JP6922921B2 - Liquid crystal composition and liquid crystal display element - Google Patents

Description

The present invention relates to a liquid crystal composition, a liquid crystal display element containing the composition, and the like. In particular, a compound having a polymerizable group and a polar group (or a polymer thereof) is contained in the branched structure at the molecular terminal, and the vertical orientation of the liquid crystal molecule can be achieved by the action of this compound, and the dielectric constant anisotropy is negative. The present invention relates to a liquid crystal composition and a liquid crystal display element.

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

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

The optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large optical anisotropy or a small optical anisotropy, that is, an appropriate optical anisotropy is required. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate value of the product depends on the type of operation mode. This value ranges from about 0.30 μm to about 0.40 μm for VA mode devices and from about 0.20 μm to about 0.30 μm for IPS or FFS mode devices. In these cases, a composition having a large optical anisotropy is preferable for a device having a small cell gap. The large permittivity anisotropy in the composition contributes to the low threshold voltage, low power consumption and large contrast ratio in the device. Therefore, a large dielectric anisotropy is preferred. A large resistivity in the composition contributes to a large voltage retention and a large contrast ratio in the device. Therefore, a composition having a large resistivity at an initial stage not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable. After long-term use, a composition having a large resistivity not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable. The stability of the composition against UV and heat is related to the life of the device. When this stability is high, the life of the device is long. Such characteristics are preferable for AM elements used in liquid crystal projectors, liquid crystal televisions, and the like.

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

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

In the AM device having the TN mode, a composition having a positive dielectric anisotropy is used. In the AM device having the VA mode, a composition having a negative dielectric anisotropy is used. In an AM device having an IPS mode or an FFS mode, a composition having positive or negative dielectric anisotropy is used. In the polymer support orientation type AM device, a composition having positive or negative dielectric anisotropy is used. Examples of liquid crystal compositions using a liquid crystal compound having a negative dielectric anisotropy and a polymerizable compound having a polar group are disclosed in Patent Documents 1 and 2 below. Patent Document 1 discloses a polymerizable self-oriented additive having a polymerizable group in the lateral direction of the compound and a polar group at the end. Patent Document 2 discloses a polymerizable self-oriented additive having a polymerizable group and a polar group at both ends of the compound, respectively. The compounds described in Patent Documents 1 and 2 are different from the compounds used in the present invention.

Japanese Unexamined Patent Publication No. 2015-168826 International Publication No. 2016/015803 Pamphlet

The problem to be solved by the present invention is to control the orientation of the liquid crystal molecules of the liquid crystal display element having no alignment film by using a compound (or a polymer thereof) having a polymerizable group and a polar group in the branched structure at the molecular terminal. It is also to provide a liquid crystal composition in which the polymerizable polar compound exhibits good compatibility.

式（１−１）において、
Ｒ^１は炭素数１から１５のアルキルであり、このＲ^１において、少なくとも１つの−ＣＨ_２−は、−Ｏ−または−Ｓ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、少なくとも１つの水素は、ハロゲンで置き換えられてもよく；
環Ａ^１および環Ａ^２は独立して、１，４−シクロへキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、ナフタレン−２，６−ジイル、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、フルオレン−２，７−ジイル、フェナントレン−２，７−ジイル、アントラセン−２，６−ジイル、ペルヒドロシクロペンタ［ａ］フェナントレン−３，１７−ジイル、または２，３，４，７，８，９，１０，１１，１２，１３，１４，１５，１６，１７−テトラデカヒドロシクロペンタ［ａ］フェナントレン−３，１７−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２から１２のアルケニル、炭素数１から１１のアルコキシ、または炭素数２から１１のアルケニルオキシで置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
ａは、０、１、２、３、または４であり；
Ｚ^１は単結合または炭素数１から６のアルキレンであり、このＺ^１において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、Ｚ^１において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
Ｓｐ^１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Ｓｐ^１において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、Ｓｐ^１において、少なくとも１つの水素は、ハロゲンで置き換えられてもよく、Ｓｐ^１において、少なくとも１つの水素は、式（１ａ）で表される基から選択された基で置き換えられていて；

式（１ａ）において、
Ｓｐ^１２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Ｓｐ^１２において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、Ｓｐ^１２において、少なくとも１つの水素は、ハロゲンで置き換えられてもよく；
Ｍ^１１およびＭ^１２は独立して、水素、ハロゲン、炭素数１から５のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から５のアルキルであり：
Ｒ^１２は炭素数１から１５のアルキルであり、このＲ^１２において、少なくとも１つの−ＣＨ_２−は、−Ｏ−または−Ｓ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、少なくとも１つの水素はハロゲンで置き換えられてもよく：
式（１−１）において、
Ｐ^１１は、式（１ｅ）および式（１ｆ）で表される基から選択された基であり；

式（１ｅ）および（１ｆ）において、
Ｓｐ^１３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Ｓｐ^１３において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＮＨ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、Ｓｐ^１３において、少なくとも１つの水素はハロゲンで置き換えられてもよく；
Ｍ^１３およびＭ^１４は独立して、水素、ハロゲン、炭素数１から５のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から５のアルキルであり；
Ｒ^１３は、式（１ｇ）、式（１ｈ）、および式（１ｉ）で表される基から選択された基であり；

式（１ｇ）、式（１ｈ）、および式（１ｉ）において、
Ｓｐ^１４およびＳｐ^１５は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＮＨ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、少なくとも１つの水素は、ハロゲンで置き換えられてもよく；
式（１ｇ）および式（１ｉ）において、Ｓ^１は、＞ＣＨ−または＞Ｎ−であり、Ｓ^２は、＞Ｃ＜または＞Ｓｉ＜であり；
Ｘ^１は、−ＯＨ、−ＮＨ_２、−ＯＲ^１５、−Ｎ（Ｒ^１５）_２、−ＣＯＯＨ、−ＳＨ、−Ｂ（ＯＨ）_２、または−Ｓｉ（Ｒ^１５）_３であり；
−ＯＲ^１５、−Ｎ（Ｒ^１５）_２、および−Ｓｉ（Ｒ^１５）_３において、
Ｒ^１５は水素または炭素数１から１０のアルキルであり、このＲ^１５において、少なくとも１つの−ＣＨ_２−は、−Ｏ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−で置き換えられてもよく、Ｒ^１５において、少なくとも１つの水素は、ハロゲンで置き換えられてもよい。The present invention is a liquid crystal composition having a negative dielectric anisotropy, containing a compound having a polymerizable group and a polar group in a branched structure at the molecular terminal, in which the liquid crystal molecules of a liquid crystal display element having no alignment film are oriented. Control using.
A liquid crystal composition containing at least one polar compound selected from the group of compounds represented by the formula (1-1) as a first additive and having a negative dielectric anisotropy.

In equation (1-1)
R ¹ is alkyl of from 1 to 15 carbon atoms, in the ^{R 1,} at least one of -CH ₂ -, -O- or -S- in may be replaced, at least one _-CH 2 CH ₂ - May be replaced with -CH = CH- or -C≡C-, and at least one hydrogen may be replaced with a halogen;
Ring ^{A 1} and ring ^{A 2} are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6 Diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine- 2,5-Diyl, Fluorene-2,7-Diyl, Phenanthrene-2,7-Diyl, Anthracene-2,6-Diyl, Perhydrocyclopenta [a] Phenanthrene-3,17-Diyl, or 2,3 4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl, at least one in these rings. Hydrogen may be replaced with fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, alkoxy with 1 to 11 carbon atoms, or alkenyloxy with 2 to 11 carbon atoms, these groups. In, at least one hydrogen may be replaced with fluorine or chlorine;
a is 0, 1, 2, 3, or 4;
Z ¹ is 6 alkylene from a single bond or 1 carbon atoms, in the ^{Z 1,} at least one of _-CH 2 -, -O -, - CO -, - COO -, - OCO-, or -OCOO- At least one -CH ₂ CH _2- may be replaced with -CH = CH- or -C≡C-, and in Z ¹ , at least one hydrogen is fluorine or chlorine. May be replaced;
Sp ¹ is alkylene of 10 a single bond or 1 carbon atoms, in the Sp ^1, at least one of _-CH 2 -, -O -, - CO -, - COO -, - OCO-, or -OCOO- At least one -CH ₂ CH _2- may be replaced with -CH = CH- or -C≡C- ^{, and at Sp 1} at least one hydrogen is replaced with a halogen. In Sp ¹ , at least one hydrogen may be replaced with a group selected from the groups represented by the formula (1a);

In formula (1a)
Sp ¹² is alkylene of 10 a single bond or 1 carbon atoms, in the ^{Sp 12,} at least one of _-CH 2 -, -O -, - CO -, - COO -, - OCO-, or -OCOO- may be replaced by at least one _-CH 2 CH ₂ - may be replaced by -CH = CH- or -C≡C-, in the ^{Sp 12,} at least one hydrogen is replaced by halogen May;
M ¹¹ and M ¹² are independently hydrogen, halogen, alkyl having 1 to 5 carbon atoms, or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced with halogen:
R ¹² is alkyl of from 1 to 15 carbon atoms, in the ^{R 12,} at least one of -CH ₂ -, -O- or -S- in may be replaced, at least one _-CH 2 CH ₂ - May be replaced with -CH = CH- or -C≡C-, and at least one hydrogen may be replaced with a halogen:
In equation (1-1)
P ¹¹ is a group selected from the group represented by the formula (1e) and formula (1f);

In equations (1e) and (1f)
Sp ¹³ is alkylene of 10 a single bond or 1 carbon atoms, in the ^{Sp 13,} at least one of _-CH 2 -, -O -, - NH -, - CO -, - 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-, in the ^{Sp 13,} at least one hydrogen halide May be replaced by;
M ¹³ and M ¹⁴ are independently hydrogen, halogen, alkyl having 1 to 5 carbon atoms, or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced by halogen;
R ¹³ is a group selected from the groups represented by the formula (1g), the formula (1h), and the formula (1i);

In formula (1g), formula (1h), and formula (1i),
Sp ¹⁴ and Sp ¹⁵ are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -NH-, -CO-, -COO. It may be replaced by −, −OCO−, or −OCOO−, and at least one −CH ₂ CH ₂₋ may be replaced by −CH = CH− or −C≡C−, and at least one hydrogen. May be replaced with halogen;
In formulas (1g) and (1i), S ¹ is> CH- or> N- and S ² is> C <or> Si <;
X ¹ is -OH, -NH ₂ , -OR ¹⁵ , -N (R ¹⁵ ) ₂ , -COOH, -SH, -B (OH) ₂ , or -Si (R ¹⁵ ) ₃ ;
At −OR ¹⁵ , −N (R ¹⁵ ) ₂ , and −Si (R ¹⁵ ) ₃ ,
R ¹⁵ is alkyl of 1 to 10 carbon hydrogen or carbon, in the ^{R 15,} at least one -CH ₂ - may be replaced by -O-, at least one _-CH 2 CH ₂ - is it may be replaced by -CH = ^CH-, in ^{R 15,} at least one hydrogen may be replaced by halogen.

