JP2019189667A - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

To provide a liquid crystal composition satisfying at least one of demands for characteristics such as a high maximum temperature, low minimum temperature, small viscosity, large optical anisotropy, large dielectric anisotropy and large elastic modulus or having an appropriate balance in at least two of the characteristics, and an AM element comprising the composition.SOLUTION: The liquid crystal composition contains a specific compound having a polymerizable group as a first additive, contains a specific compound having a negative dielectric anisotropy as a first component, and may contain a specific compound having a high maximum temperature or a small viscosity as a second component or a specific compound having a polymerizable group as a second additive.SELECTED DRAWING: None

Description

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

  In the liquid crystal display element, the classification based on the operation mode of liquid crystal molecules is as follows: PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS. Modes such as (in-plane switching), VA (vertical alignment), FFS (fringe field switching), and FPA (field-induced photo-reactive alignment). The classification based on the element driving method is PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into TFT (thin film transistor), MIM (metal insulator metal), and the like. TFTs are classified into amorphous silicon and polycrystalline 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 includes a reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both natural light and backlight.

  The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the characteristics of the composition, an AM device having good characteristics can be obtained. The relationships in these properties are summarized in Table 1 below. The characteristics of the composition will be further described based on a commercially available AM device. The temperature range of the nematic phase is related to the temperature range in which the device can be used. A preferred maximum temperature of the nematic phase is about 70 ° C. or more, and a preferred minimum temperature of the nematic phase is about −10 ° C. or less. 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 is desirable even at 1 millisecond. Therefore, a small viscosity in the composition is preferred. A small viscosity at low temperatures is even 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, ie 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 for the product depends on the type of operating mode. This value is in the range of about 0.30 μm to about 0.40 μm for the VA mode element and in the range of about 0.20 μm to about 0.30 μm for the IPS mode or FFS mode element. In these cases, a composition having a large optical anisotropy is preferable for a device having a small cell gap. A large dielectric anisotropy in the composition contributes to a low threshold voltage, a small power consumption and a large contrast ratio in the device. Therefore, a large dielectric anisotropy is preferable. A large specific resistance in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a large specific resistance in the initial stage is preferable. A composition having a large specific resistance after being used for a long time is preferred. The stability of the composition against ultraviolet rays and heat is related to the lifetime of the device. When this stability is high, the lifetime of the device is long. Such characteristics are preferable for an AM device used for a liquid crystal monitor, a liquid crystal television, and the like.

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

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

  In an AM device having a TN mode, a composition having a positive dielectric anisotropy is used. A composition having a negative dielectric anisotropy is used in an AM device having a VA mode. In an AM device having an IPS mode or an FFS mode, a composition having a positive or negative dielectric anisotropy is used. In a polymer-supported 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.

International Publication No. 2010/084823

  The object of the present invention is to provide a high upper limit temperature of the nematic phase, a lower lower limit temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, a large negative dielectric anisotropy, a large specific resistance, a high stability against ultraviolet rays, a heat It is to provide a liquid crystal composition satisfying at least one of characteristics such as high stability against the above and a large elastic constant. Another challenge is to provide a liquid crystal composition that has an appropriate balance between at least two of these properties. Another object is to provide a liquid crystal display device containing such a composition. Another object is to provide an AM device having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime.

式（１）において、Ｔ^１およびＴ^２は水素、式（Ａ）で表される基、または式（Ｂ）で表される基であり、少なくともＴ^１およびＴ^２のいずれかが、式（Ａ）で表される基、または式（Ｂ）で表される基であり; 少なくともＴ^１およびＴ^２のいずれかが、１つ以上の重合性基を有し；

式（Ａ）において、環Ａ^１は、シクロヘキシル、シクロヘキセニル、フェニル、テトラヒドロピラニル、１，３−ジオキサニル、ピリミジニル、またはピリジニルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；環Ｂ^１は、シクロヘキシレン、シクロヘキセニレン、フェニレン、テトラヒドロピランジイル、１，３−ジオキサンジイル、ピリミジンジイル、またはピリジンジイルであり、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；Ｘ^１およびＹ^１は、単結合、エチレン、カルボニルオキシ、またはメチレンオキシであり；Ｐ^１およびＰ^２は、式（Ｐ−１）から式（Ｐ−５）で表される重合性基から選択された基であり；Ｓp^１およびＳｐ^２は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ａ^１は、０または１であり；ｃ^１は、０から５の整数であり、ｄ^１は、０から４の整数であり；

式（Ｂ）において、Ｐ^３は、式（Ｐ−１）から式（Ｐ−５）で表される重合性基から選択された基であり；Ｓｐ^３は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；

式（Ｐ−１）から式（Ｐ−５）において、Ｍ^１、Ｍ^２、およびＭ^３は、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルである。
The present invention is a liquid crystal composition containing at least one compound selected from the polymerizable compounds represented by formula (1) and having a nematic phase, and a liquid crystal display device containing this composition.

In Formula (1), T ¹ and T ² are hydrogen, a group represented by Formula (A), or a group represented by Formula (B), and at least ^one of T ¹ and T ² is represented by Formula (1). A group represented by A) or a group represented by formula (B); at least ^one of T ¹ and T ² has one or more polymerizable groups;

In formula (A), ring A ¹ is cyclohexyl, cyclohexenyl, phenyl, tetrahydropyranyl, 1,3-dioxanyl, pyrimidinyl, or pyridinyl, in which at least one hydrogen is fluorine, chlorine, An alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, or an alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine may be substituted; ring B ¹ is cyclohexylene , Cyclohexenylene, phenylene, tetrahydropyrandiyl, 1,3-dioxanediyl, pyrimidinediyl, or pyridinediyl, in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, Alkoxy having 1 to 12 carbons or a small amount Both may be replaced by one of hydrogen from 1 carbon atoms are replaced by fluorine or chlorine 12 alkyl; X ¹ and Y ¹ is a single bond, ethylene, carbonyloxy or methyleneoxy,; P ¹ and P ² is a group selected from a polymerizable group represented by formula (P-1) to formula (P-5); Sp ¹ and Sp ² are a single bond or alkylene having 1 to 10 carbon atoms. And in this alkylene, at least one —CH ₂ — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, wherein at least one —CH ₂ —CH ₂ — is It may be replaced by -CH = CH- or -C≡C-, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; ^{a 1} is 0 or By and; ^{c 1} is an integer from 0 to 5, ^{d 1} is an integer from 0 to 4;

In the formula (B), P ³ is a group selected from a polymerizable group represented by the formula (P-1) to the formula (P-5); Sp ³ is a single bond or 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-, in which at least one hydrogen may be replaced by fluorine or chlorine;

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

  The advantages of the present invention are that the upper limit temperature of the nematic phase, the lower limit temperature of the nematic phase, the small viscosity, the appropriate optical anisotropy, the negative dielectric constant anisotropy, the large specific resistance, the high stability to ultraviolet rays, the heat It is to provide a liquid crystal composition satisfying at least one of characteristics such as high stability against the above and a 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 to provide a liquid crystal display device containing such a composition. Another advantage is to provide an AM device having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime.

  Terms used in this specification are 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 liquid crystal display panels and liquid crystal display modules. “Liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase and a smectic phase and does not have a liquid crystal phase, but for the purpose of adjusting characteristics such as the temperature range, viscosity, and dielectric anisotropy of the nematic phase. This is a general term for compounds mixed in the composition. This compound has, for example, a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecule (liquid crystal molecule) is rod-like. The “polymerizable compound” is a compound added for the purpose of forming a polymer in the composition. Liquid crystalline compounds having alkenyl are not classified as polymerizable in that sense.

  The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as optically active compounds and polymerizable compounds are added to this liquid crystal composition as necessary. The ratio of the liquid crystal compound is represented by a mass percentage (% by mass) based on the mass of the liquid crystal composition not containing the additive even when the additive is added. The ratio of the additive is expressed as a mass percentage (% by mass) based on the mass of the liquid crystal composition not containing the additive. That is, the ratio of the liquid crystal compound and the additive is calculated based on the total mass of the liquid crystal compound. Mass parts per million (ppm) may be used. The ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the mass of the polymerizable compound.

  “Maximum temperature of nematic phase” may be abbreviated as “maximum temperature”. “Lower limit temperature of nematic phase” may be abbreviated as “lower limit temperature”. The expression “increasing dielectric anisotropy” means that when the composition has a positive dielectric anisotropy, the value increases positively, and the composition having a negative dielectric anisotropy When it is a thing, it means that the value increases negatively. "High voltage holding ratio" means that the device has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and a large voltage not only at room temperature but also at a temperature close to the upper limit temperature after long-term use. It means having a retention rate. The characteristics of the composition and the device may be examined by a aging test.

