

Step 3 Compound (T-3) (105 g), THF (600 ml), methanol (150 ml), and water (100 ml) were placed in the reactor and cooled to 0 ° C. Lithium hydroxide monohydrate (17.4 g) was added thereto, and the mixture was stirred for 12 hours while returning to room temperature. The reaction mixture was poured into water, 6N hydrochloric acid (20 ml) was slowly added to make it acidic, and then the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to give compound (T-4) (34.0 g; 35%).

Next, a method for synthesizing compound (2-7) will be described.

Step 4 Compound (T-5) was synthesized according to the standard method. Compound (T-5) (7.5 g), tetrakis (triphenylphosphine) palladium (1.3 g), tetrabutylammonium bromide (TBAB; 1.5 g), potassium carbonate (6.4 g), 1-bromo-3, 5-Dimethoxybenzene (5 g), toluene (200 ml), 2-propanol (IPA; 80 ml) and pure water (20 ml) were placed in a reactor and stirred at 90 ° C. The reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution is concentrated under reduced pressure, the residue is purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 9: 1), and further reconstituted from a mixed solvent of heptane and toluene (volume ratio 1: 1). Purification by crystals gave compound (T-6) (7.18 g; 85%).

Step 5 Compound (T-6) (7.18 g) and dichloromethane (200 ml) were placed in a reactor and cooled to -50. Boron tribromide (2.1 ml) was added dropwise. The mixture was stirred for 5 hours while raising the temperature to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 1: 1) to give compound (T-7) (5.3 g; 80%).

Step 6 Compound (T-7) (5.3 g), ethylene carbonate (3.0 g), potassium carbonate (6.5 g), and DMF (200 ml) were placed in a reactor and stirred at 100 ° C. The reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 1: 1) to give compound (T-8) (5.5 g; 83%).

Step 7 Compound (T-8) (5.3 g), compound (T-4) (5.9 g), N, N-dimethyl-4-aminopyridine (DMAP; 1.52 g) and dichloromethane (150 ml). Was placed in a reactor and cooled to 0 ° C. A solution of N, N'-dicyclohexylcarbodiimide (DCC; 7.7 g) in dichloromethane (50 ml) was added dropwise. The mixture was stirred for 5 hours while raising the temperature to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 1: 1) to give compound (T-9) (8.3 g; 81%).

Step 8 Compound (T-9) (8.3 g) and THF (100 ml) were placed in a reactor and cooled to 0 ° C. Tetra-butyl ammonium fluoride (TBAF; 2.9 g) was added dropwise, and the mixture was stirred for 3 hours while raising the temperature to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 1: 1), and further purified by recrystallization from heptane to compound (2-7) (4). .5 g; 75%) was obtained.

¹ H-NMR (ppm; CDCl ₃ ) of compound (2-7): δ7.48-7.46 (m, 2H), 7.27-7.26 (m, 2H), 6.75 (d, J = 2.3Hz, 2H), 6.47-6.46 (m, 1H), 6.30 (s, 2H), 5.86 (d, J = 1.1Hz, 2H), 4.54 ( t, J = 4.4Hz, 4H), 4.33 (s, 4H), 4.27-4.25 (m, 4H), 2.52-2.47 (m, 1H), 2.34 ( s, 2H), 1.90 (t, J = 14Hz, 4H), 1.51-1.44 (m, 2H), 1.35-1.20 (m, 9H), 1.09-1. 02 (m, 2H), 0.90 (t, J = 6.9Hz, 3H)

Examples of the composition are shown below. The component compounds are represented by symbols based on the definitions in Table 3 below. In Table 3, the configuration for 1,4-cyclohexylene is trans. The number in parentheses after the symbolized compound represents the chemical formula to which the compound belongs. The symbol (-) means other liquid crystal compounds. The proportion (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additives. Finally, the characteristic values of the composition are summarized.

Example of element 1. The composition to which the polar compound was added was injected into the device having no raw material alignment film. After irradiating with ultraviolet rays, the vertical orientation of the liquid crystal molecules in this device was examined. First, the raw materials will be described. The raw materials were appropriately selected from the compositions (M1) to (M13), the polar compounds (PC-1) to (PC-5), and the polymerizable compounds (RM-1) to (RM-9). The composition is as follows.