By using the liquid crystal composition containing the polymerizable polar compound having a polar group of the present invention, the step of forming the alignment film becomes unnecessary, so that a liquid crystal display element with reduced manufacturing cost can be obtained.
Further, a liquid crystal composition having a negative dielectric anisotropy having good compatibility with the polymerizable polar compound can be obtained.

The usage of terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "composition" and "element", respectively. "Liquid crystal display element" is a general term for a liquid crystal display panel and a liquid crystal display module. The "liquid crystal compound" is a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and a compound having no liquid crystal phase, but is composed for the purpose of adjusting characteristics such as temperature range, viscosity, and dielectric constant anisotropy of the nematic phase. It is a general term for compounds that are mixed with substances. This compound has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod-like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are added to the liquid crystal composition as needed. NS. The liquid crystal compounds and additives are mixed in such a procedure. The ratio (content) of the liquid crystal compound is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive even when the additive is added. The ratio (addition amount) of the additive is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive. Parts per million (ppm) by weight may also be used. The proportions of polymerization initiators and polymerization inhibitors are exceptionally expressed based on the weight of the polymerizable compound.

The "upper limit temperature of the nematic phase" may be abbreviated as the "upper limit temperature". The "lower limit temperature of the nematic phase" may be abbreviated as the "lower limit temperature". "Large resistivity" means that the composition has a large resistivity not only at room temperature but also at a temperature close to the upper limit temperature at the initial stage, and after a long period of use, it has a large resistivity not only at room temperature but also at a temperature close to the upper limit temperature. Means to have. "Large voltage retention" means that the element has a large voltage retention not only at room temperature but also at a temperature close to the upper limit temperature at the initial stage, and after long-term use, it has a large voltage not only at room temperature but also at a temperature close to the upper limit temperature. It means having a retention rate. The characteristics of the composition or device may be examined before and after the aging test (including the accelerated deterioration test). The expression "increase the dielectric anisotropy" means that when the composition has a positive dielectric anisotropy, its value increases positively, and the composition has a negative dielectric anisotropy. When it is a thing, it means that its value increases negatively.

The compound represented by the formula (2) may be abbreviated as "compound (2)". At least one compound selected from the group of compounds represented by the formula (2) may be abbreviated as "Compound (2)". "Compound (2)" means one compound represented by the formula (2), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas. The expression "at least one'A'" means that the number of'A'is arbitrary. The expression "at least one'A'may be replaced by'B'" is that when the number of'A's is 1, the position of the'A'is arbitrary and the number of'A's is 2. When there is more than one, their positions can be selected without limitation. This rule also applies to the expression "at least one'A'has been replaced by a'B'". Further, in the present specification, the compound represented by the formula (1-1) and the compounds represented by the formulas (1-2) to (1-60) which are subordinate formulas thereof are collectively referred to as the compound (1). ).

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

Symbols such as A, C, D, and E enclosed in hexagons correspond to rings such as ring A, ring C, ring D, and ring E, respectively, and represent rings such as a six-membered ring and a condensed ring. The diagonal lines across this hexagon indicate that any hydrogen on the ring may be replaced by a group such as ^{-Sp 3-} P ^1. Subscripts such as'j'indicate the number of replaced groups. When the subscript'j'is 0, there is no such replacement. When the subscript'j'is 2 or more, there are a plurality of -Sp ³ -P ^{1 on the ring J.} Plural groups -Sp ³ -P ¹ represents may be the same or different.

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

Expressions such as "at least one -CH _2- may be replaced by -O-" are used herein. In this case, −CH ₂ −CH ₂ −CH ₂ − may be converted to −O—CH ₂ −O− by replacing the non-adjacent −CH _{2− with −O−.} However, the adjacent −CH ₂₋ is not replaced by −O−. This is because -O-O-CH _2- (peroxide) is produced by this replacement. That is, this expression includes both "one -CH _2- may be replaced by -O-" and "at least two non-adjacent -CH _2- may be replaced by -O-". means. This rule applies not only to the replacement with -O-, but also to the replacement with divalent groups such as -CH = CH- and -COO-. In the formula (1), R ¹ is an alkyl having 1 to 25 carbon atoms. The carbon number of this alkyl can be increased by this type of replacement. In such a case, the maximum number of carbon atoms is 30. This rule ^{applies not only to monovalent groups such as R 1} but also to divalent groups such as alkylene.

The alkyl of the liquid crystal compound is linear or branched and does not contain cyclic alkyl. Linear alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. As for the configuration of 1,4-cyclohexylene, trans is generally preferable to cis. Halogen means fluorine, chlorine, bromine and iodine. Preferred halogens are fluorine or chlorine. A more preferred halogen is fluorine.

The present invention includes the following items.

式（１−１）において、
Ｒ^１は炭素数１から１５のアルキルであり、このＲ^１において、少なくとも１つの−ＣＨ_２−は、−Ｏ−または−Ｓ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、少なくとも１つの水素は、ハロゲンで置き換えられてもよく；
環Ａ^１および環Ａ^２は独立して、１，４−シクロへキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、ナフタレン−２，６−ジイル、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、フルオレン−２，７−ジイル、フェナントレン−２，７−ジイル、アントラセン−２，６−ジイル、ペルヒドロシクロペンタ［ａ］フェナントレン−３，１７−ジイル、または２，３，４，７，８，９，１０，１１，１２，１３，１４，１５，１６，１７−テトラデカヒドロシクロペンタ［ａ］フェナントレン−３，１７−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２から１２のアルケニル、炭素数１から１１のアルコキシ、または炭素数２から１１のアルケニルオキシで置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
ａは、０、１、２、３、または４であり；
Ｚ^１は単結合または炭素数１から６のアルキレンであり、このＺ^１において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、Ｚ^１において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
Ｓｐ^１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Ｓｐ^１において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、Ｓｐ^１において、少なくとも１つの水素は、ハロゲンで置き換えられてもよく、Ｓｐ^１において、少なくとも１つの水素は、式（１ａ）で表される基から選択された基で置き換えられていて；

式（１ａ）において、
Ｓｐ^１２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Ｓｐ^１２において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、Ｓｐ^１２において、少なくとも１つの水素は、ハロゲンで置き換えられてもよく；
Ｍ^１１およびＭ^１２は独立して、水素、ハロゲン、炭素数１から５のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から５のアルキルであり：
Ｒ^１２は炭素数１から１５のアルキルであり、このＲ^１２において、少なくとも１つの−ＣＨ_２−は、−Ｏ−または−Ｓ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、少なくとも１つの水素はハロゲンで置き換えられてもよく：
式（１−１）において、
Ｐ^１１は、式（１ｅ）および式（１ｆ）で表される基から選択された基であり；

式（１ｅ）および（１ｆ）において、
Ｓｐ^１３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Ｓｐ^１３において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＮＨ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、Ｓｐ^１３において、少なくとも１つの水素はハロゲンで置き換えられてもよく；
Ｍ^１３およびＭ^１４は独立して、水素、ハロゲン、炭素数１から５のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から５のアルキルであり；
Ｒ^１３は、式（１ｇ）、式（１ｈ）、および式（１ｉ）で表される基から選択された基であり；

式（１ｇ）、式（１ｈ）、および式（１ｉ）において、
Ｓｐ^１４およびＳｐ^１５は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＮＨ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、少なくとも１つの水素は、ハロゲンで置き換えられてもよく；
式（１ｇ）および式（１ｉ）において、Ｓ^１は、＞ＣＨ−または＞Ｎ−であり、Ｓ^２は、＞Ｃ＜または＞Ｓｉ＜であり；
Ｘ^１は、−ＯＨ、−ＮＨ_２、−ＯＲ^１５、−Ｎ（Ｒ^１５）_２、−ＣＯＯＨ、−ＳＨ、−Ｂ（ＯＨ）_２、または−Ｓｉ（Ｒ^１５）_３であり；
−ＯＲ^１５、−Ｎ（Ｒ^１５）_２、および−Ｓｉ（Ｒ^１５）_３において、
Ｒ^１５は水素または炭素数１から１０のアルキルであり、このＲ^１５において、少なくとも１つの−ＣＨ_２−は、−Ｏ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−で置き換えられてもよく、Ｒ^１５において、少なくとも１つの水素は、ハロゲンで置き換えられてもよい。Item 1. A liquid crystal composition containing at least one polar compound selected from the group of compounds represented by the formula (1-1) as a first additive and having a negative dielectric anisotropy.

In equation (1-1)
R ¹ is alkyl of from 1 to 15 carbon atoms, in the ^{R 1,} at least one of -CH ₂ -, -O- or -S- in may be replaced, at least one _-CH 2 CH ₂ - May be replaced with -CH = CH- or -C≡C-, and at least one hydrogen may be replaced with a halogen;
Ring ^{A 1} and ring ^{A 2} are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6 Diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine- 2,5-Diyl, Fluorene-2,7-Diyl, Phenanthrene-2,7-Diyl, Anthracene-2,6-Diyl, Perhydrocyclopenta [a] Phenanthrene-3,17-Diyl, or 2,3 4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl, at least one in these rings. Hydrogen may be replaced with fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, alkoxy with 1 to 11 carbon atoms, or alkenyloxy with 2 to 11 carbon atoms, these groups. In, at least one hydrogen may be replaced with fluorine or chlorine;
a is 0, 1, 2, 3, or 4;
Z ¹ is 6 alkylene from a single bond or 1 carbon atoms, in the ^{Z 1,} at least one of _-CH 2 -, -O -, - CO -, - COO -, - OCO-, or -OCOO- At least one -CH ₂ CH _2- may be replaced with -CH = CH- or -C≡C-, and in Z ¹ , at least one hydrogen is fluorine or chlorine. May be replaced;
Sp ¹ is alkylene of 10 a single bond or 1 carbon atoms, in the Sp ^1, at least one of _-CH 2 -, -O -, - CO -, - COO -, - OCO-, or -OCOO- At least one -CH ₂ CH _2- may be replaced with -CH = CH- or -C≡C- ^{, and at Sp 1} at least one hydrogen is replaced with a halogen. In Sp ¹ , at least one hydrogen may be replaced with a group selected from the groups represented by the formula (1a);

In formula (1a)
Sp ¹² is alkylene of 10 a single bond or 1 carbon atoms, in the ^{Sp 12,} at least one of _-CH 2 -, -O -, - CO -, - COO -, - OCO-, or -OCOO- may be replaced by at least one _-CH 2 CH ₂ - may be replaced by -CH = CH- or -C≡C-, in the ^{Sp 12,} at least one hydrogen is replaced by halogen May;
M ¹¹ and M ¹² are independently hydrogen, halogen, alkyl having 1 to 5 carbon atoms, or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced with halogen:
R ¹² is alkyl of from 1 to 15 carbon atoms, in the ^{R 12,} at least one of -CH ₂ -, -O- or -S- in may be replaced, at least one _-CH 2 CH ₂ - May be replaced with -CH = CH- or -C≡C-, and at least one hydrogen may be replaced with a halogen:
In equation (1-1)
P ¹¹ is a group selected from the group represented by the formula (1e) and formula (1f);