上記の化合物（１ｚ）を例にして説明する。式（１ｚ）において、六角形で囲んだαおよびβの記号はそれぞれ環αおよび環βに対応し、六員環、縮合環のような環を表す。添え字‘ｘ’が２のとき、２つの環αが存在する。２つの環αが表す２つの基は、同一であってもよく、または異なってもよい。このルールは、添え字‘ｘ’が２より大きいとき、任意の２つの環αに適用される。このルールは、結合基Ｚのような、他の記号にも適用される。環βの一辺を横切る斜線は、環β上の任意の水素が置換基（−Ｓｐ−Ｐ）で置き換えられてもよいことを表す。添え字‘ｙ’は置き換えられた置換基の数を示す。添え字‘ｙ’が０のとき、そのような置き換えはない。添え字‘ｙ’が２以上のとき、環β上には複数の置換基（−Ｓｐ−Ｐ）が存在する。この場合にも、「同一であってもよく、または異なってもよい」のルールが適用される。なお、このルールは、Ｒａの記号を複数の化合物に用いた場合にも適用される。

The above compound (1z) will be described as an example. In the formula (1z), the symbols α and β surrounded by hexagons correspond to the rings α and β, respectively, and represent a ring such as a six-membered ring or a condensed ring. When the subscript 'x' is 2, there are two rings α. The two groups represented by the two rings α may be the same or different. This rule applies to any two rings α when the subscript 'x' is greater than 2. This rule also applies to other symbols such as the linking group Z. A diagonal line across one side of the ring β indicates that any hydrogen on the ring β may be replaced with a substituent (—Sp—P). The subscript “y” indicates the number of substituted substituents. When the subscript 'y' is 0, there is no such replacement. When the subscript “y” is 2 or more, a plurality of substituents (—Sp—P) exist on the ring β. Also in this case, the rule “may be the same or different” is applied. This rule also applies when the symbol of Ra is used for a plurality of compounds.

  In formula (1z), for example, the expression “Ra and Rb are alkyl, alkoxy, or alkenyl” means that Ra and Rb are independently selected from the group of alkyl, alkoxy, and alkenyl. To do. That is, the group represented by Ra and the group represented by Rb may be the same or different.

  At least one compound selected from the compounds represented by formula (1z) may be abbreviated as “compound (1z)”. “Compound (1z)” means one compound represented by the formula (1z), 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 compound selected from compounds represented by formula (1z) and formula (2z)” means at least one compound selected from the group of compound (1z) and compound (2z) .

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'” means that when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is 2 Even when there are more than two, their positions can be selected without restriction. The expression “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 non-adjacent —CH ₂ — with —O—. However, adjacent —CH ₂ — is not replaced by —O—. This replacement is -O-O-CH ₂ - is because (peroxide) is produced.

  For example, in Ra and Rb of formula (1z), alkyl is linear or branched and does not include cyclic alkyl. Linear alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl.

テトラヒドロピラン−２，５−ジイルのような二価基においても同様である。カルボニルオキシのような結合基（−ＣＯＯ−または−ＯＣＯ−）も同様である。 The configuration of 1,4-cyclohexylene is preferably trans rather than cis for increasing the maximum temperature. Since 2-fluoro-1,4-phenylene is asymmetrical, there are leftward (L) and rightward (R).

The same applies to a divalent group such as tetrahydropyran-2,5-diyl. The same applies to a linking group such as carbonyloxy (—COO— or —OCO—).

  The present invention includes the following items.

式（１）において、Ｔ^１およびＴ^２は水素、式（Ａ）で表される基、または式（Ｂ）で表される基であり、少なくともＴ^１およびＴ^２のいずれかが、式（Ａ）で表される基、または式（Ｂ）で表される基であり；少なくともＴ^１およびＴ^２のいずれかが、１つ以上の重合性基を有し；

式（Ａ）において、環Ａ^１は、シクロヘキシル、シクロヘキセニル、フェニル、テトラヒドロピラニル、１，３−ジオキサニル、ピリミジニル、またはピリジニルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；環Ｂ^１は、シクロヘキシレン、シクロヘキセニレン、フェニレン、テトラヒドロピランジイル、１，３−ジオキサンジイル、ピリミジンジイル、またはピリジンジイルであり、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；Ｘ^１およびＹ^１は、単結合、エチレン、カルボニルオキシ、またはメチレンオキシであり；Ｐ^１およびＰ^２は、式（Ｐ−１）から式（Ｐ−５）で表される重合性基から選択された基であり；Ｓp^１およびＳｐ^２は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ａ^１は、０または１であり；ｃ^１は、０から５の整数であり、ｄ^１は、０から４の整数であり；

式（Ｂ）において、Ｐ^３は、式（Ｐ−１）から式（Ｐ−５）で表される重合性基から選択された基であり；Ｓｐ^３は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；

式（Ｐ−１）から式（Ｐ−５）において、Ｍ^１、Ｍ^２、およびＭ^３は、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルである。 Item 1. A liquid crystal composition containing at least one compound selected from polymerizable compounds represented by formula (1) as a first additive and having a nematic phase.

In Formula (1), T ¹ and T ² are hydrogen, a group represented by Formula (A), or a group represented by Formula (B), and at least ^one of T ¹ and T ² is represented by Formula (1). A group represented by A) or a group represented by formula (B); at least ^one of T ¹ and T ² has one or more polymerizable groups;

In formula (A), ring ^{A 1} is cyclohexyl, cyclohexenyl, phenyl, tetrahydropyranyl, 1,3-dioxanyl, pyrimidinyl or pyridinyl, in these rings, at least one of hydrogen, fluorine, chlorine, An alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, or an alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine may be substituted; ring B ¹ is cyclohexylene , Cyclohexenylene, phenylene, tetrahydropyrandiyl, 1,3-dioxanediyl, pyrimidinediyl, or pyridinediyl, in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, Alkoxy having 1 to 12 carbons or a small amount Both may be replaced by one of hydrogen from 1 carbon atoms are replaced by fluorine or chlorine 12 alkyl; X ¹ and Y ¹ is a single bond, ethylene, carbonyloxy or methyleneoxy,; P ¹ and P ² is a group selected from a polymerizable group represented by formula (P-1) to formula (P-5); Sp ¹ and Sp ² are a single bond or alkylene having 1 to 10 carbon atoms. And in this alkylene, at least one —CH ₂ — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, wherein at least one —CH ₂ —CH ₂ — is It may be replaced by -CH = CH- or -C≡C-, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; ^{a 1} is 0 or By and; ^{c 1} is an integer from 0 to 5, ^{d 1} is an integer from 0 to 4;

In the formula (B), P ³ is a group selected from a polymerizable group represented by the formula (P-1) to the formula (P-5); Sp ³ is a single bond or 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-, in which at least one hydrogen may be replaced by fluorine or chlorine;

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

式（１−１）から式（１−６）において、Ｐ^１３およびＰ^１４は、式（Ｐ−１）から式（Ｐ−３）で表される基から選択された重合性基であり；

式（Ｐ−１）から（Ｐ−３）において、Ｍ^１、Ｍ^２、およびＭ^３は、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルであり；Ｓｐ^１３およびＳｐ^１４は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ｃ_３およびｃ_４は、０から５の整数であり、ｃ_５およびｃ_６は０または１であり、ｃ_３およびｃ_４の和は１以上であり、ｃ_５およびｃ_４の和は１以上であり、ｃ_５およびｃ_６の和は１以上である。 Item 2. Item 2. The liquid crystal composition according to item 1, comprising at least one compound selected from compounds represented by formulas (1-1) to (1-6) as a first additive.

In Formula (1-1) to Formula (1-6), P ¹³ and P ¹⁴ are polymerizable groups selected from the groups represented by Formula (P-1) to Formula (P-3);

In formulas (P-1) to (P-3), M ¹ , M ² , and M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced by fluorine or chlorine Sp ¹³ and Sp ¹⁴ are a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one —CH ₂ — is —O— or —COO—. , —OCO—, or —OCOO—, and at least one —CH ₂ —CH ₂ — may be replaced with —CH═CH— or —C≡C— , at least one of hydrogen, fluorine or may be replaced by chlorine; _{c 3} and _{c 4} is an integer from 0 to 5, _{c 5} and _{c 6} are 0 or 1, _{c 3} Oyo the sum of c ₄ is 1 or more, the sum of _{c 5} and _{c 4} is 1 or more, the sum of _{c 5} and _{c 6} is 1 or more.

Item 3. Item 3. The liquid crystal composition according to item 1 or 2, wherein the ratio of the first additive is in the range of 0.03% by mass to 10% by mass.

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

In Formula (2), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or at least 1 to 12 carbon alkyls in which one hydrogen is replaced by fluorine or chlorine; ring C and ring E are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5- Diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2 in which at least one hydrogen is replaced by fluorine or chlorine, 6-diyl, chroman-2,6-diyl, or chroma in which at least one hydrogen is replaced by fluorine or chlorine -2,6-diyl; ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1 , 4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7- Diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2,5-diyl; Z ¹ and Z ² are a single bond, ethylene, carbonyloxy, or methyleneoxy; e is 0, 1, 2, or 3; f is 0 or 1; the sum of e and f Is 3 or less.

式（２−１）から式（２−３５）において、Ｒ^１およびＲ^２は、水素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、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のアルキルである。 Item 5. Item 5. The liquid crystal composition according to any one of items 1 to 4, comprising at least one compound selected from compounds represented by formulas (2-1) to (2-35) as a first component.

In the formulas (2-1) to (2-35), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon number 2 to 12 alkenyloxy, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.

Item 6. Item 6. The liquid crystal composition according to item 4 or 5, wherein the ratio of the first component is in the range of 10% by mass to 80% by mass.

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

In the formula (3), R ³ and R ⁴ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon in which at least one hydrogen is replaced with fluorine or chlorine An alkyl having 1 to 12 carbon atoms, or an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; ring F and ring G are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ³ is a single bond, ethylene, or carbonyloxy; g is 1, 2, or 3 is there.

式（３−１）から式（３−１３）において、Ｒ^３およびＲ^４は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルである。 Item 8. Item 8. The liquid crystal composition according to any one of items 1 to 7, comprising at least one compound selected from compounds represented by formulas (3-1) to (3-13) as a second component.

In formulas (3-1) to (3-13), R ³ and R ⁴ are each an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or at least one hydrogen Is alkyl having 1 to 12 carbon atoms replaced by fluorine or chlorine, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine.