Composition (M1)
5-HXB (F, F) -F (1-1) 3%
3-HHXB (F, F) -F (1-2) 6%
3-BB (F, F) XB (F, F) -F (1-4) 6%
3-BB (2F, 3F) XB (F, F) -F (1-4) 4%
3-HHB (F, F) XB (F, F) -F (1-5) 4%
3-HBB (2F, 3F) XB (F, F) -F (1-7) 5%
5-BB (F) B (F, F) XB (F) B (F, F) -F
(1-14) 2%
3-HH-V (3-1) 22%
3-HH-V1 (3-1) 10%
5-HB-O2 (3-2) 5%
3-HHEH-3 (3-4) 3%
3-HBB-2 (3-6) 7%
5-B (F) BB-3 (3-7) 3%
3-HB-CL (4-1) 3%
3-HHB-OCF3 (4-3) 3%
3-HGB (F, F) -F (4-6) 3%
3-HB (F) B (F, F) -F (4-9) 5%
3-HHBB (F, F) -F (4-14) 6%
NI = 77.2 ° C; Tc <-20 ° C; Δn = 0.101; Δε = 5.8; Vth = 1.88V; η = 13.7mPa · s; γ1 = 61.3mPa · s.

Composition (M2)
5-HXB (F, F) -F (1-1) 6%
3-HHXB (F, F) -F (1-2) 6%
2-BB (F) B (F, F) XB (F) -F (1-10) 3%
3-BB (F) B (F, F) XB (F) -F (1-10) 3%
4-BB (F) B (F, F) XB (F) -F (1-10) 4%
2-HH-5 (3-1) 8%
3-HH-V (3-1) 10%
3-HH-V1 (3-1) 7%
4-HH-V (3-1) 10%
4-HH-V1 (3-1) 8%
5-HB-O2 (3-2) 7%
4-HHEH-3 (3-4) 3%
V2-BB (F) B-1 (3-8) 3%
5-HB-CL (4-1) 5%
V-HB (F) B (F, F) -F (4-9) 5%
3-HHB (F) B (F, F) -F (4-15) 7%
1O1-HBBH-3 (-) 5%
NI = 78.5 ° C; Tc <-20 ° C; Δn = 0.095; Δε = 3.4; Vth = 1.50V; η = 8.4mPa · s; γ1 = 54.2mPa · s.

Composition (M3)
3-HHXB (F, F) -F (1-2) 7%
3-BB (F, F) XB (F, F) -F (1-4) 10%
5-HHB (F, F) XB (F, F) -F (1-5) 6%
3-HBB (2F, 3F) XB (F, F) -F (1-7) 5%
2-HH-3 (3-1) 8%
3-HH-V (3-1) 20%
3-HH-V1 (3-1) 7%
4-HH-V (3-1) 6%
5-HB-O2 (3-2) 5%
V2-B2BB-1 (3-9) 3%
3-HHEBH-3 (3-11) 5%
3-HHEBH-5 (3-11) 5%
3-HHEB (F, F) -F (4-5) 5%
5-HBEB (F, F) -F (4-10) 5%
2-HHB (F) B (F, F) -F (4-15) 3%
NI = 90.3 ° C; Tc <-20 ° C; Δn = 0.088; Δε = 5.4; Vth = 1.69V; η = 13.7 mPa · s; γ1 = 60.6 mPa · s.

Composition (M4)
3-BB (F, F) XB (F, F) -F (1-4) 12%
3-HBBXB (F, F) -F (1-7) 3%
3-BB (F) B (F, F) XB (F) -F (1-10) 3%
3-BB (F) B (F, F) XB (F, F) -F
(1-10) 3%
4-BB (F) B (F, F) XB (F, F) -F
(1-10) 5%
5-BB (F) B (F, F) XB (F, F) -F
(1-10) 4%
2-HH-3 (3-1) 6%
3-HH-5 (3-1) 6%
3-HH-V (3-1) 25%
3-HH-VFF (3-1) 6%
5-HB-O2 (3-2) 7%
V-HHB-1 (3-5) 6%
V-HBB-2 (3-6) 5%
3-HHBB (F, F) -F (4-14) 5%
4-HHBB (F, F) -F (4-14) 4%
NI = 78.3 ° C; Tc <-20 ° C; Δn = 0.107; Δε = 7.0; Vth = 1.55V; η = 11.6mPa · s; γ1 = 55.6mPa · s.