In equations (1e) and (1f)
Sp ¹³ is alkylene of 10 a single bond or 1 carbon atoms, in the ^{Sp 13,} at least one of _-CH 2 -, -O -, - NH -, - CO -, - 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-, in the ^{Sp 13,} at least one hydrogen halide May be replaced by;
M ¹³ and M ¹⁴ are independently hydrogen, halogen, alkyl having 1 to 5 carbon atoms, or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced by halogen;
R ¹³ is a group selected from the groups represented by the formula (1g), the formula (1h), and the formula (1i);

In formula (1g), formula (1h), and formula (1i),
Sp ¹⁴ and Sp ¹⁵ are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -NH-, -CO-, -COO. It may be replaced by −, −OCO−, or −OCOO−, and at least one −CH ₂ CH ₂₋ may be replaced by −CH = CH− or −C≡C−, and at least one hydrogen. May be replaced with halogen;
In formulas (1g) and (1i), S ¹ is> CH- or> N- and S ² is> C <or> Si <;
X ¹ is -OH, -NH ₂ , -OR ¹⁵ , -N (R ¹⁵ ) ₂ , -COOH, -SH, -B (OH) ₂ , or -Si (R ¹⁵ ) ₃ ;
At −OR ¹⁵ , −N (R ¹⁵ ) ₂ , and −Si (R ¹⁵ ) ₃ ,
R ¹⁵ is alkyl of 1 to 10 carbon hydrogen or carbon, in the ^{R 15,} at least one -CH ₂ - may be replaced by -O-, at least one _-CH 2 CH ₂ - is it may be replaced by -CH = ^CH-, in ^{R 15,} at least one hydrogen may be replaced by halogen.

式（１−２）および式（１−３）において、
Ｒ^１は炭素数１から１２のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；
環Ａ^１および環Ａ^２は独立して、１，４−シクロへキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、ナフタレン−２，６−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、フルオレン−２，７−ジイル、フェナントレン−２，７−ジイル、ペルヒドロシクロペンタ［ａ］フェナントレン−３，１７−ジイル、または２，３，４，７，８，９，１０，１１，１２，１３，１４，１５，１６，１７−テトラデカヒドロシクロペンタ［ａ］フェナントレン−３，１７−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、炭素数１から８のアルキル、炭素数２から８のアルケニル、炭素数１から７のアルコキシ、または炭素数２から７のアルケニルオキシで置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；
ａは、０、１、２、３、または４であり；
Ｚ ^１ は単結合または炭素数１から６のアルキレンであり、このＺ ^１ において、少なくとも１つの−ＣＨ _２ −は、−Ｏ−、−ＣＯ−、−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、Ｚ ^１ 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；
ｌは、０、１、２、３、４、５、または６であり、このアルキレンの少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；
Ｓｐ^１２は単結合または炭素数１から５のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく；
Ｍ^１１およびＭ^１２は独立して、水素、フッ素、メチル、エチル、またはトリフルオロメチルであり；
Ｒ^１２は水素または炭素数１から５のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−または−Ｓ−で置き換えられてもよく、少なくとも１つの−（ＣＨ_２）_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、フッ素で置き換えられてもよく：
Ｓｐ^１３は、単結合または炭素数１から５のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、または−ＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；
Ｍ^１３およびＭ^１４は独立して、水素、フッ素、メチル、エチル、またはトリフルオロメチルであり；
Ｓｐ^１４は、単結合または炭素数１から５のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、または−ＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；
Ｘ^１は、−ＯＨまたは−Ｎ（Ｒ^１５）_２であり；
−Ｎ（Ｒ^１５）_２において、
Ｒ^１５は水素または炭素数１から５のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよい。


Item 2. Item 2. The liquid crystal composition according to Item 1, wherein the first additive is at least one polymerizable compound selected from the group of compounds represented by the formulas (1-2) to (1-3).

In equations (1-2) and (1-3),
R ¹ is an alkyl having 1 to 12 carbon atoms, in which at least one −CH ₂ − may be replaced by −O −, and at least one −CH ₂ CH ₂ − is −CH =. It may be replaced by CH- or -C≡C-, and in these groups at least one hydrogen may be replaced by fluorine;
Ring ^{A 1} and ring ^{A 2} are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl , 1,3-dioxane-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, perhydrocyclopenta [a] phenanthrene-3,17-diyl, or 2,3,4 , 7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl, at least one hydrogen in these rings. May be replaced with fluorine, alkyl with 1 to 8 carbon atoms, alkenyl with 2 to 8 carbon atoms, alkoxy with 1 to 7 carbon atoms, or alkenyloxy with 2 to 7 carbon atoms, at least in these groups. One hydrogen may be replaced by fluorine;
a is 0, 1, 2, 3, or 4;
Z ¹ is 6 alkylene from a single bond or 1 carbon atoms, in the ^{Z 1,} at least one of _-CH 2 -, -O -, - CO -, - COO -, - OCO-, or -OCOO- At least one -CH ₂ CH _2- may be replaced with -CH = CH- or -C≡C-, and in Z ¹ , at least one hydrogen is fluorine or chlorine. May be replaced;
l is 0, 1, 2, 3, 4, 5, or 6, and at least one −CH ₂ − of this alkylene is −O−, −CO−, −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 these groups, at least one hydrogen is fluorine. May be replaced by;
Sp ¹² is a single bond or an alkylene with 1 to 5 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, -OCO-, or -OCOO-. It may be 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. Well;
M ¹¹ and M ¹² are independently hydrogen, fluorine, methyl, ethyl, or trifluoromethyl;
R ¹² is hydrogen or an alkyl having 1 to 5 carbon atoms, in which at least one −CH ₂ − may be replaced by −O− or −S−, and at least one − (CH ₂ ). ₂ − may be replaced by −CH = CH − or −C≡C−, and in these groups at least one hydrogen may be replaced by fluorine:
Sp ¹³ is a single bond or an alkylene having 1 to 5 carbon atoms, in which at least one -CH _2- may be replaced with -O-, -CO-, or -COO-, at least. One -CH ₂ CH _2- may be replaced by -CH = CH- or -C≡C-, and in these groups at least one hydrogen may be replaced by fluorine;
M ¹³ and M ¹⁴ are independently hydrogen, fluorine, methyl, ethyl, or trifluoromethyl;
Sp ¹⁴ is a single bond or an alkylene having 1 to 5 carbon atoms, in which at least one -CH ₂ − may be replaced with -O-, -CO-, or -COO-, at least. One -CH ₂ CH _2- may be replaced by -CH = CH- or -C≡C-, and in these groups at least one hydrogen may be replaced by fluorine;
X ¹ is -OH or -N (R ¹⁵ ) ₂ ;
At −N (R ¹⁵ ) ₂ ,
R ¹⁵ is hydrogen or an alkyl having 1 to 5 carbon atoms, in which at least one −CH ₂ − may be replaced by −O − and at least one −CH ₂ CH ₂ − is −. It may be replaced by CH = CH-, and in these groups, at least one hydrogen may be replaced by fluorine.

式（１−４）から式（１−６０）において、
Ｒ^１は炭素数１から１０のアルキルであり；
Ｚ^１、Ｚ^１２、およびＺ^１３は独立して、単結合、−ＣＨ_２ＣＨ_２−、または−（ＣＨ_２）_４−であり；
Ｓｐ^１２、Ｓｐ^１３、およびＳｐ^１４は独立して、単結合または炭素数１から５のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−で置き換えられてもよく；
Ｌ^１、Ｌ^２、Ｌ^３、Ｌ^４、Ｌ^５、Ｌ^６、Ｌ^７、Ｌ^８、Ｌ^９、Ｌ^１０、Ｌ^１１、およびＬ^１２は独立して、水素、フッ素、メチル、またはエチルであり；
ｌは、０、１、２、３、４、５、または６である。Item 3. Item 2. The liquid crystal composition according to Item 1, wherein the first additive is at least one polymerizable compound selected from the group of compounds represented by the formulas (1-4) to (1-60).

In equations (1-4) to (1-60),
R ¹ is an alkyl with 1 to 10 carbon atoms;
Z ^{1, Z 12,} and ^{Z 13} are independently a single bond, _-CH 2 CH ₂ -, or - _{(CH 2) 4} - a and;
Sp ¹² , Sp ¹³ , and Sp ¹⁴ are independently single-bonded or 1 to 5 carbon alkylenes, in which at least one -CH ₂ − may be replaced by -O-;
L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ , L ⁸ , L ⁹ , L ¹⁰ , L ¹¹ , and L ¹² are independently hydrogen, fluorine, methyl, or ethyl. can be;
l is 0, 1, 2, 3, 4, 5, or 6.

Item 4. Item 2. The liquid crystal composition according to any one of Items 1 to 3, wherein the ratio of the first additive is 10% by weight or less based on the weight of the liquid crystal composition.

式（２）において、Ｒ^３およびＲ^４は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、または炭素数２から１２のアルケニルオキシであり；環Ｃおよび環Ｅは独立して、１，４−シクロへキシレン、１，４−シクロへキセニレン、１，４−フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレン、またはテトラヒドロピラン−２，５−ジイルであり；環Ｄは、２，３−ジフルオロ−１，４−フェニレン、２−クロロ−３−フルオロ−１，４−フェニレン、２，３−ジフルオロ−５−メチル−１，４−フェニレン、３，４，５−トリフルオロナフタレン−２，６−ジイル、または７，８−ジフルオロクロマン−２，６−ジイルであり；Ｚ^２およびＺ^３は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、または−ＯＣＯ−であり；ｂは、１、２、または３であり、ｃは０または１であり、そしてｂとｃとの和は３以下である。Item 5. Item 6. The liquid crystal composition according to any one of Items 1 to 4, which contains at least one compound selected from the group of compounds represented by the formula (2) as a first component.

In formula (2), R ³ and R ⁴ are independently composed of an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, or an alkenyloxy having 2 to 12 carbon atoms. Yes; Rings C and E are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4- at least one hydrogen replaced with fluorine or chlorine. Phenylene, or tetrahydropyran-2,5-diyl; ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro- 5-Methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl; Z ² and Z ³ are independent. Te single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or a is -OCO-; b is 1, 2, or 3,, c is 0 or It is 1, and the sum of b and c is 3 or less.

式（２−１）から式（２−２２）において、Ｒ^３およびＲ^４は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、または炭素数２から１２のアルケニルオキシである。Item 6. Item 2. The liquid crystal composition according to any one of Items 1 to 5, which contains at least one compound selected from the group of compounds represented by the formulas (2-1) to (2-22) as the first component. thing.

In formulas (2-1) to (2-22), R ³ and R ⁴ are independently alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or It is an alkoxyoxy having 2 to 12 carbon atoms.