Item 9. Item 9. The liquid crystal composition according to item 7 or 8, wherein the ratio of the second component is in the range of 15% by mass to 80% by mass.

式（４）において、環Ｉおよび環Ｋは、シクロヘキシル、シクロヘキセニル、フェニル、１−ナフチル、２−ナフチル、テトラヒドロピラン−２−イル、１，３−ジオキサン−２−イル、ピリミジン−２−イル、またはピリジン−２−イルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；環Ｊ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^４およびＺ^５は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ_３）−、または−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｐ^４、Ｐ^５、およびＰ^６は重合性基であり；Ｓｐ^４、Ｓｐ^５、およびＳｐ^６は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ｈは、０、１、または２であり；ｉ、ｊ、およびｋは、０、１、２、３、または４であり；そしてｉ、ｊ、およびｋの和は、１以上である。 Item 10. Item 10. The liquid crystal composition according to any one of items 1 to 9, containing at least one compound selected from polymerizable compounds represented by formula (4) as the second additive.

In formula (4), ring I and ring K are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl Or, in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is fluorine or chlorine. And may be substituted with alkyl having 1 to 12 carbon atoms replaced by: Ring J 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-dii 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 from fluorine, chlorine, 1 carbon 12 alkyls, alkoxys having 1 to 12 carbons, or alkyls having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine; Z ⁴ and Z ⁵ may be a single bond or carbon alkylene from C 1 10, in the alkylene, at least one of _-CH 2 -, -O -, - CO -, - COO-, or May be replaced by OCO-, at least one _-CH 2 -CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, or -C (CH ₃ ) ═C (CH ₃ ) — may be replaced, in which at least one hydrogen may be replaced by fluorine or chlorine; P ⁴ , P ⁵ , and P ⁶ are polymerized Sp ⁴ , Sp ⁵ , and Sp ⁶ are a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, —COO—, -OCO-, or it may be replaced by -OCOO-, at least one _-CH 2 -CH ₂ - may be replaced by -CH = CH- or -C≡C-, and in the groups, At least One hydrogen may be replaced by fluorine or chlorine; h is 0, 1, or 2; i, j, and k are 0, 1, 2, 3, or 4; and i , J, and k are 1 or more.

式（Ｐ−６）から式（Ｐ−１０）において、Ｍ^４、Ｍ^５、およびＭ^６は、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルである。 Item 11. Item 11. The liquid crystal according to item 10, wherein in formula (4), P ⁴ , P ⁵ and P ⁶ are groups selected from the polymerizable groups represented by formula (P-6) to formula (P-10). Composition.

In Formula (P-6) to Formula (P-10), M ⁴ , M ⁵ , and M ⁶ are hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced with fluorine or chlorine And alkyl having 1 to 5 carbon atoms.

式（４−１）から式（４−２９）において、Ｐ^７、Ｐ^８、およびＰ^９は、式（Ｐ−６）から式（Ｐ−８）で表される基から選択された重合性基であり；

式（Ｐ−６）から（Ｐ−８）において、Ｍ^４、Ｍ^５、およびＭ^６は、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルであり；Ｓｐ^４、Ｓｐ^５、およびＳｐ^６は、単結合、または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。 Item 12. Item 12. The liquid crystal composition according to any one of items 1 to 11, comprising at least one polymerizable compound selected from compounds represented by formulas (4-1) to (4-29):

In the formulas (4-1) to (4-29), P ⁷ , P ⁸ , and P ⁹ are polymerizable selected from the groups represented by the formulas (P-6) to (P-8) A group;

In formulas (P-6) to (P-8), M ⁴ , M ⁵ , and M ⁶ are hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced by fluorine or chlorine is alkyl of 1 to 5 carbon ^atoms; Sp 4, Sp ^5, and Sp ⁶ is a single bond or alkylene having 1 to 10 carbon atoms, in the alkylene, at least one of -CH ₂ -, -O —, —COO—, —OCO—, or —OCOO— may be substituted, and at least one —CH ₂ —CH ₂ — may be substituted with —CH═CH— or —C≡C—. In these groups, at least one hydrogen may be replaced by fluorine or chlorine.

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

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

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

Item 16. 14. A polymer-supported alignment type liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 13, or a polymerizable compound in the liquid crystal composition being polymerized.

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

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

  The present invention also includes the following items. (A) As a third additive, at least one of additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound The above composition further comprising: (B) An AM device containing the above composition. (C) A polymer-supported orientation (PSA) type AM device containing the above composition. (D) A polymer-supported orientation (PSA) type AM device comprising the above-described composition, wherein the polymerizable compound in the composition is polymerized. (E) A device containing the above composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA. (F) A transmissive device containing the above composition. (G) Use of the above composition as a composition having a nematic phase. (H) Use of an optically active composition obtained by adding an optically active compound to the above composition.

  The composition of the present invention will be described in the following order. First, the composition of the composition will be described. Second, the main characteristics of the component compounds and the main effects of the compounds on the composition and the device will be described. Third, combinations of component compounds in the composition, desirable ratios, and the basis thereof will be described. Fourth, a preferred form of the component compound 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 the component compounds will be described. Finally, the use of the composition will be described.

  First, the composition of the composition will be described. This composition contains a plurality of liquid crystal compounds. The composition may contain additives. Additives include optically active compounds, antioxidants, ultraviolet absorbers, quenchers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. This composition is classified into a composition A and a composition B from the viewpoint of a liquid crystal compound. The composition A may further contain other liquid crystal compounds, additives and the like in addition to the liquid crystal compound selected from the compound (2) and the compound (3). The “other liquid crystal compound” is a liquid crystal compound different from the compound (2) and the compound (3). Such compounds are mixed into the composition for the purpose of further adjusting the properties.

  Composition B consists essentially of a liquid crystalline compound selected from compound (2) and compound (3). “Substantially” means that the composition B may contain an additive but does not contain any other liquid crystal compound. Composition B has fewer components than composition A. From the viewpoint of reducing the cost, the composition B is preferable to the composition A. The composition A is preferable to the composition B from the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds.

  Second, the main characteristics of the component compounds and the main effects of the compounds on the composition and the device will be described. The main characteristics of the component compounds are summarized in Table 2 based on the effects of the present invention. In the symbols in Table 2, L means large or high, M means moderate, and S means small or low. The symbols L, M, and S are classifications based on a qualitative comparison among the component compounds, and the symbol 0 (zero) means smaller than S (small).

  The main effects of the component compounds on the properties of the composition are as follows. Compound (1) and Compound (4) give a polymer by polymerization, and this polymer shortens the response time of the device and improves image burn-in. Compound (2) increases the dielectric anisotropy and decreases the minimum temperature. Compound (3) decreases the viscosity or increases the maximum temperature.

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

  A polymerizable compound such as compound (1) is added to the composition for the purpose of adapting to a polymer-supported orientation type device. A desirable ratio of the additive is approximately 0.03% by mass or more for aligning liquid crystal molecules, and approximately 10% by mass or less for preventing display defects of the device. A more desirable ratio is in the range of approximately 0.05% by mass to approximately 2.0% by mass. A particularly desirable ratio is in the range of approximately 0.05% by mass to approximately 1.0% by mass.

  A desirable ratio of compound (2) is approximately 10% by mass or more for increasing the dielectric anisotropy or increasing the maximum temperature, and approximately 80% by mass or less for decreasing the minimum temperature. A more desirable ratio is in the range of approximately 15% by mass to approximately 75% by mass. A particularly desirable ratio is in the range of approximately 20% by mass to approximately 70% by mass.

  A desirable ratio of compound (3) is approximately 15% by mass or more for decreasing the viscosity, and approximately 80% by mass or less for decreasing the minimum temperature. A more desirable ratio is in the range of approximately 20% by mass to approximately 65% by mass. A particularly desirable ratio is in the range of approximately 25% by mass to approximately 60% by mass.

  A polymerizable compound such as compound (4) is added to the composition for the purpose of adapting it to a polymer-supported orientation type device. A desirable ratio of the additive is approximately 0.03% by mass or more for aligning liquid crystal molecules, and approximately 10% by mass or less for preventing display defects of the device. A more desirable ratio is in the range of approximately 0.05% by mass to approximately 2.0% by mass. A particularly desirable ratio is in the range of approximately 0.05% by mass to approximately 1.0% by mass.

  Fourth, a preferred form of the component compound will be described. First, a 1st additive and a 2nd additive are demonstrated, and the 1st component and 2nd component which are two liquid crystalline compounds are demonstrated collectively.

(A) In the first additive formula (1), T ¹ and T ² are hydrogen, a group represented by the formula (A), or a group represented by the formula (B), and at least T ¹ and T ² Is a group represented by the formula (A) or a group represented by the formula (B), and at least one of T1 and T2 has one or more polymerizable groups. T ¹ and T ² are preferably a group represented by the formula (A) or a group represented by the formula (B). The wavy line in Formula (A) and Formula (B) indicates the site to be bound.

In formula (A), ring A ¹ is cyclohexyl, cyclohexenyl, phenyl, tetrahydropyranyl, 1,3-dioxanyl, pyrimidinyl, or pyridinyl, in which at least one hydrogen is fluorine, chlorine, Alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine may be substituted. Preferred ring A ¹ is cyclohexyl or phenyl. Ring B ¹ is cyclohexylene, cyclohexenylene, phenylene, tetrahydropyrandiyl, 1,3-dioxanediyl, pyrimidinediyl, or pyridinediyl, in which at least one hydrogen is fluorine, chlorine, carbon Alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine may be substituted. Preferred ring B ¹ is phenylene.