Composition (M5)
3-HHXB (F, F) -F (1-2) 6%
3-BB (F, F) XB (F, F) -F (1-4) 8%
3-BB (F) B (F, F) XB (F, F) -F
(1-10) 3%
4-BB (F) B (F, F) XB (F, F) -F
(1-10) 6%
5-BB (F) B (F, F) XB (F, F) -F
(1-10) 5%
3-HH-V (3-1) 30%
3-HH-V1 (3-1) 5%
F3-HH-V (3-1) 15%
3-HHB-O1 (3-5) 2%
V-HHB-1 (3-5) 5%
2-BB (F) B-3 (3-8) 6%
3-HHBB (F, F) -F (4-14) 5%
4-HHBB (F, F) -F (4-14) 4%
NI = 82.0 ° C; Tc <-20 ° C; Δn = 0.104; Δε = 5.7; Vth = 1.43V; η = 11.8 mPa · s; γ1 = 62.1 mPa · s.

Composition (M6)
3-GB (F, F) XB (F, F) -F (1-3) 5%
3-HGB (F, F) XB (F, F) -F (1-6) 5%
2-dhBB (F, F) XB (F, F) -F (1-8) 4%
3-dhB (F, F) B (F, F) XB (F) B (F, F) -F
(1-13) 3%
3-BB (2F, 5F) B-3 (3) 3%
2-HH-3 (3-1) 14%
2-HH-5 (3-1) 4%
3-HH-V (3-1) 26%
1V2-HH-3 (3-1) 5%
1V2-BB-1 (3-3) 3%
3-HB (F) HH-2 (3-10) 4%
5-HBB (F) B-2 (3-13) 6%
7-HB (F, F) -F (4-2) 3%
3-HGB (F, F) -F (4-6) 3%
5-GHB (F, F) -F (4-7) 4%
3-BB (F) B (F, F) -CF3 (4-13) 2%
3-HHBB (F, F) -F (4-14) 4%
3-GBB (F) B (F, F) -F (4-16) 2%
NI = 78.3 ° C; Tc <-20 ° C; Δn = 0.094; Δε = 5.9; Vth = 1.25V; η = 12.8 mPa · s; γ1 = 61.9 mPa · s.

Composition (M7)
3-BB (F) B (F, F) XB (F, F) -F
(1-10) 3%
4-BB (F) B (F, F) XB (F, F) -F
(1-10) 5%
3-BB (F, F) XB (F) B (F, F) -F
(1-12) 3%
5-BB (F) B (F, F) XB (F) B (F, F) -F
(1-14) 4%
2-HH-5 (3-1) 8%
3-HH-V (3-1) 25%
3-HH-V1 (3-1) 7%
4-HH-V1 (3-1) 6%
5-HB-O2 (3-2) 5%
7-HB-1 (3-2) 5%
VFF-HHB-O1 (3-5) 8%
VFF-HHB-1 (3-5) 3%
3-HH2BB (F, F) -F (4) 3%
4-HH2BB (F, F) -F (4) 3%
3-HBB (F, F) -F (4-8) 5%
5-HBB (F, F) -F (4-8) 4%
3-BB (F) B (F, F) -F (4-12) 3%
NI = 80.0 ° C; Tc <-20 ° C; Δn = 0.101; Δε = 4.6; Vth = 1.71V; η = 11.0 mPa · s; γ1 = 47.2 mPa · s.