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

式（３）において、Ｒ^５およびＲ^６は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルであり；環Ｆおよび環Ｇは独立して、１，４−シクロへキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、または２，５−ジフルオロ−１，４−フェニレンであり；Ｚ^４は、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、または−ＯＣＯ−であり；ｄは、１、２、または３である。Item 8. Item 6. The liquid crystal composition according to any one of Items 1 to 7, which contains at least one compound selected from the group of compounds represented by the formula (3) as the second component.

In formula (3), R ⁵ and R ⁶ are independently replaced by an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, and at least one hydrogen being replaced with fluorine or chlorine. Alkyl with 1 to 12 carbon atoms, or alkenyl with 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; ring F and ring G are independently 1,4-cyclohexylene. , 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ⁴ is a single bond, -CH ₂ CH _{2- , -CH 2} O -, -OCH _2- , -COO-, or -OCO-; d is 1, 2, or 3.

式（３−１）から式（３−１３）において、Ｒ^５およびＲ^６は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルである。Item 9. Item 2. The liquid crystal composition according to any one of Items 1 to 8, which contains at least one compound selected from the group of compounds represented by the formulas (3-1) to (3-13) as the second component. thing.

In formulas (3-1) to (3-13), R ⁵ and R ⁶ are independently alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or at least. An alkyl having 1 to 12 carbon atoms in which one hydrogen has been replaced with fluorine or chlorine, or an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine.

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

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

In formula (4), ring J and ring P are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-. It is 2-yl or pyridine-2-yl, and in these rings at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least one hydrogen. It may be replaced with an alkyl having 1 to 12 carbon atoms replaced with fluorine or chlorine; ring K is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1, 2-Diyl, Naphthalene-1,3-Diyl, Naphthalene-1,4-Diyl, Naphthalene-1,5-Diyl, Naphthalene-1,6-Diyl, Naphthalene-1,7-Diyl, Naphthalene-1,8- Diyl, Naphthalene-2,3-Diyl, Naphthalene-2,6-Diyl, Naphthalene-2,7-Diyl, Tetrahydropyran-2,5-Diyl, 1,3-Dioxane-2,5-Diyl, Pyrimidine-2 , 5-Diyl, or pyridine-2,5-Diyl, in which at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least 1 One hydrogen may be replaced with an alkyl having 1 to 12 carbon atoms replaced with fluorine or chlorine; Z ⁵ and Z ⁶ are independently single-bonded or alkylenes having 1 to 10 carbon atoms, and this Z ⁵ And in Z ⁶ , at least one −CH ₂ − may be replaced by −O −, −CO−, −COO−, or −OCO−, and at least one −CH ₂ CH ₂₋ It may be replaced by CH = CH −, −C (CH ₃ ) = CH −, −CH = C (CH ₃ ) −, or −C (CH ₃ ) = C (CH ₃ ) −, and at least one hydrogen. ^{May be} replaced with fluorine or chlorine; P ¹ , P ² , and P ³ are polymerizable groups; Sp ³ , Sp ⁴ , and Sp 5 are independent from a single bond or 1 carbon. It is an alkylene of 10, and in Sp ³ , Sp ⁴ , and Sp ⁵ , at least one -CH _2- may be replaced with -O-, -COO-, -OCO-, or -OCOO-. And at least one -CH ₂ CH ₂ − may be replaced by −CH = CH − or −C≡C−, and at least one hydrogen may be replaced by fluorine or chlorine; q is 0, 1, or 2; j. , K, and p are independently 0, 1, 2, 3, or 4, and the sum of j, k, and p is greater than or equal to 1.

式（Ｐ−１）から式（Ｐ−５）において、Ｍ^１、Ｍ^２、およびＭ^３は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルである。Item 12. In the formula ^(4), which is P 1, the polymerizable ^{group P 2,} and ^{P 3} are independently selected from the formula (P-1) from the group of radicals represented by the formula (P-5), section 11. The liquid crystal composition according to 11.

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

式（４−１）から式（４−２９）において、Ｐ^１、Ｐ^２、およびＰ^３は独立して、式（Ｐ−１）から式（Ｐ−３）で表される基の群から選択された重合性基であり、ここでＭ^１、Ｍ^２、およびＭ^３は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルであり；

Ｓｐ^３、Ｓｐ^４、およびＳｐ^５は独立して、単結合または炭素数１から１０のアルキレンであり、このＳｐ^３、Ｓｐ^４、およびＳｐ^５において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、そして少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、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 13. Item 6. The item according to any one of Items 1 to 12, wherein the second additive is at least one polymerizable compound selected from the group of compounds represented by the formulas (4-1) to (4-29). Liquid crystal composition.

In formulas (4-1) to (4-29), P ¹ , P ² , and P ³ are independently from the group of groups represented by formulas (P-1) to (P-3). The polymerizable groups of choice, where M ¹ , M ² , and M ³ were independently replaced with hydrogen, fluorine, alkyl with 1 to 5 carbon atoms, or at least one hydrogen with fluorine or chlorine. Alkyl with 1 to 5 carbon atoms;

Sp ³ , Sp ⁴ , and Sp ⁵ are independently single bonds or alkylenes with 1 to 10 carbon atoms, and in these Sp ³ , Sp ⁴ , and Sp ⁵ , at least one -CH ₂ -is -O. -, -COO-, -OCO-, or -OCOO- may be replaced, and at least one -CH ₂ CH _2- may be replaced with -CH = CH- or -C≡C-. , At least one hydrogen may be replaced with fluorine or chlorine.

Item 14. Item 2. The liquid crystal composition according to any one of Items 11 to 13, wherein the ratio of the second additive is in the range of 0.03% by weight to 10% by weight based on the weight of the liquid crystal composition.

式（５）において、Ｒ^５０は、水素、ハロゲン、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルであり；Ｒ^５１は、−ＯＨ、−ＮＨ_２、−ＯＲ^５３、−Ｎ(Ｒ^５３)_２、または−Ｓｉ（Ｒ^５３）_３で表される基であり、ここで、Ｒ^５３は、水素または炭素数１から５のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−で置き換えられてもよく、少なくとも１つの−（ＣＨ_２）_２−は、−ＣＨ＝ＣＨ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；環Ａ^５０および環Ｂ^５０は独立して、１，４−シクロへキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、ナフタレン−１，２−ジイル、ナフタレン−１，３−ジイル、ナフタレン−１，４−ジイル、ナフタレン−１，５−ジイル、ナフタレン−１，６−ジイル、ナフタレン−１，７−ジイル、ナフタレン−１，８−ジイル、ナフタレン−２，３−ジイル、ナフタレン−２，６−ジイル、ナフタレン−２，７−ジイル、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、フルオレン−２，７−ジイル、フェナントレン−２，７−ジイル、アントラセン−２，６−ジイル、ペルヒドロシクロペンタ［ａ］フェナントレン−３，１７−ジイル、または２，３，４，７，８，９，１０，１１，１２，１３，１４，１５，１６，１７−テトラデカヒドロシクロペンタ［ａ］フェナントレン−３，１７−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^５０は、単結合、−（ＣＨ_２）_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、または−ＣＦ＝ＣＦ−であり；Ｓｐ^５１およびＳｐ^５２は独立して、単結合または炭素数１から７のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；ａ^５０は、０、１、２、３、または４である。Item 15. Item 6. The liquid crystal composition according to any one of Items 1 to 14, which contains at least one polymerizable compound selected from the group of compounds represented by the formula (5) as a third additive.

In formula (5), ^R50 was hydrogen, halogen, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, and at least one hydrogen was 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 with fluorine or chlorine; R ⁵¹ is -OH, -NH ₂ , -OR ⁵³ , -N (R). ⁵³ ) A group represented by ₂ or -Si (R ⁵³ ) ₃ ^{, where R 53} is hydrogen or an alkyl having 1 to 5 carbon atoms, in which at least one -CH _2- May be replaced with −O−, at least one − (CH ₂ ) ₂ − may be replaced with −CH = CH−, and in these groups at least one hydrogen is replaced with fluorine. Ring A ⁵⁰ and Ring B ⁵⁰ may independently be 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1. , 3-Xylene, 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, pyridine- 2,5-Diyl, Fluoren-2,7-Diyl, Phenantren-2,7-Dyle, Anthracen-2,6-Diyl, Perhydrocyclopenta [a] Phenantren-3,17-Diyl, or 2,3 4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl, at least one in these rings. Hydrogen may be replaced with fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or alkyl with 1 to 12 carbons in which at least one hydrogen has been replaced with fluorine or chlorine; Z ⁵⁰ is a single bond,-(CH ₂ ) _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ O -, -OCH _2- , or -CF = CF-; Sp ⁵¹ And Sp ⁵² are independently single-bonded or 1 to 7 carbon alkylenes, in which at least one -CH ₂ − is replaced by -O-, -COO-, or -OCO-. Also, at least one −CH ₂ CH ₂ − may be replaced by −CH = CH −, and in these groups, at least one hydrogen may be replaced by fluorine; a ⁵⁰ is 0. 1, 2, 3, or 4.

Item 16. Item 2. The liquid crystal composition according to Item 15, wherein the proportion of the third additive is in the range of 0.3% by weight to 10% by weight based on the weight of the liquid crystal composition.

Item 17. A liquid crystal display device containing the liquid crystal composition according to any one of Items 1 to 16.

Item 18. Item 17. The liquid crystal display element according to Item 17, 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 drive method of the liquid crystal display element is an active matrix method.

Item 19. A polymer-supported oriented liquid crystal display element containing the liquid crystal composition according to any one of Items 1 to 16 and polymerized with a polymerizable compound in the liquid crystal composition.

Item 20. A liquid crystal display element having no alignment film and containing the liquid crystal composition according to any one of Items 1 to 16, wherein the polymerizable compound in the liquid crystal composition is polymerized.

Item 21. Use of the liquid crystal composition according to any one of Items 1 to 16 in a liquid crystal display element.

Item 22. Use of the liquid crystal composition according to any one of Items 1 to 16 in a polymer-supported orientation type liquid crystal display device.

Item 23. Use of the liquid crystal composition according to any one of Items 1 to 16 in a liquid crystal display device having no alignment film.

The present invention also includes the following sections. (A) The above liquid crystal composition is arranged between two substrates, irradiated with light while a voltage is applied to the composition, and a polymerizable group is added to the branched structure at the molecular terminal contained in the composition. A method for producing the above liquid crystal display element by polymerizing a compound having a polar group. (B) The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C.) is 0.08 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C.). ) Is -2 or less, the above liquid crystal composition.