X ¹ and Y ¹ are a single bond, ethylene, carbonyloxy, or methyleneoxy. Preferred X ¹ and Y ¹ are a single bond.

P ¹ and P ² are groups selected from polymerizable groups represented by formula (P-1) to formula (P-5). P ¹ and P ² are preferably groups represented by the formula (P-1), the formula (P-2), or the formula (P-3). Further preferred P ¹ and P ² are groups represented by the formula (P-1). A preferred group represented by the formula (P-1) is —OCO—CH═CH ₂ or —OCO—C (CH ₃ ) ═CH ₂ . The wavy line from formula (P-1) to formula (P-5) indicates the site to be bound.

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

Sp ¹ and Sp ² are a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO—, —OCO—, or —OCOO—. And at least one —CH ₂ —CH ₂ — may be replaced by —CH═CH— or —C≡C—, in which at least one hydrogen is fluorine or chlorine May be replaced. Preferred Sp ¹ or Sp ² is a single _{bond, -OCH 2 -CH 2 -, -} CH 2 -CH 2 -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CO-CH = CH-, or -CH = CH-CO-. Further preferred Sp ¹ or Sp ² is a single bond or —OCH ₂ —CH ₂ —.

a ₁ is 0 or 1, and preferred a ₁ is 0.

c ₁ is an integer from 0 to 5, d ₁ is an integer from 0 to 4, preferred c ₁ and d ₁ are 0, ₁ , 2, and more preferred c ₁ and d ₁ are 0 Or it is 1.

In the formula (B), P ³ is a group selected from the polymerizable groups represented by the formulas (P-1) to (P-5). Preferred ^{P 3} has the formula (P-1), formula (P-2), or a group represented by the formula (P-3). Further preferred P ³ is a group represented by formula (P-1). A preferred group represented by the formula (P-1) is —OCO—CH═CH ₂ or —OCO—C (CH ₃ ) ═CH ₂ . The wavy line from formula (P-1) to formula (P-5) indicates the site to be bound.

In the formula (P-1) from the formula ^{(P-5), M 1} , M 2, and ^{M 3} is hydrogen, fluorine, alkyl of 1 to 5 carbon atoms or at least one hydrogen is replaced by fluorine or chlorine And alkyl having 1 to 5 carbon atoms. Preferred M ¹ , M ² or M ³ is hydrogen or methyl for increasing the reactivity. More preferred M ¹ is hydrogen or methyl, and more preferred M ² or M ³ is hydrogen.

Sp ³ is a single bond or alkylene having 1 to 10 carbon atoms, in the alkylene, at least one of _-CH 2 -, -O -, - COO -, - OCO-, or -OCOO- in replaced 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. Preferred Sp ³ represents a single _{bond, -OCH 2 -CH 2 -, -} CH 2 -CH 2 -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CO-CH = CH- Or —CH═CH—CO—. Further preferred Sp ³ is a single bond or —OCH ₂ —CH ₂ —.

(B) In the second additive formula (4), ring I and ring K are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2- Yl, pyrimidin-2-yl, or pyridin-2-yl, in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least One hydrogen may be replaced by alkyl having 1 to 12 carbons replaced by fluorine or chlorine. Preferred ring I or ring K is phenyl. Ring J 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, At least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is fluorine or chlorine. From the obtained 1 carbon atoms may be replaced by alkyl of 12. Preferred ring J is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁴ and Z ⁵ are a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, —CO—, —COO—, or —OCO—. may be replaced, 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 ) —, in which at least one hydrogen may be replaced by fluorine or chlorine. Preferred Z ⁴ or Z ⁵ is a single bond, —CH ₂ —CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, or —OCO—. Further preferred Z ⁴ or Z ⁵ is a single bond.

P ⁴ , P ⁵ , and P ⁶ are polymerizable groups. Preferred P ⁴ , P ⁵ , or P ⁶ is a group selected from a polymerizable group represented by formula (P-6) to formula (P-10). Further preferred P ⁴ , P ⁵ or P ⁶ is a group represented by the formula (P-6), the formula (P-7) or the formula (P-8). Particularly preferred P ⁴ , P ⁵ or P ⁶ is a group represented by the formula (P-6). A preferred group represented by formula (P-6) is —OCO—CH═CH ₂ or —OCO—C (CH ₃ ) ═CH ₂ . The wavy line from Formula (P-6) to Formula (P-10) indicates the site to be bound.

In the formula (P-10) from the formula ^{(P-6), M 4} , M 5, and ^{M 6} is hydrogen, fluorine, alkyl of 1 to 5 carbon atoms or at least one hydrogen is replaced by fluorine or chlorine And alkyl having 1 to 5 carbon atoms. Preferred M ⁴ , M ⁵ or M ⁶ is hydrogen or methyl for increasing the reactivity. More preferred M ⁴ is hydrogen or methyl, and more preferred M ⁵ or M ⁶ is hydrogen.

Sp ⁴ , Sp ⁵ , and Sp ⁶ are a single bond or alkylene having 1 to 10 carbon atoms, and in the alkylene, at least one —CH ₂ — is —O—, —COO—, —OCO—, or It may be replaced by -OCOO-, at least one _-CH 2 -CH ₂ - may be replaced by -CH = CH- or -C≡C-, and in the groups, at least one hydrogen , Fluorine or chlorine may be substituted. Preferred Sp ⁴ , Sp ⁵ or Sp ⁶ is a single bond, —OCH ₂ —CH ₂ —, —CH ₂ —CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, -CO-CH = CH- or -CH = CH-CO-. Further preferred Sp ⁴ , Sp ⁵ or Sp ⁶ is a single bond or —OCH ₂ —CH ₂ —.

  i, j, and k are 0, 1, 2, 3, or 4. Preferred i, j, or k is 1 or 2. h is 0, 1, or 2. Preferred h is 0 or 1.

(C) In the liquid crystal compound formulas (2) and (3), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, C2-C12 alkenyloxy or C1-C12 alkyl in which at least one hydrogen is replaced by fluorine or chlorine. Desirable R ¹ or R ² is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat, and alkoxy having 1 to 12 carbons for increasing the dielectric anisotropy. R ³ and R ⁴ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine Or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Desirable R ³ or R ⁴ is alkenyl having 2 to 12 carbons for decreasing the viscosity, and alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat.

  Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. More desirable alkyl is methyl, ethyl, propyl, butyl or pentyl for decreasing the viscosity.

  Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. More desirable alkoxy is methoxy or ethoxy for decreasing the viscosity.

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

  Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. More preferable alkenyloxy is allyloxy or 3-butenyloxy for decreasing the viscosity.

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

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

  Ring C and Ring E are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1 in which at least one hydrogen is replaced by fluorine or chlorine , 4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl, chroman-2,6-diyl, in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen is fluorine or chlorine Chroman-2,6-diyl replaced by Preferred ring C or ring E is 1,4-cyclohexylene for decreasing the viscosity or increasing the maximum temperature, and 1,4-phenylene for increasing the optical anisotropy.

Ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4, 5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl (FLF4), 4,6- Difluorodibenzofuran-3,7-diyl (BFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2), or 1,1,6,7-tetrafluoroindane-2,5-diyl (InF4) It is. Preferred ring D is 2,3-difluoro-1,4-phenylene for increasing the dielectric anisotropy.

  Ring F and ring G are 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 for decreasing the viscosity or increasing the maximum temperature, and 1,4-phenylene for increasing the optical anisotropy.

Z ¹ and Z ² are a single bond, ethylene, carbonyloxy, or methyleneoxy. Desirable Z ¹ or Z ² is a single bond for decreasing the viscosity, and methyleneoxy for increasing the dielectric anisotropy. Z ³ is a single bond, ethylene, or carbonyloxy. Desirable Z ³ is a single bond for decreasing the viscosity.

A divalent group such as methyleneoxy is asymmetrical. In methyleneoxy, —CH ₂ O— is preferred to —OCH ₂ —. In carbonyloxy, —COO— is preferred to —OCO—.

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

  Fifth, preferred component compounds are shown. Desirable compounds (1) are the compounds (1-1) to (1-6) described in item 2. In these compounds, it is preferable that at least one of the first additives is the compound (1-1), the compound (1-4), or the compound (1-6). It is preferable that at least two of the first additives are a combination of the compound (1-1) and the compound (1-4), the compound (1-1) and the compound (1-6).

  Desirable compound (2) is the compound (2-1) to the compound (2-35) according to item 5. In these compounds, at least one of the first components is compound (2-1), compound (2-3), compound (2-6), compound (2-8), compound (2-10), compound ( 2-13), a compound (2-14), or a compound (2-18) is preferable. At least two of the first components are compound (2-1) and compound (2-8), compound (2-1) and compound (2-14), compound (2-3) and compound (2-8), Compound (2-3) and Compound (2-10), Compound (2-3) and Compound (2-14), Compound (2-6) and Compound (2-8), Compound (2-6) and Compound A combination of (2-10), compound (2-6) and compound (2-18), or compound (2-10) and compound (2-14) is preferred.

  Desirable compound (3) is the compound (3-1) to the compound (3-13) according to item 8. In these compounds, at least one of the second components is a compound (3-1), a compound (3-2), a compound (3-3), a compound (3-4), a compound (3-5), a compound ( 3-6), compound (3-8), compound (3-11) or compound (3-13) is preferred. A combination of compound (3-1) and compound (3-3), compound (3-1) and compound (3-5), compound (3-1) and compound (3-6), wherein at least two of the second components are It is preferable that

  Desirable compound (4) is the compound (4-1) to the compound (4-29) according to item 12. In these compounds, at least one of the second additives is compound (4-1), compound (4-2), compound (4-24), compound (4-25), compound (4-26), or It is preferable that it is a compound (4-27). At least two of the second additives are compound (4-1) and compound (4-2), compound (4-1) and compound (4-18), compound (4-2) and compound (4-24). , Compound (4-2) and compound (4-25), compound (4-2) and compound (4-26), compound (4-25) and compound (4-26), or compound (4-18) And a combination of compounds (4-24).