Composition (M8)
3-BB (F, F) XB (F, F) -F (1-4) 10%
3-GB (F) B (F, F) XB (F, F) -F
(1-9) 6%
5-GB (F, F) XB (F) B (F, F) -F
(1-11) 5%
5-HBBH-3 (3) 5%
3-HH-V (3-1) 30%
3-HH-V1 (3-1) 10%
1V2-HH-3 (3-1) 8%
3-HH-VFF (3-1) 8%
V2-BB-1 (3-3) 2%
5-HB (F) BH-3 (3-12) 5%
3-HHB (F, F) -F (4-4) 8%
3-GB (F) B (F, F) -F (4-11) 3%
NI = 76.6 ° C; Tc <-20 ° C; Δn = 0.088; Δε = 5.5; Vth = 1.81V; η = 12.1mPa · s; γ1 = 60.2mPa · s.

Composition (M9)
3-HHB (F, F) XB (F, F) -F (1-5) 5%
5-HHB (F, F) XB (F, F) -F (1-5) 3%
3-HGB (F, F) XB (F, F) -F (1-6) 5%
3-GB (F) B (F, F) XB (F, F) -F
(1-9) 5%
4-GB (F) B (F, F) XB (F, F) -F
(1-9) 5%
2-HH-5 (3-1) 3%
3-HH-5 (3-1) 5%
3-HH-V (3-1) 24%
4-HH-V (3-1) 5%
1V2-HH-3 (3-1) 5%
3-HHEH-3 (3-4) 5%
5-B (F) BB-2 (3-7) 3%
5-B (F) BB-3 (3-7) 2%
5-HEB (F, F) -F (4) 3%
5-HB-CL (4-1) 5%
3-HHB-OCF3 (4-3) 4%
3-HHEB (F, F) -F (4-5) 4%
3-HBEB (F, F) -F (4-10) 3%
5-HBEB (F, F) -F (4-10) 3%
3-BB (F) B (F, F) -F (4-12) 3%
NI = 78.6 ° C; Tc <-20 ° C; Δn = 0.091; Δε = 6.8; Vth = 1.52V; η = 15.5 mPa · s; γ1 = 59.3 mPa · s.

Composition (M10)
3-HHXB (F, F) -F (1-2) 9%
3-BB (F, F) XB (F, F) -F (1-4) 5%
3-HH-V (3-1) 25%
3-HH-V1 (3-1) 10%
5-HB-O2 (3-2) 10%
7-HB-1 (3-2) 5%
V2-BB-1 (3-3) 3%
3-HHB-1 (3-5) 4%
1V-HBB-2 (3-6) 5%
5-HBB (F) B-2 (3-13) 6%
3-HBB (F, F) -F (4-8) 3%
3-BB (F) B (F, F) -F (4-12) 4%
3-BB (F) B (F, F) -CF3 (4-13) 4%
3-GBB (F) B (F, F) -F (4-16) 3%
4-GBB (F) B (F, F) -F (4-16) 4%
NI = 79.6 ° C; Tc <-20 ° C; Δn = 0.111; Δε = 4.7; Vth = 1.86V; η = 9.7mPa · s; γ1 = 49.9mPa · s.

Composition (M11)
3-BB (F, F) XB (F, F) -F (1-4) 14%
3-dhB (F, F) B (F, F) XB (F) B (F, F) -F
(1-13) 7%
3-BB (2F, 5F) B-3 (3) 3%
2-HH-5 (3-1) 5%
3-HH-V (3-1) 30%
3-HH-V1 (3-1) 3%
3-HH-VFF (3-1) 10%
3-HHB-1 (3-5) 4%
3-HHB-3 (3-5) 5%
3-HHB-O1 (3-5) 3%
3-HHEBH-3 (3-11) 3%
3-HHEBH-4 (3-11) 4%
3-HHEBH-5 (3-11) 3%
7-HB (F, F) -F (4-2) 6%
NI = 82.7 ° C; Tc <-20 ° C; Δn = 0.085; Δε = 5.1; Vth = 1.70V; η = 8.0mPa · s; γ1 = 53.9mPa · s.