The present invention also includes the following sections. (C) Compounds (5) to (7) described in JP-A-2006-199941 are liquid crystal compounds having a positive dielectric anisotropy, but at least selected from the group of these compounds. The above composition containing one compound. (D) The above composition containing at least two compounds (1-1) having a polymerizable group and a polar group in the branched structure at the molecular terminal. (E) The above composition further containing a polar compound different from the compound (1-1) having a polymerizable group and a polar group in the branched structure at the molecular terminal. (F) One, two, or at least three additives such as optically active compounds, antioxidants, UV absorbers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds. The above composition containing one. (G) AM device containing the above composition. (H) A device containing the above composition and having a mode of TN, ECB, OCB, IPS, FFS, VA, or FPA. (I) A transmissive device containing the above composition. (J) The above composition is used as a composition having a nematic phase. (K) Use as an optically active composition by adding an optically active compound to the above composition.

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

First, the composition of the composition will be described. The compositions of the present invention are classified into composition A and composition B. The composition A 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. Additives include optically active compounds, antioxidants, UV absorbers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like.

The composition B is substantially composed of only the liquid crystal compound selected from the compound (2) and the compound (3). "Substantially" means that the composition may contain additives but does not contain other liquid crystal compounds. The composition B has a smaller number of components than the composition A. The composition B is preferable to the composition A from the viewpoint of reducing the cost. Composition A is preferable to composition B from the viewpoint that the properties can be further adjusted by mixing other liquid crystal compounds.

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

When the component compounds are mixed with the composition, the main effects of the component compounds on the properties of the composition are: Compound (1) is adsorbed on the substrate surface by the action of polar groups to control the orientation of liquid crystal molecules. In order to obtain the desired effect, it is essential that the compound (1) has high compatibility with the liquid crystal compound. Compound (1) has a rod-shaped molecular structure having a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and has a branched structure at one end of the molecular structure. It is most suitable for this purpose because it is considered that the compatibility can be improved. Compound (1) gives a polymer by polymerization. This polymer stabilizes the orientation of the liquid crystal molecules, thus shortening the response time of the device and improving image burn-in. Compound (2) increases the dielectric anisotropy and lowers the lower limit temperature. Compound (3) lowers the viscosity. Compound (4) gives a polymer by polymerization. This polymer stabilizes the orientation of the liquid crystal molecules, thus reducing the response time of the device and improving image burn-in. From the viewpoint of the orientation of the liquid crystal molecules, it is presumed that the polymer of the compound (1) is more effective than the polymer of the compound (4) because it has an interaction with the surface of the substrate. Compound (5) has a polar group and a polymerizable group linearly at the end of its molecular structure, and controls and promotes the orientation of liquid crystal molecules in the same manner as compound (1).

Third, the combination of ingredients in the composition, the preferred proportions of the ingredients and the rationale thereof will be described. A preferred combination of components in the composition is compound (1) + compound (2) + compound (3) or compound (1) + compound (2) + compound (3) + compound (4). Compound (5) may be further combined with these combinations.

Compound (1) is added to the composition for the purpose of controlling the orientation of the liquid crystal molecules. The preferable ratio of the compound (1) is about 0.05% by weight or more for aligning the liquid crystal molecules, and about 10% by weight or less for preventing display defects of the device. A more preferred ratio is in the range of about 0.1% by weight to about 7% by weight. A particularly preferred ratio is in the range of about 0.5% by weight to about 5% by weight.

The preferable ratio of the compound (2) is about 10% by weight or more in order to increase the dielectric anisotropy, and about 90% by weight or less in order to lower the lower limit temperature. A more preferred ratio is in the range of about 20% by weight to about 85% by weight. A particularly preferred proportion is in the range of about 30% by weight to about 85% by weight.

The preferred proportion of compound (3) is about 10% by weight or more to raise the upper limit temperature or lower the lower limit temperature, and about 90% by weight or less to increase the dielectric anisotropy. A more preferred ratio is in the range of about 15% by weight to about 75% by weight. A particularly preferred ratio is in the range of about 15% by weight to about 60% by weight.

Compound (4) is added to the composition for the purpose of adapting to a polymer support oriented device. The preferable ratio of the compound (4) is about 0.03% by weight or more in order to improve the long-term reliability of the device, and about 10% by weight or less in order to prevent display defects of the device. A more preferred ratio is in the range of about 0.1% by weight to about 2% by weight. A particularly preferred ratio is in the range of about 0.2% by weight to about 1.0% by weight.

Compound (5) is added to the composition for the purpose of controlling and promoting the orientation of the liquid crystal molecules. The preferable ratio of the compound (5) is about 0.05% by weight or more for aligning the liquid crystal molecules, and about 10% by weight or less for preventing display defects of the device. A more preferred ratio is in the range of about 0.1% by weight to about 7% by weight. A particularly preferable ratio is in the range of about 0.3% by weight to about 5% by weight.

Fourth, preferable forms of the component compounds will be described. ^{In formula (1-1), X 1} of formula (1f), formula (1g), formula (1h) and formula (1i) is a polar group. Compound (1-1) is preferably stable because it is added to the composition. When compound (1-1) is added to the composition, it is preferable that this compound does not lower the voltage retention of the device. Compound (1-1) preferably has low volatility. The preferred molar mass is 130 g / mol or more. A more preferred molar mass is in the range of 150 g / mol to 800 g / mol. Preferred compounds (1-1) have polymerizable groups such as acryloyloxy (-OCO-CH = CH ₂ ), methacryloyloxy (-OCO- (CH ₃ ) C = CH ₂ ), α-hydroxyalkyl acrylates. ..

In formula (1f), formula (1g), formula (1h) and formula (1i), X ¹ is -OH, -NH ₂ , -OR ¹⁵ , -N (R ¹⁵ ) ₂ , -COOH, -SH, A group represented by −B (OH) ₂ or −Si (R ¹⁵ ) ₃ ^{, where R 15} is hydrogen or an alkyl having 1 to 5 carbon atoms, in which at least one −CH ₂ − may be replaced by −O −, at least one −CH ₂ CH ₂ − may be replaced by −CH = CH −, and in these groups, at least one hydrogen is fluorine. It may be replaced. From the viewpoint of high solubility in the liquid crystal composition, it is particularly preferable that ^{X 1} is −OH or −NH _2. -OH is preferred over -O-, -CO-, or -COO- because it has a high anchoring force. Groups with multiple heteroatoms (nitrogen, oxygen) are particularly preferred. Compounds with such polar groups are effective even at low concentrations.

In formula (1-1), ^{R 1} is alkyl of 1 to 15 carbon atoms, in the ^{R 1,} at least one -CH ₂ - may be replaced by -O- or -S-, At least one -CH ₂ CH _2- may be replaced with -CH = CH- or -C≡C- and at least one hydrogen may be replaced with a halogen.
Ring ^{A 1} and ring ^{A 2} are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6 Diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine- 2,5-Diyl, Fluorene-2,7-Diyl, Phenanthrene-2,7-Diyl, Anthracene-2,6-Diyl, Perhydrocyclopenta [a] Phenanthrene-3,17-Diyl, or 2,3 4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl, at least one in these rings. Hydrogen may be replaced with fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, alkoxy with 1 to 11 carbon atoms, or alkenyloxy with 2 to 11 carbon atoms, these groups. In, at least one hydrogen may be replaced with fluorine or chlorine. Preferred ring A ¹ or ring A ² is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, naphthalene-2,6-diyl, or 3-ethyl-1,4. -Phenylene.

In formula (1-1), Z ¹ is a single bond or an alkylene having 1 to 6 carbon atoms, and in this Z ¹ , at least one −CH ₂ − is −O−, −CO−, −COO−. , -OCO-, or -OCOO-, at least one -CH ₂ CH _2- may be replaced by -CH = CH- or -C≡C-, and at least one hydrogen , Fluorine or chlorine may be replaced. Preferred Z ¹ is single bond, -CH ₂ CH _{2- , -CH 2} O-, -OCH _2- , -COO-, or -OCO-. A more preferred Z ¹ is a single bond.

In formula (1-1), a is 0, 1, 2, 3, or 4. Preferred a is 0, 1, 2, or 3. A more preferable a is 0, 1, or 2. Particularly preferred a is 1 or 2.

式（１ａ）において、
Ｓｐ^１２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Ｓｐ^１２において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、少なくとも１つの水素は、ハロゲンで置き換えられてもよい。好ましいＳｐ^１２は単結合、炭素数１から５のアルキレン、または１つの−ＣＨ_２−が−Ｏ−で置き換えられた炭素数１から５のアルキレンである。さらに好ましいＳｐ^１２は、単結合、炭素数１から３のアルキレン、または１つの−ＣＨ_２−が−Ｏ−で置き換えられた炭素数１から３のアルキレンである。
Ｍ^１１およびＭ^１２は独立して、水素、ハロゲン、炭素数１から５のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から５のアルキルである。好ましいＭ^１１またはＭ^１２は、反応性を上げるために水素またはメチルである。さらに好ましいＭ^１１またはＭ^１２は水素である。
Ｒ^１２は炭素数１から１５のアルキルであり、このＲ^１２において、少なくとも１つの−ＣＨ_２−は、−Ｏ−または−Ｓ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、少なくとも１つの水素はハロゲンで置き換えられてもよい。好ましいＲ^１２は、水素、または炭素数１から５のアルキレン、または１つの−ＣＨ_２−が−Ｏ−で置き換えられた炭素数１から５のアルキレンである。さらに好ましいＲ^１２は、水素、または炭素数１から３のアルキレン、または１つの−ＣＨ_２−が−Ｏ−で置き換えられた炭素数１から３のアルキレンである。特に好ましいＲ^１２は、水素またはメチルである。Ｒ^１２が−ＣＨ_２−ＯＨである場合、分子内に２つの水酸基が存在する効果で低濃度添加での垂直配向が期待される。
式（１−１）において、好ましいＳｐ^１は、炭素数１から５のアルキレン、または１つの−ＣＨ_２−が−Ｏ−で置き換えられた炭素数１から５のアルキレンである。さらに好ましいＳｐ^１は、炭素数１から３のアルキレン、または１つの−ＣＨ_２−が−Ｏ−で置き換えられた炭素数１から３のアルキレンであり、これらの基において、少なくとも１つの水素は、式（１ａ）で表される重合性基で置き換えられる。
Ｐ^１１は、式（１ｅ）および式（１ｆ）で表される基から選択された基であり、