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

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

  Since the compound (6-2) has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after the device has been used for a long time. A desirable ratio of the antioxidant is approximately 50 ppm or more for achieving its effect, and is approximately 600 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 300 ppm.

Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Also preferred are light stabilizers such as sterically hindered amines. Preferred examples of the light stabilizer include compounds (7-1) to (7-16). A desirable ratio of these absorbers and stabilizers is approximately 50 ppm or more for achieving the effect thereof, and approximately 10,000 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 10,000 ppm.

The quencher is a compound that prevents the decomposition of the liquid crystalline compound by receiving the light energy absorbed by the liquid crystalline compound and converting it into thermal energy. Preferred examples of the quencher include the compound (8-1) to the compound (8-7). A desirable ratio of these quenchers is about 50 ppm or more for achieving the effect thereof, and about 20000 ppm or less for decreasing the minimum temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 10,000 ppm.

  A dichroic dye such as an azo dye or an anthraquinone dye is added to the composition in order to adapt to a GH (guest host) mode device. A preferred ratio of the dye is in the range of approximately 0.01% by mass to approximately 10% by mass. In order to prevent foaming, an antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is added to the composition. A desirable ratio of the antifoaming agent is approximately 1 ppm or more for obtaining the effect thereof, and approximately 1000 ppm or less for preventing a display defect. A more desirable ratio is in the range of approximately 1 ppm to approximately 500 ppm.

  A polymerizable compound is used to adapt to a polymer support alignment (PSA) type device. Compound (1) and compound (4) are suitable for this purpose. A polymerizable compound different from these compounds may be added to the composition together with the compound (1) and the compound (4). Preferable examples of other polymerizable compounds are compounds such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. Further preferred examples are acrylate and methacrylate. Combining the compound (1) or compound (4) with a polymerizable compound different from the compound (1) or compound (4) in an appropriate ratio by changing the type of the compound (1) or compound (4). Thus, the reactivity of the polymerizable compound and the pretilt angle of the liquid crystal molecules can be adjusted. By optimizing the pretilt angle, a short response time of the element can be achieved. Since the alignment of the liquid crystal molecules is stabilized, a large contrast ratio and a long lifetime can be achieved.

  A polymerizable compound such as compound (1) or compound (4) is polymerized by ultraviolet irradiation. The polymerization may be performed in the presence of a suitable polymerization initiator such as a photopolymerization initiator. Appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those skilled in the art and are described in the literature. For example, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF), which are photoinitiators, are suitable for radical polymerization. A desirable ratio of the photopolymerization initiator is in the range of approximately 0.1% by mass to approximately 5% by mass based on the mass of the polymerizable compound. A more desirable ratio is in the range of approximately 1% by mass to approximately 3% by mass.

  When storing a polymerizable compound such as compound (1) or compound (4), a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone derivatives such as hydroquinone and methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine and the like.

The polar compound is an organic compound having polarity. Here, a compound having an ionic bond is not included. Atoms such as oxygen, sulfur, and nitrogen are more electronegative and tend to have partial negative charges. Carbon and hydrogen tend to be neutral or have a partial positive charge. Polarity arises from the fact that partial charges are not evenly distributed among different types of atoms in a compound. For example, the polar compound has at least one of partial structures such as —OH, —COOH, —SH, —NH ₂ ,> NH, and> N—.

  Seventh, a method for synthesizing the component compounds will be described. These compounds can be synthesized by known methods. A synthesis method is illustrated. Synthesis examples of compound (1) are described in the Examples section. Compound (2-8) is synthesized by the method described in JP-T-2-503441. Compound (3-5) is synthesized by the method described in JP-A-59-176221. Compound (4-19) is synthesized by the method described in JP-A-7-101900. Antioxidants are commercially available. Compound (6-1) is available from Sigma-Aldrich Corporation. Compound (6-2) and the like are synthesized by the method described in US Pat. No. 3,660,505.

  Compounds that have not been described as synthetic methods include Organic Synthesis (John Wiley & Sons, Inc.), Organic Reactions (John Wiley & Sons, Inc.), Comprehensive Organic Synthesis ( Comprehensive Organic Synthesis, Pergamon Press), New Experimental Chemistry Course (Maruzen), etc. The composition is prepared from the compound thus obtained by known methods. For example, the component compounds are mixed and dissolved in each other by heating.

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

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

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

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

  The invention is explained in more detail by means of examples. The invention is not limited by these examples. The present invention includes a mixture of the composition of Example 1 and the composition of Example 2. The invention also includes a mixture of at least two of the example compositions. The synthesized compound was identified by a method such as NMR analysis. The characteristics of the compound, composition and device were measured by the methods described below.

NMR analysis: For measurement, DRX-500 manufactured by Bruker BioSpin Corporation was used. ^In the measurement of ¹ H-NMR, the sample was dissolved in a deuterated solvent such as CDCl _3, and the measurement was performed at room temperature under conditions of 500 MHz and 16 integrations. Tetramethylsilane was used as an internal standard. ^{For 19} 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 a singlet, d is a doublet, t is a triplet, q is a quartet, quint is a quintet, sex is a sextet, m is a multiplet, and br is broad.

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

  As a solvent for diluting the sample, chloroform, hexane or the like may be used. In order to separate the component compounds, the following capillary column may be used. 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 made by SGE International Pty. Ltd (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm). In order to prevent compound peaks from overlapping, 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.

  The ratio of the liquid crystal compound contained in the composition may be calculated by the following method. The mixture of liquid crystalline compounds is analyzed by gas chromatography (FID). The area ratio of peaks in the gas chromatogram corresponds to the ratio (mass ratio) 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 ratio (% by mass) of the liquid crystal compound can be calculated from the peak area ratio.

  Measurement sample: When measuring the characteristics of the composition and the device, the composition was used as it was as a sample. When measuring the characteristics of the compound, a sample for measurement was prepared by mixing this compound (15% by mass) with the mother liquid crystal (85% by mass). The characteristic value of the compound was calculated from the value obtained by the measurement by extrapolation. (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 and the mother liquid crystal is 10% by mass: 90% by mass, 5% by mass: 95% by mass, and 1% by mass: 99% by mass in this order. changed. By this extrapolation method, the maximum temperature, optical anisotropy, viscosity, and dielectric anisotropy values for the compound were determined.

The following mother liquid crystals were used. The ratio of the component compound is indicated by mass%.

  Measuring method: The characteristics were measured by the following method. Many of these methods have been modified by a method described in the JEITA standard (JEITA ED-2521B) established by the Japan Electronics and Information Technology Industries Association (hereinafter referred to as JEITA) or a modification thereof. Was the way. A thin film transistor (TFT) was not attached to the element used for the measurement.

(1) Maximum temperature of nematic phase (NI; ° C.): A sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when a part of the sample changed from a nematic phase to an isotropic liquid. The 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, when the sample remained in the nematic phase at −20 ° C. and changed to a crystalline or smectic phase at −30 ° C., the _TC was described as <−20 ° 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 viscometer manufactured by Tokyo Keiki Co., Ltd. was used for the measurement.

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

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

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

(7) Voltage holding ratio (VHR-1; measured at 25 ° C .;%): The TN device used for the measurement had a polyimide alignment film, and the distance between two glass substrates (cell gap) was 5 μm. . This element was sealed with an adhesive that was cured with ultraviolet rays after the sample was placed. The TN device was charged by applying a pulse voltage (60 microseconds at 5 V). The decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined. Area B was the area when it was not attenuated. The voltage holding ratio was expressed as a percentage of area A with respect to area B.

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

(9) Voltage holding ratio (VHR-3; measured at 25 ° C .;%): After irradiation with ultraviolet rays, the voltage holding ratio was measured and the stability against ultraviolet rays was evaluated. The TN device used for the measurement had a polyimide alignment film, and the cell gap was 5 μm. A sample was injected into this element and irradiated with light for 20 minutes. The light source was an ultra-high pressure mercury lamp USH-500D (made by USHIO Inc.), and the distance between the element and the light source was 20 cm. In the measurement of VHR-3, a decaying voltage was measured for 16.7 milliseconds. A composition having a large VHR-3 has a large stability to ultraviolet light. VHR-3 is preferably 90% or more, and more preferably 95% or more.

(10) Voltage holding ratio (VHR-4; measured at 25 ° C .;%): The TN device injected with the sample is heated in a thermostatic bath at 80 ° C. for 500 hours, and then the voltage holding ratio is measured, and stability against heat. Evaluated. In the measurement of VHR-4, a decaying voltage was measured for 16.7 milliseconds. A composition having a large VHR-4 has a large stability to heat.