Composition (M12)
3-BB (F) B (F, F) XB (F, F) -F
(1-10) 3%
4-BB (F) B (F, F) XB (F, F) -F
(1-10) 5%
3-BB (F, F) XB (F) B (F, F) -F
(1-12) 3%
5-BB (F) B (F, F) XB (F) B (F, F) -F
(1-14) 4%
2-HH-5 (3-1) 8%
3-HH-V (3-1) 28%
4-HH-V1 (3-1) 7%
5-HB-O2 (3-2) 2%
7-HB-1 (3-2) 5%
VFF-HHB-O1 (3-5) 8%
VFF-HHB-1 (3-5) 3%
3-HH2BB (F, F) -F (4) 3%
4-HH2BB (F, F) -F (4) 3%
3-HBB (F, F) -F (4-8) 5%
5-HBB (F, F) -F (4-8) 4%
3-BB (F) B (F, F) -F (4-12) 3%
2-BB (2F, 3F) B-3 (5-9) 4%
3-HBB (2F, 3F) -O2 (5-10) 2%
NI = 81.9 ° C; Tc <-20 ° C; Δn = 0.109; Δε = 4.8; Vth = 1.75V; η = 13.3 mPa · s; γ1 = 57.4 mPa · s.

Composition (M13)
5-HHB (F, F) XB (F, F) -F (1-5) 3%
3-HGB (F, F) XB (F, F) -F (1-6) 4%
3-HBBXB (F, F) -F (1-7) 6%
3-GB (F) B (F, F) XB (F, F) -F
(1-9) 5%
4-GB (F) B (F, F) XB (F, F) -F
(1-9) 5%
3-HH-5 (3-1) 4%
3-HH-V (3-1) 21%
3-HH-V1 (3-1) 3%
4-HH-V (3-1) 4%
1V2-HH-3 (3-1) 6%
F3-HH-V (3-1) 3%
5-B (F) BB-2 (3-7) 3%
5-B (F) BB-3 (3-7) 2%
5-HEB (F, F) -F (4) 3%
5-HB-CL (4-1) 2%
3-HHB-OCF3 (4-3) 4%
3-HHEB (F, F) -F (4-5) 4%
3-HBEB (F, F) -F (4-10) 3%
5-HBEB (F, F) -F (4-10) 3%
3-BB (F) B (F, F) -F (4-12) 3%
3-HB (2F, 3F) -O2 (5-1) 3%
3-BB (2F, 3F) -O2 (5-4) 2%
3-HHB (2F, 3F) -O2 (5-6) 4%
NI = 78.1 ° C; Tc <-20 ° C; Δn = 0.100; Δε = 6.6; Vth = 1.50V; η = 16.2 mPa · s; γ1 = 61.8 mPa · s.

The first additive is from polar compounds (PC-1) to (PC-5).

The second additive is a polymerizable compound (RM-1) to (RM-9).

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

Examples 2 to 13
A device having no alignment film was produced using a mixture prepared by adding a polar compound having a polymerizable group to the composition. The presence or absence of light leakage was observed by the same method as in Example 1. The results are summarized in Table 4. In Example 13, a polymerizable compound (RM-1) was also added in a proportion of 0.5% by weight.

As can be seen from Table 4, in Examples 1 to 13, the types of the composition and the polar compound were changed, but no light leakage was observed. This result indicates that the vertical orientation is good even if the device does not have an alignment film, and the liquid crystal molecules are stably oriented. In Example 13, a polymerizable compound (RM-1) was further added, and similar results were obtained.

The liquid crystal composition of the present invention can be used for liquid crystal projectors, liquid crystal televisions and the like.

Claims (27)