式（１ｅ）において、Ｒ^１３は、式（１ｇ）、式（１ｈ）、および式（１ｉ）で表される基から選択された基である。

式（１ｅ）および（１ｆ）において、
Ｓｐ^１３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Ｓｐ^１３において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＮＨ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素はハロゲンで置き換えられてもよい。好ましいＳｐ^１３は、炭素数１から７のアルキレン、または１つの−ＣＨ_２−が−Ｏ−で置き換えられた炭素数１から５のアルキレンである。さらに好ましいＳｐ^１３は、炭素数１から５のアルキレン、または１つの−ＣＨ_２−が−Ｏ−で置き換えられた炭素数１から５のアルキレンである。特に好ましいＳｐ^１３は、−ＣＨ_２−である。
式（１ｅ）において、Ｍ^１３およびＭ^１４は独立して、水素、ハロゲン、炭素数１から５のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から５のアルキルであり、好ましいＭ^１３またはＭ^１４は、反応性を上げるために水素またはメチルである。さらに好ましいＭ^１３またはＭ^１４は水素である。
式（１ｅ）において、Ｒ^１３は式（１ｇ）、式（１ｈ）、および式（１ｉ）で表される極性基の群から選択された基であり、好ましいＲ^１３は、式（１ｇ）または式（１ｈ）で表される極性基である。さらに好ましいＲ^１３は、式（１ｇ）で表される極性基である。
式（１ｇ）、式（１ｈ）、および式（１ｉ）において、Ｓｐ^１４およびＳｐ^１５は独立して、単結合または炭素数１から１０のアルキレンであり、このＳｐ^１４およびＳｐ^１５において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＮＨ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、ハロゲンで置き換えられてもよい。好ましいＳｐ^１４またはＳｐ^１５は、炭素数１から７のアルキレン、または１つの−ＣＨ_２−が−Ｏ−で置き換えられた炭素数１から５のアルキレンである。さらに好ましいＳｐ^１４またはＳｐ^１５は、炭素数１から５のアルキレン、または１つの−ＣＨ_２−が−Ｏ−で置き換えられた炭素数１から５のアルキレンである。特に好ましいＳｐ^１４またはＳｐ^１５は、−ＣＨ_２−である。
式（１ｈ）および式（１ｉ）において、Ｓ^１は、＞ＣＨ−または＞Ｎ−であり、そしてＳ^２は、＞Ｃ＜または＞Ｓｉ＜である。好ましいＳ^１は、＞ＣＨ−であり、好ましいＳ^２は、＞Ｃ＜である。
式（１ｆ）、式（１ｇ）、および式（１ｉ）において、Ｘ^１は、−ＯＨ、−ＮＨ_２、−ＯＲ^５、−Ｎ(Ｒ^１５)_２、−ＣＯＯＨ、−ＳＨ、−Ｂ（ＯＨ）_２、または−Ｓｉ（Ｒ^１５）_３であり、ここで、Ｒ^１５は、水素または炭素数１から１０のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。好ましいＸ^１は、−ＯＨ、−ＮＨ_２、または−Ｎ(Ｒ^１５)_２であり、ここで、Ｒ^１５は、水素または炭素数１から１０のアルキルであり、このＲ^１５において、少なくとも１つの−ＣＨ_２−は、−Ｏ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−で置き換えられてもよく、少なくとも１つの水素は、ハロゲンで置き換えられてもよい。好ましいＸ^１は、炭素数１から５のアルキルまたは炭素数１から４のアルコキシである。さらに好ましいＸ^１は、−ＯＨ、−ＮＨ_２、または−Ｎ(Ｒ^１５)_２である。特に好ましいＸ^１は、−ＯＨである。In formula (1-1), Sp ¹ is a single bond or an alkylene having 1 to 10 carbon atoms, and in this Sp ¹ , at least one −CH ₂ − is −O−, −CO−, −COO−,. It may be replaced by −OCO−, or −OCOO−, at least one −CH ₂ CH ₂₋ may be replaced by −CH = CH− or −C≡C−, and at least one hydrogen. It may be replaced with a halogen, in which at least one hydrogen is replaced with a group selected from the groups represented by formula (1a);

In formula (1a)
Sp ¹² is alkylene of 10 a single bond or 1 carbon atoms, in the ^{Sp 12,} at least one of _-CH 2 -, -O -, - CO -, - COO -, - OCO-, or -OCOO- At least one -CH ₂ CH _2- may be replaced with -CH = CH- or -C≡C-, and at least one hydrogen may be replaced with a halogen. Preferred Sp ¹² is a single bond, an alkylene having 1 to 5 carbon atoms, or an alkylene having 1 to 5 carbon atoms in which one −CH ₂ − is replaced with −O−. More preferred Sp ¹² is a single bond, an alkylene with 1 to 3 carbon atoms, or an alkylene with 1 to 3 carbon atoms in which one −CH ₂ − is replaced with −O−.
M ¹¹ and M ¹² are independently hydrogen, halogen, alkyl having 1 to 5 carbon atoms, or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced with halogen. Preferred M ¹¹ or M ¹² is hydrogen or methyl to increase reactivity. A more preferred M ¹¹ or M ¹² is hydrogen.
R ¹² is alkyl of from 1 to 15 carbon atoms, in the ^{R 12,} at least one of -CH ₂ -, -O- or -S- in may be replaced, at least one _-CH 2 CH ₂ - May be replaced with −CH = CH− or −C≡C−, and at least one hydrogen may be replaced with a halogen. Preferred ^{R 12} is hydrogen or alkylene having 1 to 5 carbon atoms or one -CH _2, - is alkylene having a carbon number of 1 5 has been replaced by -O-. A more preferred R ¹² is hydrogen, or an alkylene having 1 to 3 carbon atoms, or an alkylene having 1 to 3 carbon atoms in which one -CH ₂ − is replaced with -O-. Particularly preferred ^{R 12} is hydrogen or methyl. When R ¹² is −CH _2- OH, vertical orientation is expected at low concentration due to the presence of two hydroxyl groups in the molecule.
In formula (1-1), the preferred Sp ¹ is an alkylene having 1 to 5 carbon atoms, or an alkylene having 1 to 5 carbon atoms in which one −CH ₂ − is replaced with −O−. A more preferred Sp ¹ is an alkylene having 1 to 3 carbon atoms, or an alkylene having 1 to 3 carbon atoms in which one -CH ₂ − is replaced with -O-, and in these groups, at least one hydrogen is contained. It is replaced with a polymerizable group represented by the formula (1a).
P ¹¹ is a group selected from the group represented by the formula (1e) and formula (1f),

In formula (1e), R ¹³ is a group selected from the groups represented by formula (1g), formula (1h), and formula (1i).

In equations (1e) and (1f)
Sp ¹³ is alkylene of 10 a single bond or 1 carbon atoms, in the ^{Sp 13,} at least one of _-CH 2 -, -O -, - NH -, - CO -, - COO -, - OCO-, Alternatively, it may be replaced by -OCOO-, at least one -CH ₂ CH _2- may be replaced by -CH = CH- or -C≡C-, and in these groups at least one hydrogen It may be replaced with halogen. Preferred Sp ¹³ is an alkylene having 1 to 7 carbon atoms, or an alkylene having 1 to 5 carbon atoms in which _{one -CH 2- has been replaced with -O-.} A more preferred Sp ¹³ is an alkylene having 1 to 5 carbon atoms, or an alkylene having 1 to 5 carbon atoms in which one −CH ₂ − is replaced with −O−. Particularly preferred ^{Sp 13} is, -CH ₂ - is.
In formula (1e), M ¹³ and M ¹⁴ are independently hydrogen, halogen, alkyl having 1 to 5 carbon atoms, or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced with halogen, which is preferable. M ¹³ or M ¹⁴ is hydrogen or methyl to increase reactivity. A more preferred M ¹³ or M ¹⁴ is hydrogen.
In formula (1e), R ¹³ is a group selected from the group of polar groups represented by formula (1g), formula (1h), and formula (1i), with preferred R ¹³ being formula (1g) or It is a polar group represented by the formula (1h). A more preferable R ¹³ is a polar group represented by the formula (1 g).
In formulas (1g), (1h), and (1i), Sp ¹⁴ and Sp ¹⁵ are independently single bonds or alkylenes having 1 to 10 carbon atoms, and at least 1 in ^{Sp 14} and Sp ^15. One −CH ₂₋ may be replaced by −O−, −NH−, −CO−, −COO−, −OCO−, or −OCOO−, and at least one −CH ₂ CH ₂₋ It may be replaced by CH = CH- or −C≡C−, and in these groups at least one hydrogen may be replaced by a halogen. Preferred Sp ¹⁴ or Sp ¹⁵ is an alkylene having 1 to 7 carbon atoms, or an alkylene having 1 to 5 carbon atoms in which _{one -CH 2- has been replaced with -O-.} More preferred Sp ¹⁴ or Sp ¹⁵ are alkylenes having 1 to 5 carbon atoms, or alkylenes having 1 to 5 carbon atoms in which one -CH _2- has been replaced with -O-. Particularly preferred ^{Sp 14} or ^{Sp 15} is, -CH ₂ - is.
In formulas (1h) and (1i), S ¹ is> CH- or> N-, and S ² is> C <or> Si <. Preferred S ¹ is> CH− and preferred S ² is> C <.
In formulas (1f), formula (1g), and formula (1i), X ¹ is -OH, -NH ₂ , -OR ⁵ , -N (R ¹⁵ ) ₂ , -COOH, -SH, -B (OH). ) ₂ , or -Si (R ¹⁵ ) ₃ , where R ¹⁵ is hydrogen or an alkyl having 1 to 10 carbon atoms, in which at least one -CH ₂ -is replaced by -O-. At least one -CH ₂ CH _2- may be replaced with -CH = CH-, and in these groups at least one hydrogen may be replaced with fluorine or chlorine. Preferred X ¹ is -OH, -NH ₂ , or -N (R ¹⁵ ) ₂ , where R ¹⁵ is hydrogen or an alkyl having 1 to 10 carbon atoms, at least one in ^{this R 15.} -CH ₂ − may be replaced by −O −, at least one −CH ₂ CH ₂ − may be replaced by −CH = CH −, and at least one hydrogen may be replaced by halogen. May be good. Preferred X ¹ is an alkyl having 1 to 5 carbon atoms or an alkoxy having 1 to 4 carbon atoms. More preferred X ¹ is -OH, -NH ₂ , or -N (R ¹⁵ ) ₂ . Particularly preferred X ¹ is −OH.

In equations (1-4) to (1-60),
R ¹ is an alkyl with 1 to 10 carbon atoms;
Z ^{1, Z 12,} and ^{Z 13} are independently a single bond, _-CH 2 CH ₂ -, or - _{(CH 2) 4} - a and;
Sp ¹² , Sp ¹³ , and Sp ¹⁴ are independently single-bonded or 1 to 5 carbon alkylenes, in which at least one -CH ₂ − may be replaced by -O-;
L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ , L ⁸ , L ⁹ , L ¹⁰ , L ¹¹ , and L ¹² are independently hydrogen, fluorine, methyl, or ethyl. be.

In formulas (2) and (3), R ³ and R ⁴ are independently derived from an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, or 2 carbon atoms. Twelve alkoxyoxys. Preferred R ³ or R ⁴ is an alkyl having 1 to 12 carbon atoms to increase stability and an alkoxy having 1 to 12 carbon atoms to increase dielectric anisotropy. R ⁵ and R ⁶ are independently from alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, and 1 carbon with at least one hydrogen replaced by fluorine or chlorine. Twelve alkyls, or alkenyl with 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. Preferred R ⁵ or R ^6, in order to lower the viscosity, alkenyl of 2 to 12 carbons, alkyl of 1 to 12 carbons for increasing the stability. The alkyl of the liquid crystal compound is linear or branched and does not contain cyclic alkyl. Linear alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl.