(11) Response time (τ; measured at 25 ° C .; ms): An LCD5200 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. The low-pass filter (Low-pass filter) was set to 500 Hz.
A distance (cell gap) between two glass substrates was 3.2 μm, and a sample was put in a normally black mode PSA element. The device was irradiated with 76 mW / cm ² of ultraviolet light while applying a voltage of 15 V, and the pretilt angle was set to 0.9 ± 0.2 °. A metal halide lamp (US4-X0401FKTN) manufactured by Eye Graphic Co., Ltd. was used for ultraviolet irradiation. Next, ultraviolet rays of 3.8 mW / cm ² were irradiated for 60 minutes without applying a voltage. A black light (F40T10) manufactured by Eye Graphic Co., Ltd. was used for ultraviolet irradiation. A rectangular wave (30 Hz, 7.5 V, 1 second) was applied to this element. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. It was considered that the transmittance was 100% when the light amount was the maximum, and the transmittance was 0% when the light amount was the minimum. The response time was expressed as the time required to change the transmittance from 90% to 10% (fall time; millisecond).

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

(13) Specific resistance (ρ; measured at 25 ° C .; Ωcm): A sample (1.0 mL) was injected into a container equipped with electrodes. A DC voltage (10 V) was applied to the container, and the DC current after 10 seconds was measured. The specific resistance was calculated from the following equation. (Resistivity) = {(Voltage) × (Capacity of container)} / {(DC current) × (Dielectric constant of vacuum)}.

(14) Pretilt angle (Pt; °) of PSA element: A sample was prepared by adding a polymerizable compound to a liquid crystal composition and dissolving it. The sample was injected into a cell with ITO coated with a polyimide alignment film that induces vertical alignment with a cell gap of 3.5 μm. The pretilt angle (crystal rotation method) at this time is set to 0 °. While applying a voltage of 15 V, ultraviolet rays of 80 mW / cm ² were irradiated for 375 seconds. For ultraviolet irradiation, an eye ultraviolet curing device manufactured by Eye Graphics Co., Ltd. was used. Thereafter, the pretilt angle of this cell was measured. Here, a large value (that is, a large deviation from 0 °) means a large pretilt angle.

(15) Threshold voltage of PSA element (Vth; measured at 25 ° C .; V): The element obtained in (14) was measured using an LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. The light source was a halogen lamp. The voltage (60 Hz, rectangular wave) applied to the element was increased stepwise from 0V to 20V by 0.02V. At this time, the device was sandwiched between two orthogonal polarizers, and the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount reached the maximum and the transmittance was 0% when the light amount was the minimum. The threshold voltage was expressed as a voltage when the transmittance reached 10%.

[Synthesis Example 1]
Synthesis of compound (1-1-1)

First Step Compound (T-1) (manufactured by Tokyo Chemical Industry Co., Ltd., 5.00 g), methacrylic acid (T-2) (3.07 g), 4-dimethylaminopyridine (DMAP) (1.74 g), and toluene (80.0 ml) was charged to the reactor and cooled to 0 ° C. A solution of N, N′-dicyclohexylcarbodiimide (DCC) (7.36 g) in toluene (20.0 ml) was slowly added dropwise thereto, and the mixture was stirred for 12 hours while returning to room temperature. The insoluble material was filtered off, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The obtained 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 (toluene). Further purification by recrystallization from ethyl acetate gave compound (1-1-1) (4.30 g; 62%).

The NMR analysis value of the obtained compound (1-1-1) is as follows.
¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.79 (d, J = 7.5 Hz, 2H), 7.43-7.37 (m, 4H), 7.33-7.22 (M, 6H), 7.03-6.98 (m, 4H), 6.33 (s, 2H), 5.75 (s, 2H), 2.06 (s, 6H).

The physical properties of the compound (1-1-1) were as follows.
Transition temperature: C 113 C 143 I.I.

[Synthesis Example 2]
Synthesis of compound (1-1-2)

First Step Compound (T-1) (5.00 g), potassium carbonate (7.89 g), and N, N-dimethylformamide (DMF) (100 ml) were placed in a reactor and stirred at 115 ° C. for 30 minutes. Ethylene carbonate (T-3) (3.14 g) was added thereto, and the mixture was stirred at 115 ° C. for 3 hours. The reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The obtained 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 recrystallization from toluene to obtain Compound (T-4) (6.12 g; 98%).

Second Step Compound (T-4) (5.00 g), triethylamine (4.77 ml), and THF (200 ml) were placed in a reactor and cooled to 0 ° C. Acryloyl chloride (T-5) (2.32 ml) was slowly added dropwise thereto, and the mixture was stirred for 3 hours while returning to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The obtained 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 = 10: 1). Further purification by recrystallization from toluene gave compound (1-1-2) (2.59 g; 42%).

The NMR analysis value of the obtained compound (1-1-2) is as follows.
¹ H-NMR: Chemical shift _{δ (ppm; CDCl 3):} 7.75 (d, J = 7.5Hz, 2H), 7.38-7.32 (m, 4H), 7.29-7.23 (M, 2H), 7.14-7.08 (m, 4H), 6.79-6.73 (m, 4H), 6.41 (dd, J = 17.2 Hz, J = 1.2 Hz, 2H), 6.13 (dd, J = 17.2 Hz, J = 10.6 Hz, 2H), 5.83 (dd, J = 10.6 Hz, J = 1.2 Hz, 2H), 4.47 (t , J = 4.9 Hz, 4H), 4.14 (t, J = 4.8 Hz, 4H).

The physical properties of the compound (1-1-2) were as follows.
Transition temperature: C 74.5

  The compounds in Examples were represented by symbols based on the definitions in Table 3 below. In Table 3, the configuration regarding 1,4-cyclohexylene is trans. The number in parentheses after the symbol corresponds to the compound number. The symbol (−) means other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is a mass percentage (% by mass) based on the mass of the liquid crystal composition. Finally, the characteristic values of the composition are summarized.

As the first additive, the following compound (1-1-1) and compound (1-1-2) were used.

As a comparative example, Example 5 was selected from the compositions disclosed in WO2010 / 084823. This composition contains a compound (4-1-1).

[Comparative Example 1]
V-HB (2F, 3F) -O2 (2-1) 10%
V-HB (2F, 3F) -O4 (2-1) 10%
3-H2B (2F, 3F) -O2 (2-2) 13%
5-H2B (2F, 3F) -O2 (2-2) 12%
3-HBB (2F, 3F) -O2 (2-14) 11%
4-HBB (2F, 3F) -O2 (2-14) 4%
5-HBB (2F, 3F) -O2 (2-14) 9%
3-HH-4 (3-1) 2%
3-HHEH-3 (3-4) 2%
3-HHEH-5 (3-4) 2%
4-HHEH-3 (3-4) 2%
4-HHEH-5 (3-4) 2%
3-HHB-1 (3-5) 4%
3-HHB-3 (3-5) 7%
3-HHB-O1 (3-5) 4%
3-HHEBH-3 (3-11) 3%
3-HHEBH-5 (3-11) 3%
To this composition, the compound (4-1-1) was added in a proportion of 0.30% by mass.
NI = 91.2 ° C .; Δn = 0.108; Δε = −4.4; Pt = 1.2 °; Vth = 1.42V.

[Example 1]
A composition obtained by replacing the compound (4-1-1) with the compound (1-1-2) in the composition of Comparative Example 1 was taken as Example 1.
V-HB (2F, 3F) -O2 (2-1) 10%
V-HB (2F, 3F) -O4 (2-1) 10%
3-H2B (2F, 3F) -O2 (2-2) 13%
5-H2B (2F, 3F) -O2 (2-2) 12%
3-HBB (2F, 3F) -O2 (2-14) 11%
4-HBB (2F, 3F) -O2 (2-14) 4%
5-HBB (2F, 3F) -O2 (2-14) 9%
3-HH-4 (3-1) 2%
3-HHEH-3 (3-4) 2%
3-HHEH-5 (3-4) 2%
4-HHEH-3 (3-4) 2%
4-HHEH-5 (3-4) 2%
3-HHB-1 (3-5) 4%
3-HHB-3 (3-5) 7%
3-HHB-O1 (3-5) 4%
3-HHEBH-3 (3-11) 3%
3-HHEBH-5 (3-11) 3%
To this composition, the compound (1-1-2) was added in a proportion of 0.30% by mass.
NI = 91.2 ° C .; Δn = 0.108; Δε = −4.4; Pt = 3.2 °; Vth = 1.32V

[Example 2]
3-DhB (2F, 3F) -O2 (2-4) 4%
3-BB (2F, 3F) -O2 (2-6) 9%
5-BB (2F, 3F) -O2 (2-6) 9%
2-HHB (2F, 3F) -O2 (2-8) 3%
3-HHB (2F, 3F) -O2 (2-8) 5%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 10%
V-HHB (2F, 3F) -O4 (2-8) 9%
3-HDhB (2F, 3F) -O2 (2-13) 10%
3-BB (F) B (2F, 3F) -O2 (2-21) 4%
V-HH2BB (2F, 3F) -O2 (2-24) 2%
3-HH-V (3-1) 14%
3-HH-VFF (3-1) 4%
7-HB-1 (3-2) 2%
1-BB-3 (3-3) 1%
V-HHB-1 (3-5) 1%
3-HBB-2 (3-6) 2%
V-HBB-2 (3-6) 3%
2-BB (F) B-5 (3-8) 2%
3-HB (F) HH-2 (3-10) 2%
To this composition, the compound (1-1-2) was added at a ratio of 0.15% by mass.
NI = 93.1 ° C .; Δn = 0.125; Δε = −4.2; Pt = 1.8 °; Vth = 1.42V.