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

In formulas (1) and (2), R ¹ is an alkyl with 1 to 12 carbons, an alkoxy with 1 to 12 carbons, or an alkenyl with 2 to 12 carbons; rings A and B are independent. 1,4-Cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine -2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; rings C and E are independently cyclohexyl, cyclohexenyl, phenyl, 1-. It is naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl, or pyridine-2-yl, and in these rings at least one hydrogen is fluorine. , Chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, alkyl with 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine, or at least 1 One hydrogen may be replaced with an alkenyl having 2 to 12 carbons replaced by fluorine or chlorine; ring D 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 which at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, An alkenyl having 2 to 12 carbon atoms, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine, or an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine. Z ¹ and Z ² may be independently single-bonded, -CH ₂ CH _2- , -CH = CH-, -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CF ₂ O- or -O CF ₂ −; Z ³ and Z ⁴ are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which 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 )-and at least one hydrogen in these groups may be replaced with fluorine or chlorine; X ¹ and X ² Are independently hydrogen or fluorine; Y ¹ is fluorine, chlorine, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, and at least one hydrogen is replaced by fluorine or chlorine. An alkoxy having 1 to 12 carbon atoms, or an alkenyloxy having 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine; Sp ¹ , Sp ² , and Sp ³ are independently single-bonded or It is an alkylene having 1 to 10 carbon atoms, in which at least one -CH _2- may be replaced by -O-, -COO-, -OCO-, or -OCOO-, and at least one. −CH ₂ CH ₂₋ may be replaced by −CH = CH− or −C≡C−, and in these groups at least one hydrogen may be replaced by fluorine or chlorine; 1, 2, 3, or 4; b is 0, 1, 2, or 3, and the sum of a and b is less than or equal to 4; c is 0, 1, 2, 3, or 4 E, f, and g are independently 0, 1, 2, 3, or 4, and the sum of e, f, and g is 2 or greater; P ¹ , P ² , and. P ³ is independently a polymerizable group represented by the formula (PA);

In formula (PA), Sp ⁴ is a single bond or an alkylene with 1 to 7 carbon atoms, in which at least one -CH ₂ − is -O-, -COO-, or -OCO-. At least one −CH ₂ CH ₂ − may be replaced with −CH = CH −, and in these groups at least one hydrogen may be replaced with fluorine; ² is a group represented by -OH, -OR ⁰ , -NH ₂ , -NHR ⁰ , or -N (R ⁰ ) ₂ , where R ⁰ is hydrogen or an alkyl having 1 to 12 carbon atoms. Yes; M ⁴ and M ⁵ are independently hydrogen, fluorine, alkyl with 1 to 5 carbon atoms, or alkyl with 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. In the formula (2) according to claim 1, the rings C and E are independently cyclohexyl, phenyl, 1-naphthyl, or 2-naphthyl, and in these rings, at least one hydrogen is fluorine. Chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, alkyl with 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine, or at least one Hydrogen may be replaced with an alkenyl having 2 to 12 carbon atoms in which hydrogen is replaced with fluorine or chlorine; ring D is 1,4-cyclohexylene, 1,4-phenylene, naphthalene-1,2-diyl, or naphthalene. In these rings, at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, at least 1 One hydrogen may be replaced with an alkyl having 1 to 12 carbon atoms with fluorine or chlorine replaced, or at least one hydrogen with an alkenyl having 2 to 12 carbon atoms replaced with fluorine or chlorine; c is 0 or The liquid crystal composition according to claim 1, which is 1. The liquid crystal composition according to claim 1 or 2, which contains at least one compound selected from the group of compounds represented by formulas (1-1) to (1-14) as a first component.

In formulas (1-1) to (1-14), R ¹ is an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, or an alkenyl having 2 to 12 carbon atoms; X ¹ , X. ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , and X ¹⁴ are independently hydrogen or fluorine; Y ¹ is fluorine, chlorine, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine, an alkoxy having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine, or at least 1 One hydrogen is an alkenyloxy having 2 to 12 carbon atoms in which fluorine or chlorine is replaced. The invention according to any one of claims 1 to 3, wherein the first additive is at least one compound selected from the group of polar compounds represented by the formulas (2-1) to (2-13). Liquid crystal composition.