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

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

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

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

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

Preferred examples of alkenyl in which at least one hydrogen is replaced with fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro. -4-pentenyl, or 6,6-difluoro-5-hexenyl. A more preferred example is 2,2-difluorovinyl or 4,4-difluoro-3-butenyl to reduce the viscosity.

または

であり、好ましくは

である。
Rings C and E are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine, Or tetrahydropyran-2,5-diyl. Preferred examples of "1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine" are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, or 2-chloro. -3-Fluoro-1,4-phenylene. Preferred ring C or ring E is 1,4-cyclohexylene to reduce viscosity, tetrahydropyran-2,5-diyl to increase dielectric anisotropy, and to increase optical anisotropy. It is 1,4-phenylene. The configuration for 1,4-cyclohexylene is preferably trans over cis in order to raise the upper temperature limit. Tetrahydropyran-2,5-diyl is

or

And preferably

Is.

Ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4. 5-Trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl. The preferred ring D is 2,3-difluoro-1,4-phenylene to reduce the viscosity, 2-chloro-3-fluoro-1,4-phenylene to reduce the optical anisotropy, and the dielectric constant. 7,8-Difluorochroman-2,6-diyl to increase anisotropy.

Rings F and G are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. Preferred ring F or ring G is 1,4-cyclohexylene for lowering the viscosity or raising the upper temperature limit and 1,4-phenylene for lowering the lower limit temperature. The configuration for 1,4-cyclohexylene is preferably trans over cis in order to raise the upper temperature limit.

Z ² and Z ³ are independently single-bonded, -CH ₂ CH _{2- , -CH 2} O-, -OCH _2- , -COO-, or -OCO-. Preferred Z ² or Z ³ are single bonds to reduce the viscosity, −CH ₂ CH _{2 − to lower the lower limit temperature, and −CH 2} O− or −OCH to increase the dielectric anisotropy. _2- . Z ⁴ is a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or -OCO-. Preferred Z ⁴ is a single bond to lower the viscosity, −CH ₂ CH ₂ − to lower the lower limit temperature, and −COO − or −OCO − to raise the upper limit temperature.

b is 1, 2, or 3, c is 0 or 1, and the sum of b and c is 3 or less. The preferred b is 1 for lowering the viscosity and 2 or 3 for raising the upper temperature limit. The preferred c is 0 to lower the viscosity and 1 to lower the lower limit temperature. d is 1, 2, or 3. The preferred d is 1 for lowering the viscosity and 2 or 3 for raising the upper temperature limit.

In formula (4), P ¹ , P ² , and P ³ are independently polymerizable groups. Preferred P ¹ , P ² , or P ³ are polymerizable groups selected from the group of groups represented by formulas (P-1) to (P-5). More preferred P ¹ , P ² , or P ³ is a group represented by formula (P-1), formula (P-2), or formula (P-3). Particularly preferred P ¹ , P ² , or P ³ is a group represented by the formula (P-1) or the formula (P-2). The most preferable P ¹ , P ² , or P ³ is a group represented by the formula (P-1). The preferred group represented by the formula (P-1) is -OCO-CH = CH ₂ or -OCO-C (CH ₃ ) = CH ₂ . The wavy lines of the formulas (P-1) to (P-5) indicate the sites to be combined.

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

Sp ³ , Sp ⁴ , and Sp ⁵ are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -COO-, -OCO. -Or -OCOO- may be replaced, and at least one -CH ₂ CH _2- may be replaced with -CH = CH- or -C≡C-, at least 1 in these groups. One hydrogen may be replaced with fluorine or chlorine. Preferred Sp ³ , Sp ⁴ , or Sp ⁵ are single bonds, -CH ₂ CH _{2- , -CH 2} O-, -OCH _2- , -COO-, -OCO-, -CO-CH = CH-, or. -CH = CH-CO-. More preferred Sp ³ , Sp ⁴ , or Sp ⁵ are single bonds.

Ring J and Ring P are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl, or pyridine. -2-yl, in these rings at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least one hydrogen is replaced with fluorine or chlorine. It may be replaced with an alkyl having 1 to 12 carbon atoms. The preferred ring J or ring P is phenyl. Ring K is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene. -1,5-Diyl, Naphthalene-1,6-Diyl, Naphthalene-1,7-Diyl, Naphthalene-1,8-Diyl, Naphthalene-2,3-Diyl, Naphthalene-2,6-Diyl, Naphthalene-2 , 7-Diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings. At least one hydrogen is replaced with fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, or alkyl with 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. May be good. The preferred ring K is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁵ and Z ⁶ are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, or-. It may be replaced by OCO-, and at least one -CH ₂ CH _2- may be -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C. It may be replaced by (CH ₃ ) = C (CH ₃ ) −, and in these groups at least one hydrogen may be replaced by fluorine or chlorine. Preferred Z ⁵ or Z ⁶ are single bond, -CH ₂ CH _{2- , -CH 2} O-, -OCH _2- , -COO-, or -OCO-. A more preferred Z ⁵ or Z ⁶ is a single bond.

q is 0, 1, or 2. The preferred q is 0 or 1. j, k, and p are independently 0, 1, 2, 3, or 4, and the sum of j, k, and p is greater than or equal to 1. Preferred j, k, or p is 1 or 2.

Fifth, preferred component compounds are shown. Preferred compounds (1-1) are the compound (1-2) and the compound (1-3) according to Item 2. More preferable compounds (1-1) are compounds (1-4) to compounds (1-60) according to Item 3. In these compounds, at least one of the first additives is compound (1-4), compound (1-5), compound (1-6), compound (1-12), compound (1-20), compound. (1-22), compound (1-23), compound (1-24), compound (1-25), compound (1-42), compound (1-43), compound (1-44). Is preferable.
It is preferred that at least two of the first additives are compound (1-4) and compound (1-5), or a combination of compound (1-5) and compound (1-6).

Preferred compounds (2) are compounds (2-1) to compounds (2-22) according to Item 6. In these compounds, at least one of the first components is compound (2-1), compound (2-3), compound (2-4), compound (2-6), compound (2-8), or compound. (2-10) is preferable. At least two of the first components are compound (2-1) and compound (2-6), compound (2-1) and compound (2-10), compound (2-3) and compound (2-6), It is preferably a combination of compound (2-3) and compound (2-10), compound (2-4) and compound (2-6), or compound (2-4) and compound (2-8).

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

Preferred compounds (4) are compounds (4-1) to compounds (4-29) according to Item 13. 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), compound. It is preferably (4-27) or compound (4-29). 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 compound (4-24) is preferred.

Examples of preferred compound (5) are compound (5-1) to compound (5-10). The preferred proportion of compound (5) is in the range of about 0.3% by weight to about 10% by weight.

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

Antioxidants are composed to prevent a decrease in resistivity due to heating in the atmosphere, or to maintain a large voltage retention not only at room temperature but also at temperatures close to the upper limit temperature after long-term use of the device. It is added to the thing. Preferred examples of the antioxidant are compound (7) in which n is an integer of 1 to 9.

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

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

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

Polymerizable compounds are used to adapt to polymer support orientation (PSA) type devices. Compound (1) and compound (4) are suitable for this purpose. Compound (5) may be added to the composition together with compound (1) and compound (4). Further, along with the compound (1) and the compound (4), other polymerizable compounds different from the compound (1), the compound (4) and the compound (5) may be added to the composition. Preferred examples of other polymerizable compounds are compounds such as acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxylane, oxetane), vinyl ketones and the like. More preferred examples are acrylates or methacrylates. The preferred proportion of compound (1), compound (4) and compound (5) is about 10% by weight or more based on the total weight of the polymerizable compound. A more preferable ratio is about 50% by weight or more. A more preferable ratio is about 80% by weight or more. A particularly preferable ratio is also 100% by weight. By varying the types of compound (1), compound (4) and compound (5), or by combining compound (1), compound (4) and compound (5) with other polymerizable compounds in appropriate proportions. , The reactivity of the polymerizable compound and the pretilt angle of the liquid crystal molecule can be adjusted. By optimizing the pre-tilt angle, a short response time of the device can be achieved. Since the orientation of the liquid crystal molecules is stabilized, a large contrast ratio and a long life can be achieved.

Polymerizable compounds such as compound (1), compound (4) and compound (5) are polymerized by UV irradiation. Polymerization may be carried out in the presence of a suitable initiator such as a photopolymerization initiator. Appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those of skill in the art and are described in the literature. For example, the photopolymerization initiators Irgacure651®, Irgacure184® (registered trademark; BASF), or Darocur1173® are suitable for radical polymerization. The preferred proportion of photopolymerization initiator is in the range of about 0.1% by weight to about 5% by weight based on the total weight of the polymerizable compound. A more preferred ratio is in the range of about 1% by weight to about 3% by weight.

When storing polymerizable compounds such as compound (1), compound (4) and compound (5), a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine and the like.

Seventh, a method for synthesizing a component compound will be described. These compounds can be synthesized by known methods. An example of the synthesis method. The method for synthesizing compound (1) is described in the section of Examples. Compound (2-1) is synthesized by the method described in JP-A-2-503441. Compound (3-5) is synthesized by the method described in JP-A-57-165328. Compound (5) is synthesized by the method described in International Publication No. 2016/015803 pamphlet. Compound (4-18) is synthesized by the method described in JP-A-7-101900. Some of compound (7) are commercially available. The compound of formula (7) where n is 1 can be obtained from Sigma-Aldrich Corporation. Compound (7) and the like having n of 7 are synthesized by the method described in US Pat. No. 3,660,505.

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

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

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

An example of a conventional method for manufacturing a polymer-supported orientation type device is as follows. An element having two substrates called an array substrate and a color filter substrate is assembled. This substrate has an alignment film. At least one of the substrates has an electrode layer. Liquid crystal compounds are mixed to prepare a liquid crystal composition. A polymerizable compound is added to this composition. Additional additives may be added as needed. This composition is injected into the device. Light is irradiated while a voltage is applied to this element. Ultraviolet rays are preferred. The polymerizable compound is polymerized by light irradiation. This polymerization produces a composition containing the polymer. The polymer support orientation type device is manufactured by such a procedure.

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

When compound (1), that is, a compound having a polymerizable group and a polar group in the branched structure at the molecular terminal is used, an alignment film is not required on the substrate of the device. Devices that do not have an alignment film are manufactured according to the procedure described in the previous paragraph, except that a substrate that does not have an alignment film is used.

In this procedure, compound (1) is arranged on the substrate because the polar groups interact with the surface of the substrate. The liquid crystal molecules are oriented according to this arrangement. When a voltage is applied, the orientation of the liquid crystal molecules is further promoted. Since the polymerizable group is polymerized by ultraviolet rays in this state, a polymer that maintains this orientation is produced. Due to the effect of this polymer, the orientation of the liquid crystal molecules is additionally stabilized, and the response time of the device is shortened. Since the burn-in of the image is a malfunction of the liquid crystal molecules, the burn-in is also improved at the same time by the effect of this polymer.