[Example 3]
3-HB (2F, 3F) -O2 (2-1) 5%
V1O-chB (2F, 3F) -O2 (2-5) 5%
2-BB (2F, 3F) -O2 (2-6) 7%
V2-BB (2F, 3F) -O2 (2-6) 8%
2O-B (2F) B (2F, 3F) -O2 (2-7) 6%
2-HHB (2F, 3F) -O2 (2-8) 3%
3-HHB (2F, 3F) -O2 (2-8) 4%
5-HHB (2F, 3F) -O2 (2-8) 3%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 6%
V-HHB (2F, 3F) -O4 (2-8) 4%
3-HH2B (2F, 3F) -O2 (2-9) 9%
3-BB (2F) B (2F, 3F) -O2 (2-20) 3%
2-BB2B (2F, 3F) -3 (2-23) 3%
3-HH-V (3-1) 10%
5-HH-V (3-1) 4%
1-BB-3 (3-3) 2%
V-HHB-1 (3-5) 5%
V2-HHB-1 (3-5) 5%
3-HBB (F) B-2 (3-13) 4%
To the composition, 0.05% by mass of compound (1-1-1) and 0.20% by mass of compound (1-1-2) were added.
NI = 83.2 ° C .; Δn = 0.123; Δε = −3.8; Pt = 2.1 °; Vc = 1.78 V.

[Example 4]
V-HB (2F, 3F) -O2 (2-1) 7%
2-BB (2F, 3F) -O2 (2-6) 6%
3-BB (2F, 3F) -O2 (2-6) 8%
3-HHB (2F, 3F) -O2 (2-8) 8%
5-HHB (2F, 3F) -O2 (2-8) 8%
V-HHB (2F, 3F) -O2 (2-8) 6%
3-HH2B (2F, 3F) -O2 (2-9) 8%
2-HBB (2F, 3F) -O2 (2-14) 3%
3-HBB (2F, 3F) -O2 (2-14) 6%
4-HBB (2F, 3F) -O2 (2-14) 3%
V-HBB (2F, 3F) -O2 (2-14) 3%
5-HFLF4-3 (2-28) 3%
3-HH-V (3-1) 31%
To this composition, 0.05% by mass of compound (1-1-1) and 0.25% by mass of compound (1-1-2) were added.
NI = 78.5 ° C .; Δn = 0.098; Δε = −4.0; η = 17.8 mPa · s; Pt = 1.9 °; Vc = 1.52V.

[Example 5]
3-HB (2F, 3F) -O2 (2-1) 4%
2-H1OB (2F, 3F) -O2 (2-3) 6%
2-HH1OB (2F, 3F) -O2 (2-10) 16%
3-HH1OB (2F, 3F) -O2 (2-10) 12%
V-HchB (2F, 3F) -O2 (2-12) 6%
3-HB (2F, 3F) B-O2 (2-17) 4%
3-HB (2F) B (2F, 3F) -O2 (2-18) 8%
2-B2BB (2F, 3F) -O2 (2-22) 4%
3-H2BBB (2F, 3F) -O2 (2-25) 2%
2-HH-3 (3-1) 6%
2-HH-5 (3-1) 3%
3-HH-4 (3-1) 3%
3-HH-5 (3-1) 3%
3-HB-O2 (3-2) 3%
1-BB-3 (3-3) 4%
1-BB-5 (3-3) 3%
3-HHB-1 (3-5) 2%
3-HBB-2 (3-6) 3%
2-BB (F) B-2V (3-8) 3%
3-HHEBH-3 (3-11) 5%
To this composition, the compound (1-1-2) was added at a ratio of 0.12% by mass.
NI = 97.1 ° C .; Δn = 0.121; Δε = −4.0; η = 18.9 mPa · s; Pt = 1.5 °; Vth = 1.72V.

[Example 6]
5-HB (2F, 3F) -O2 (2-1) 6%
3-BB (2F, 3F) -O2 (2-6) 7%
2-HHB (2F, 3F) -O2 (2-8) 5%
3-HHB (2F, 3F) -O2 (2-8) 8%
5-HHB (2F, 3F) -O2 (2-8) 4%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 5%
3-HH2B (2F, 3F) -O2 (2-9) 10%
3-HDhB (2F, 3F) -O2 (2-13) 7%
3-dhBB (2F, 3F) -O2 (2-16) 8%
3-HH-V (3-1) 28%
3-HH-V1 (3-1) 5%
V2-BB-1 (3-3) 3%
To this composition, the compound (1-1-2) was added at a ratio of 0.25% by mass.
NI = 87.5 ° C .; Δn = 0.096; Δε = −3.8; η = 19.3 mPa · s; Pt = 1.8 °; Vth = 1.84 V.

[Example 7]
3-BB (2F, 3F) -O2 (2-6) 12%
V2-BB (2F, 3F) -O2 (2-6) 10%
V-HHB (2F, 3F) -O2 (2-8) 10%
3-HH1OB (2F, 3F) -O2 (2-10) 15%
3-HDhB (2F, 3F) -O2 (2-13) 8%
2-BB (2F, 3F) B-3 (2-19) 7%
2-HH-3 (3-1) 12%
3-HH-O1 (3-1) 3%
3-HH-V1 (3-1) 3%
1V2-HH-3 (3-1) 3%
5-HB-O2 (3-2) 2%
3-HHEH-3 (3-4) 2%
3-HHB-O1 (3-5) 3%
V-HHB-1 (3-5) 3%
V2-HHB-1 (3-5) 5%
1O1-HBBH-5 (-) 2%
To this composition, 0.05% by mass of compound (1-1-1) and 0.15% by mass of compound (1-1-2) were added.
NI = 87.1 ° C .; Δn = 0.120; Δε = −3.8; η = 21.7 mPa · s; Pt = 1.8 ° Vth = 1.78 V.

[Example 8]
3-H1OB (2F, 3F) -O2 (2-3) 3%
3-BB (2F, 3F) -O2 (2-6) 9%
5-BB (2F, 3F) -O2 (2-6) 9%
3-HDhB (2F, 3F) -O2 (2-13) 7%
2-HBB (2F, 3F) -O2 (2-14) 3%
3-HBB (2F, 3F) -O2 (2-14) 12%
5-HBB (2F, 3F) -O2 (2-14) 9%
3-dhBB (2F, 3F) -O2 (2-16) 10%
3-H1OCro (7F, 8F) -5 (2-26) 2%
3-HH1OCro (7F, 8F) -5 (2-27) 3%
2-HH-3 (3-1) 10%
1V2-BB-1 (3-3) 3%
5-B (F) BB-2 (3-7) 4%
5-B (F) BB-3 (3-7) 4%
2-BB (F) B-3 (3-8) 3%
2-BB2B-3 (3-9) 5%
5-HB (F) BH-5 (3-12) 4%
To this composition, the compound (1-1-2) was added at a ratio of 0.18% by mass.
NI = 88.6 ° C .; Δn = 0.152; Δε = −4.9; η = 44.3 mPa · s; Pt = 2.1 ° Vth = 1.16 V.

[Example 9]
3-H2B (2F, 3F) -O2 (2-2) 14%
5-H2B (2F, 3F) -O2 (2-2) 14%
3-DhB (2F, 3F) -O2 (2-4) 4%
3-HHB (2F, 3Cl) -O2 (2-11) 2%
4-HHB (2F, 3Cl) -O2 (2-11) 2%
5-HHB (2F, 3Cl) -O2 (2-11) 2%
3-HBB (2F, 3F) -O2 (2-14) 9%
3-HBB (2F, 3Cl) -O2 (2-15) 9%
4-HBB (2F, 3Cl) -O2 (2-15) 6%
5-HBB (2F, 3Cl) -O2 (2-15) 8%
3-HH-V (3-1) 18%
V-HHB-1 (3-5) 9%
5-HBB (F) B-2 (3-13) 3%
To this composition, the compound (1-1-2) was added at a ratio of 0.20% by mass.
NI = 80.3 ° C .; Δn = 0.103; Δε = −3.5; η = 25.2 mPa · s; Pt = 2.1 °; Vth = 2.17V.

[Example 10]
3-H1OB (2F, 3F) -O2 (2-3) 6%
3-BB (2F, 3F) -O2 (2-6) 10%
V-HHB (2F, 3F) -O2 (2-8) 11%
2-HH1OB (2F, 3F) -O2 (2-10) 6%
3-HH1OB (2F, 3F) -O2 (2-10) 19%
2-BB (2F, 3F) B-3 (2-19) 13%
3-HH-V (3-1) 29%
V-HH-V (3-1) 4%
3-HBB (F) B-2 (3-13) 2%
To this composition, the compound (1-1-2) was added in a proportion of 0.30% by mass.
NI = 76.8 ° C .; Δn = 0.106; Δε = −3.4; η = 22.7 mPa · s; Pt = 1.8 °; Vth = 2.02 V.

[Example 11]
V2-BB (2F, 3F) -O2 (2-6) 4%
3-BB (2F, 3F) -O2 (2-6) 10%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 10%
V-HHB (2F, 3F) -O4 (2-8) 10%
2-HHB (2F, 3F) -O2 (2-8) 3%
3-HHB (2F, 3F) -O2 (2-8) 5%
3-dhBB (2F, 3F) -O2 (2-16) 8%
V-HH2BB (2F, 3F) -O2 (2-24) 4%
3-HH-V (3-1) 42%
To this composition, the compound (1-1-1) was added in a proportion of 0.30% by mass.
NI = 83.8 ° C .; Δn = 0.091; Δε = −3.1; η = 19.3 mPa · s; Pt = 1.8 °; Vth = 2.31 V.