In formulas (2-1) to (2-13), R ² is a group represented by -OH, -OR ⁰ , -NH ₂ , -NHR ⁰ , or -N (R ⁰ ) ₂ . Here, R ⁰ is hydrogen or an alkyl having 1 to 12 carbon atoms; R ³ is hydrogen, fluorine, chlorine, an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, and 2 to 12 carbon atoms. An alkenyl, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine, or an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen has been replaced by fluorine or chlorine; Z ³ and Z ⁴ independently is a single bond or alkylene having 1 to 10 carbon atoms, in the alkylene, at least one of _-CH 2 -, -O -, - CO -, - COO-, or replaced by -OCO- at best, and at least one _-CH 2 CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, or -C _(CH 3) = It may be replaced with C (CH ₃ )-and at least one hydrogen in these groups may be replaced with fluorine or chlorine; Sp ¹ and Sp ³ are independently single-bonded or 1 carbon. To 10 alkylenes, in which at least one -CH ₂ − may be replaced by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ − may be replaced by −CH = CH − or −C≡C−, in these groups at least one hydrogen may be replaced by fluorine or chlorine; Sp ⁴ is a single bond. Alternatively, it is an alkylene having 1 to 7 carbon atoms, in which at least one -CH ₂ − may be replaced by -O-, -COO-, or -OCO-, and at least one -CH ₂ CH. ₂ − may be replaced by −CH = CH−, and in these groups at least one hydrogen may be replaced by fluorine; L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁵ , and L ⁶ are each independently hydrogen, fluorine, methyl or ethyl. Claim that the proportion of the first component is in the range of 5% by weight to 55% by weight and the proportion of the first additive is in the range of 0.05% by weight to 10% by weight based on the weight of the liquid crystal composition. The liquid crystal composition according to any one of 1 to 4. The liquid crystal composition according to any one of claims 1 to 5, which contains at least one compound selected from the group of compounds represented by the formula (3) as a second component.

In formula (3), R ⁴ and R ⁵ are independent of an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, or at least one hydrogen being fluorine or chlorine. It is an alkenyl having 2 to 12 carbon atoms replaced; ring F and ring G are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5. -Difluoro-1,4-phenylene; Z ⁵ is single-bonded, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-; h is 1, 2, or 3. The liquid crystal according to any one of claims 1 to 6, which contains at least one compound selected from the group of compounds represented by formulas (3-1) to (3-13) as a second component. Composition.

In the formula (3-13) from equation (3-1), independently of ^{R 4} and ^{R 5,} alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, from 2 to 12 carbons, alkenyl or, An alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. The liquid crystal composition according to claim 6 or 7, wherein the proportion 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. The liquid crystal composition according to any one of claims 1 to 8, which contains at least one compound selected from the group of compounds represented by the formula (4) as a third component.

In formula (4), R ⁶ is an alkyl with 1 to 12 carbons, an alkoxy with 1 to 12 carbons, or an alkenyl with 2 to 12 carbons; ring I is 1,4-cyclohexylene, 1,4. -Phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane -2,5-diyl, or tetrahydropyran-2,5-diyl; Z ⁶ is single bond, -CH ₂ CH _2- , -COO-, or -OCO-; X ¹⁵ and X ¹⁶ are Independently, hydrogen or fluorine; Y ² is fluorine, chlorine, an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, and at least one hydrogen is replaced by fluorine or chlorine. An alkoxy having 1 to 12 carbon atoms, or an alkenyloxy having 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine; i is 1, 2, 3, or 4. The liquid crystal according to any one of claims 1 to 9, which contains at least one compound selected from the group of compounds represented by formulas (4-1) to (4-16) as a third component. Composition.

In formulas (4-1) to (4-16), R ⁶ is an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, or an alkenyl having 2 to 12 carbon atoms. The liquid crystal composition according to claim 9 or 10, wherein the proportion of the third component is in the range of 5% by weight to 50% by weight based on the weight of the liquid crystal composition. The liquid crystal composition according to any one of claims 1 to 11, which contains at least one compound selected from the group of compounds represented by the formula (5) as the fourth component.

In formula (5), R ⁷ and R ⁸ are independently composed of an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, or an alkenyloxy having 2 to 12 carbon atoms. Yes; Ring J and Ring L are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine. , Or tetrahydropyran-2,5-diyl; ring K is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5. - methyl-1,4-phenylene, it is a 3,4,5-trifluoro-2,6-diyl or 7,8-difluoro-chroman-2,6-diyl,; ^{Z 7} and ^{Z 8} are independently a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or a -OCO-; j is 1, 2 or 3,, k is 0 or 1 And the sum of j and k is less than or equal to 3. The liquid crystal according to any one of claims 1 to 12, which contains at least one compound selected from the group of compounds represented by the formulas (5-1) to (5-22) as the fourth component. Composition.

In formulas (5-1) to (5-22), R ⁷ and R ⁸ are independently alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or It is an alkoxyoxy having 2 to 12 carbon atoms. The liquid crystal composition according to claim 12 or 13, wherein the proportion of the fourth component is in the range of 3% by weight to 40% by weight based on the weight of the liquid crystal composition. The liquid crystal composition according to any one of claims 1 to 14, which contains at least one compound selected from the group of polymerizable compounds represented by the formula (6) as a second additive.

In formula (6), rings T and V are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-. 2-Il or pyridine-2-yl, in these rings at least one hydrogen may be fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least one hydrogen. It may be replaced with an alkyl having 1 to 12 carbon atoms replaced with fluorine or chlorine; ring U 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 which at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least 1 One hydrogen may be replaced with an alkyl having 1 to 12 carbon atoms replaced with fluorine or chlorine; Z ¹¹ and Z ¹² are independently single-bonded or alkylenes having 1 to 10 carbon atoms, and in this alkylene. , 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 at least one in these groups. hydrogen may be replaced by fluorine or chlorine; P ^{4, P 5,} and P ⁶ is the polymerizable group represented by the formula (P-a) of claim 1 with a different polymerizable groups Yes; Sp ¹⁰ , Sp ¹¹ , and Sp ¹² are independently single-bonded or 1 to 10 carbon alkylenes, in which at least one -CH _2- is -O-, -COO-, Replaced by -OCO- or -OCOO- And at least one −CH ₂ CH ₂₋ may be replaced by −CH = CH− or −C≡C−, in which at least one hydrogen is replaced by fluorine or chlorine. May be; t is 0, 1, or 2; u, v, and w are independently 0, 1, 2, 3, or 4, and the sum of u, v, and w is 1 or more. In the formula (6) according to claim 15, P ⁴ , P ⁵ , and P ⁶ are independently selected from the group of polymerizable groups represented by the formulas (P-1) to (P-5). The liquid crystal composition according to claim 15, which is a base.

In formulas (P-1) to (P-5), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine. It is an alkyl having 1 to 5 carbon atoms replaced with. The second additive is any one of claims 1 to 16, which comprises at least one compound selected from the group of polymerizable compounds represented by formulas (6-1) to (6-28). The liquid crystal composition described.

In the formula (6-28) from equation ^(6-1), P 4, ^{P 5,} and ^{P 6} are each independently of the polymerizable group represented by the formula (P-1) by the formula (P-3) A group selected from the group

Here, M ¹ , M ² , and M ³ are independently hydrogen, fluorine, an alkyl having 1 to 5 carbon atoms, or an alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. Sp ¹⁰ , Sp ¹¹ , and Sp ¹² are independently single-bonded or alkylenes with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -COO-,-. It may be replaced by OCO-, or -OCOO-, and at least one -CH ₂ CH _2- may be replaced by -CH = CH- or -C≡C-, at least in these groups. One hydrogen may be replaced with fluorine or chlorine. The liquid crystal composition according to any one of claims 15 to 17, wherein the ratio of the second additive is in the range of 0.03% by weight to 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 to 18. The liquid crystal display element according to claim 19, wherein the operation mode of the liquid crystal display element is an IPS mode, a TN mode, an FFS mode, or an FPA mode, and the drive method of the liquid crystal display element is an active matrix method. A polymer-supported oriented liquid crystal display device containing the liquid crystal composition according to any one of claims 1 to 14 and polymerized with the first additive contained in the liquid crystal composition. A polymer-supported oriented liquid crystal display containing the liquid crystal composition according to any one of claims 15 to 18, wherein the first additive and the second additive contained in the liquid crystal composition are polymerized. element. A liquid crystal display device having no alignment film, which contains the liquid crystal composition according to any one of claims 1 to 14, and is polymerized with the first additive contained in the liquid crystal composition. A liquid crystal display device containing the liquid crystal composition according to any one of claims 15 to 18, wherein the first additive and the second additive contained in the liquid crystal composition are polymerized and do not have an alignment film. .. Use of the liquid crystal composition according to any one of claims 1 to 18 in a liquid crystal display element. Use of the liquid crystal composition according to any one of claims 1 to 18 in a polymer-supported oriented liquid crystal display device. Use of the liquid crystal composition according to any one of claims 1 to 18 in a liquid crystal display device having no alignment film.