[Example 12]
3-HHB (2F, 3F) -1 (2-8) 14%
3-HHB (2F, 3F) -O2 (2-8) 12%
5-HHB (2F, 3F) -O2 (2-8) 11%
3-HH1OB (2F, 3F) -1 (2-10) 4%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 9%
3-HBB (2F, 3F) -O2 (2-14) 9%
5-HH-O1 (3-1) 9%
5-HH-3 (3-1) 10%
5-HB-3 (3-2) 14%
2-HHB-3 (3-5) 4%
To this composition, 0.05% by mass of compound (1-1-1) and 0.10% by mass of compound (1-1-2) were added.
Added.
NI = 95.2 ° C .; Δn = 0.086; Δε = −4.8; γ1 = 160.8 mPa · s; Pt = 1.5 °; Vth = 1.16 V.

  The pretilt angle of the PSA element obtained from the composition of Comparative Example 1 was 1.2 °. On the other hand, the pretilt angle of the PSA element obtained from the composition of Example 1 was 3.2 °. Further, the threshold voltage Vth of the PSA element obtained from the composition of Comparative Example 1 was 1.42V. On the other hand, the threshold voltage Vth of the PSA element obtained from the composition of Example 1 was 1.32V. Since the PSA element made of the composition of Example 1 has a larger pretilt angle than the PSA element made of the composition of Comparative Example 1, it has a lower threshold voltage Vth. Therefore, it is concluded that a device having excellent characteristics can be obtained by using the liquid crystal composition of the present invention.

  The liquid crystal composition of the present invention has a high maximum temperature, a low minimum temperature, a small viscosity, a large optical anisotropy, a large negative dielectric anisotropy, a large specific resistance, a high stability to ultraviolet light, a high stability to heat, etc. The characteristics satisfy at least one characteristic or have an appropriate balance with respect to at least two characteristics. A liquid crystal display device containing this composition has characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime, and can be used for a liquid crystal monitor, a liquid crystal television, and the like. .

Claims (18)

A liquid crystal composition containing at least one compound selected from polymerizable compounds represented by formula (1) as a first additive and having a nematic phase.

In Formula (1), T ¹ and T ² are hydrogen, a group represented by Formula (A), or a group represented by Formula (B), and at least ^one of T ¹ and T ² is represented by Formula (1). A group represented by A) or a group represented by formula (B); at least ^one of T ¹ and T ² has one or more polymerizable groups;

In formula (A), ring A ¹ is cyclohexyl, cyclohexenyl, phenyl, tetrahydropyranyl, 1,3-dioxanyl, pyrimidinyl, or pyridinyl, in which at least one hydrogen is fluorine, chlorine, An alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, or an alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine may be substituted; ring B ¹ is cyclohexylene , Cyclohexenylene, phenylene, tetrahydropyrandiyl, 1,3-dioxanediyl, pyrimidinediyl, or pyridinediyl, in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, Alkoxy having 1 to 12 carbons or a small amount Both may be replaced by one of hydrogen from 1 carbon atoms are replaced by fluorine or chlorine 12 alkyl; X ¹ and Y ¹ is a single bond, ethylene, carbonyloxy or methyleneoxy,; P ¹ and P ² is a group selected from a polymerizable group represented by formula (P-1) to formula (P-5); Sp ¹ and Sp ² are a single bond or alkylene having 1 to 10 carbon atoms. And in this alkylene, at least one —CH ₂ — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, wherein at least one —CH ₂ —CH ₂ — is It may be replaced by -CH = CH- or -C≡C-, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; ^{a 1} is 0 or By and; ^{c 1} is an integer from 0 to 5, ^{d 1} is an integer from 0 to 4;

In the formula (B), P ³ is a group selected from a polymerizable group represented by the formula (P-1) to the formula (P-5); Sp ³ is a single bond or 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-, in which at least one hydrogen may be replaced by fluorine or chlorine;

In Formula (P-1) to Formula (P-5), M ¹ , M ² , and M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced with fluorine or chlorine And alkyl having 1 to 5 carbon atoms.
2. The liquid crystal composition according to claim 1, comprising at least one compound selected from compounds represented by formulas (1-1) to (1-6) as a first additive.

In Formula (1-1) to Formula (1-6), P ¹³ and P ¹⁴ are polymerizable groups selected from the groups represented by Formula (P-1) to Formula (P-3);

In formulas (P-1) to (P-3), M ¹ , M ² , and M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced by fluorine or chlorine Sp ¹³ and Sp ¹⁴ are a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one —CH ₂ — is —O— or —COO—. , -OCO-, or may be replaced by -OCOO-, at least one _-CH 2 -CH ₂ - may be replaced by -CH = CH- or -C≡C-, and in the groups , at least one of hydrogen, fluorine or may be replaced by chlorine; _{c 3} and _{c 4} is an integer from 0 to 5, _{c 5} and _{c 6} are 0 or 1, _{c 3} Oyo the sum of c ₄ is 1 or more, the sum of _{c 5} and _{c 4} is 1 or more, the sum of _{c 5} and _{c 6} is 1 or more.   The liquid crystal composition according to claim 1 or 2, wherein the ratio of the first additive is in the range of 0.03% by mass to 10% by mass. The liquid crystal composition according to any one of claims 1 to 3, comprising at least one compound selected from compounds represented by formula (2) as a first component.

In Formula (2), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or at least 1 to 12 carbon alkyls in which one hydrogen is replaced by fluorine or chlorine; ring C and ring E are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5- Diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2 in which at least one hydrogen is replaced by fluorine or chlorine, 6-diyl, chroman-2,6-diyl, or chroma in which at least one hydrogen is replaced by fluorine or chlorine -2,6-diyl; ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1 , 4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7- Diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2,5-diyl; Z ¹ and Z ² are a single bond, ethylene, carbonyloxy, or methyleneoxy; e is 0, 1, 2, or 3; f is 0 or 1; the sum of e and f Is 3 or less. 5. The liquid crystal composition according to claim 1, comprising at least one compound selected from compounds represented by formulas (2-1) to (2-35) as a first component. .

In the formulas (2-1) to (2-35), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon number 2 to 12 alkenyloxy, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.   The liquid crystal composition according to claim 4 or 5, wherein the ratio of the first component is in the range of 10% by mass to 80% by mass. The liquid crystal composition according to claim 1, comprising at least one compound selected from compounds represented by formula (3) as the second component.

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

In formulas (3-1) to (3-13), R ³ and R ⁴ are each an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or at least one hydrogen Is alkyl having 1 to 12 carbon atoms replaced by fluorine or chlorine, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine.   The liquid crystal composition according to claim 7 or 8, wherein the ratio of the second component is in the range of 15% by mass to 80% by mass. 10. The liquid crystal composition according to claim 1, comprising at least one compound selected from the polymerizable compounds represented by formula (4) as the second additive.

In formula (4), ring I and ring K are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl Or, in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is fluorine or chlorine. And may be substituted with alkyl having 1 to 12 carbon atoms replaced by: Ring J 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-dii 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 from fluorine, chlorine, 1 carbon 12 alkyls, alkoxys having 1 to 12 carbons, or alkyls having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine; Z ⁴ and Z ⁵ may be a single bond or carbon alkylene from C 1 10, in the alkylene, at least one of _-CH 2 -, -O -, - CO -, - COO-, or May be replaced by OCO-, at least one _-CH 2 -CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, or -C (CH ₃ ) ═C (CH ₃ ) — may be replaced, in which at least one hydrogen may be replaced by fluorine or chlorine; P ⁴ , P ⁵ , and P ⁶ are polymerized Sp ⁴ , Sp ⁵ , and Sp ⁶ are a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, —COO—, -OCO-, or it may be replaced by -OCOO-, at least one _-CH 2 -CH ₂ - may be replaced by -CH = CH- or -C≡C-, and in the groups, At least One hydrogen may be replaced by fluorine or chlorine; h is 0, 1, or 2; i, j, and k are 0, 1, 2, 3, or 4; and i , J, and k are 1 or more.
The formula (4), wherein P ⁴ , P ⁵ , and P ⁶ are groups selected from a polymerizable group represented by the formula (P-6) to the formula (P-10). Liquid crystal composition.

In Formula (P-6) to Formula (P-10), M ⁴ , M ⁵ , and M ⁶ are hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced with fluorine or chlorine And alkyl having 1 to 5 carbon atoms. 12. The liquid crystal composition according to claim 1, comprising at least one polymerizable compound selected from compounds represented by formulas (4-1) to (4-29).

In the formula (4-29) from equation ^(4-1), P 7, ^{P 8,} and ^{P 9} are formulas polymerizable selected from the group represented by the formula (P-8) from (P-6) A group;

In formulas (P-6) to (P-8), M ⁴ , M ⁵ , and M ⁶ are hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced by fluorine or chlorine Sp ⁴ , Sp ⁵ , and Sp ⁶ are a single bond or alkylene having 1 to 10 carbons, in which at least one —CH ₂ — is —O —, —COO—, —OCO—, or —OCOO— may be substituted, and at least one —CH ₂ —CH ₂ — may be substituted with —CH═CH— or —C≡C—. In these groups, at least one hydrogen may be replaced by fluorine or chlorine.   The liquid crystal composition according to any one of claims 10 to 12, wherein a ratio of the second additive is in a range of 0.03% by mass to 10% by mass.   The liquid crystal display element containing the liquid-crystal composition of any one of Claim 1 to 13.   The liquid crystal display element according to claim 14, wherein an operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and a driving method of the liquid crystal display element is an active matrix method.   14. A polymer-supported alignment type liquid crystal display element comprising the liquid crystal composition according to any one of claims 1 to 13, or a polymerizable compound in the liquid crystal composition being polymerized.   Use of the liquid crystal composition according to any one of claims 1 to 13 in a liquid crystal display device.   Use of the liquid crystal composition according to any one of claims 1 to 13 in a polymer supported alignment type liquid crystal display element.