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

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

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

Chloroform, hexane or the like may be used as the solvent for diluting the sample. The following capillary columns may be used to separate the constituent compounds. HP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc., Rtx-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Restek Corporation, BP-1 manufactured by SGE International Pty. Ltd (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm). A capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Shimadzu Corporation may be used for the purpose of preventing overlapping of compound peaks.

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

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

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

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

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

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

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

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

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

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

(7) Threshold voltage (Vth; measured at 25 ° C.; V): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. A sample is placed in a VA element in normally black mode in which the distance (cell gap) between two glass substrates is 4 μm and the rubbing direction is anti-parallel, and an adhesive that cures this element with ultraviolet rays is applied. Sealed using. The voltage (60 Hz, square wave) applied to this device was gradually increased by 0.02 V from 0 V to 20 V. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the amount of light was maximum and the transmittance was 0% when the amount of light was minimum. The threshold voltage is expressed as the voltage when the transmittance reaches 10%.

(8) Voltage retention rate (VHR-1; measured at 25 ° C.;%): The TN element used for the measurement had a polyimide alignment film, and the distance (cell gap) between the two glass substrates was 5 μm. .. This device was sealed with an adhesive that cures with UV light after injecting the sample. A pulse voltage (60 microseconds at 5 V) was applied to the TN element to charge it. The decaying voltage was measured with a high-speed voltmeter for 16.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit period was determined. Area B was the area when there was no attenuation. The voltage holding ratio is expressed as a percentage of the area A with respect to the area B.

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

(10) Voltage retention rate (VHR-3; measured at 25 ° C.;%): After irradiation with ultraviolet rays, the voltage retention rate was measured to evaluate the stability against ultraviolet rays. The TN device used for the measurement had a polyimide alignment film, and the cell gap was 5 μm. A sample was injected into this device and irradiated with light for 20 minutes. The light source was an ultra-high pressure mercury lamp USH-500D (manufactured by Ushio, Inc.), and the distance between the element and the light source was 20 cm. In the VHR-3 measurement, the voltage decayed for 16.7 milliseconds was measured. Compositions with large VHR-3 have great stability to UV light. VHR-3 is preferably 90% or more, more preferably 95% or more.

(11) Voltage retention rate (VHR-4; measured at 25 ° C.;%): After heating the TN element into which the sample was injected in a constant temperature bath at 80 ° C. for 500 hours, the voltage retention rate was measured and stability against heat was measured. Was evaluated. In the VHR-4 measurement, the voltage decayed for 16.7 milliseconds was measured. Compositions with large VHR-4 have great stability to heat.

(12) Response time (τ; measured at 25 ° C.; ms): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The low-pass filter was set to 5 kHz. The sample was placed in a VA element having a distance (cell gap) between two glass substrates of 3.5 μm and having no alignment film. This element was sealed with an adhesive that cures with UV light. ^{This device was irradiated with ultraviolet rays of 78 mW / cm 2} (405 nm) for 449 seconds (35 J) while applying a voltage of 30 V. For the irradiation of ultraviolet rays, a multi-metal lamp M04-L41 for ultraviolet curing manufactured by Eye Graphics Co., Ltd. was used. A square wave (120 Hz) was applied to this device. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. It was considered that the transmittance was 100% when the amount of light was maximum, and the transmittance was 0% when the amount of light was minimum. The maximum voltage of the square wave was set so that the transmittance was 90%. The minimum voltage of the square wave was set to 2.5V where the transmittance was 0%. The response time was expressed as the time required for the transmittance to change from 10% to 90% (rise time; rise time; millisecond).

(13) Elastic constant (K11: splay elastic constant, K33: bend elastic constant; measured at 25 ° C; pN): For measurement, use an EC-1 type elastic constant measuring device manufactured by Toyo Technica Co., Ltd. Using. The sample was injected into a vertically oriented element in which the distance (cell gap) between the two glass substrates was 20 μm. A charge of 20 to 0 volts was applied to this device, and the capacitance and applied voltage were measured. Fitting the measured capacitance (C) and applied voltage (V) values using the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), equations (2.98) and (2.11) on page 75. Then, the value of the elastic constant was obtained from the equation (2.10).

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

(15) Pre-tilt angle (degrees): A spectroscopic ellipsometer M-2000U (manufactured by JA Woollam Co., Inc.) was used for measuring the pre-tilt angle.

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

Synthesis example 1
Compound (1-23-1) was synthesized by the following method.

First step Compound (T-1) (40.0 g), triethyl phosphonoacetate (40.7 g) and toluene (800 ml) were placed in a reactor and cooled to 0 ° C. Sodium ethoxide (20% ethanol solution) (61.8 g) was slowly added dropwise thereto, and the mixture was stirred for 12 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 4: 1) to give compound (T-2) (42.0 g; 83%).

Step 2 Add compound (T-2) (42.0 g), toluene (400 ml) and isopropyl alcohol (400 ml) to the reactor and add Pd / C (0.7 g) for 24 hours at room temperature in a hydrogen atmosphere. Stirred. The reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 4: 1) to give compound (T-3) (40.1 g; 95%).

Step 3 Compound (T-3) (40.1 g) and THF (400 ml) were placed in the reactor and cooled to -60 ° C. Lithium diisopropylamide (LDA) (1.13 M; THF solution; 142 ml) was slowly added dropwise and stirred for 1 hour. Methyl chloroformate (11.0 ml) was slowly added dropwise thereto, and the mixture was stirred for 5 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 4: 1) to give compound (T-4) (30.5 g; 65%).

Step 4 Lithium aluminum hydride (1.7 g) and THF (300 ml) were placed in a reactor and ice-cooled. A solution of compound (T-4) (30.5 g) in THF (600 ml) was slowly added, 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 combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 1: 1). Further purification by recrystallization from heptane gave compound (T-5) (20.1 g; 80%).

Step 5 Compound (T-5) (20.1 g), triethylamine (10.3 ml) and THF (200 ml) were placed in the reactor and cooled to 0 ° C. Methacryloyl chloride (6.0 ml) was slowly added dropwise thereto, and the mixture was stirred for 4 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution is concentrated under reduced pressure and the residue is purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 9: 1) to give compound (1-23-1) (7.7 g; 32%). rice field.

The NMR analysis values of the obtained compound (1-23-1) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.11 (s, 1H), 5.58 (s, 1H), 4.29-4.26 (m, 1H), 4.14- 4.11 (m, 1H), 3.60-3.57 (m, 1H), 3.50-3.47 (m, 1H), 1.98-1.95 (m, 5H), 1. 78-1.67 (m, 8H), 1.32-1.11 (m, 12H), 0.99-0.81 (m, 13H)

The physical characteristics of compound (1-23-1) were as follows.
Transition temperature: C 65.0 I.

[Synthesis Example 2]
Synthesis of compound (1-4-1)

Step 1 Paraformaldehyde (30.0 g), 1,4 diazabicyclo [2.2.2] octane (DABCO) (56.0 g), and water (600 ml) were placed in the reactor and stirred at room temperature for 15 minutes. A solution of compound (T-6) (50.0 g) in THF (1200 ml) was added dropwise thereto, and the mixture was stirred at room temperature for 72 hours. The reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 4: 1) to give compound (T-7) (43.2 g; 65%).

Second step Using compound (T-7) (42.2 g) as a raw material, imidazole (26.3 g) and dichloromethane (800 ml) were placed in a reactor and cooled to 0 ° C. A solution of t-butyldiphenylchlorosilane (TBDPSCl) (106.4 g) in dichloromethane (100 ml) was slowly added dropwise thereto, and the mixture was stirred for 12 hours while returning to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate = 10: 1) to give compound (T-8) (107.0 g; 90%).

Step 3 Compound (T-8) (107.0 g), THF (800 ml), methanol (200 ml), and water (100 ml) were placed in the reactor and cooled to 0 ° C. Lithium hydroxide monohydrate (24.3 g) was added thereto, and the mixture was stirred for 12 hours while returning to room temperature. The reaction mixture was poured into water, 6N hydrochloric acid (100 ml) was slowly added to make it acidic, and then the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and purified by recrystallization from heptane to give compound (T-9) (47.4 g; 48%).

Step 4 Compound (1-23-1) (7.7 g), compound (T-9) (8.0 g), DMAP (1.0 g), and dichloromethane (200 ml) were placed in a reactor and brought to 0 ° C. Cooled. A solution of N, N'-dicyclohexylcarbodiimide (DCC) (4.8 g) in dichloromethane (60 ml) was slowly added dropwise thereto, and the mixture was stirred for 12 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate = 19: 1) to give compound (T-10) (9.8 g; 70%).

Step 5 Compound (T-10) (9.8 g) and THF (100 ml) were placed in a reactor and cooled to 0 ° C. Tetra-n-butylammonium fluoride (TBAF) (1.00 M; THF solution; 16.5 ml) was slowly added thereto, and the mixture was stirred for 1 hour while returning to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 9: 1). Further purification by recrystallization from heptane gave compound (1-4-1) (3.1 g; 47%).

The NMR analysis values of the obtained compound (1-4-1) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.25 (s, 1H), 6.10 (s, 1H), 5.85 (s, 1H), 5.57 (s, 1H) 4.33 (d, J = 4.5Hz, 2H), 4.27-4.16 (m, 2H), 4.13-4.08 (m, 2H), 2.31 (s, 1H) 2.26-2.22 (m, 1H), 1.94 (s, 3H), 1.81-1.61 (m, 8H), 1.32-1.08 (m, 12H), 1 .00-0.79 (m, 13H).

The physical characteristics of compound (1-4-1) were as follows.
Transition temperature: C 49.6 I.

[Synthesis Example 3]
Synthesis of compound (1-4-2)

Step 1 Compound (T-11) (15.0 g), N, N-dimethyl-4-aminopyridine (DMAP) (9.33 g), Meldrum's acid (9.54 g) and dichloromethane (250 ml) in the reactor And cooled to 0 ° C. N, N'-dicyclohexylcarbodiimide (DCC) (15.7 g) was slowly added thereto, and the mixture was stirred for 12 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure. The residue, ethanol (250 ml), was placed in a reactor and stirred at 70 ° C. After filtering the insoluble material, the reaction mixture was poured into a saline solution, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, heptane: toluene = 1: 1) to give compound (T-12) (10.2 g; 55%).

Second step Lithium aluminum hydride (0.6 g) and THF (100 ml) were placed in a reactor and ice-cooled. A solution of compound (T-12) (10.2 g) in THF (100 ml) was slowly added, and the mixture was stirred for 3 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 1: 1) to give compound (T-13) (7.35 g; 81%).

Step 3 Compound (T-13) (7.35 g), triethylamine (3.75 ml), N, N-dimethyl-4-aminopyridine (DMAP) (0.27 g), dichloromethane (200 ml) are placed in the reactor. , Cooled to 0 ° C. TIPSCl (triisopropylsilyl chloride) (5.05 ml) was slowly added dropwise, and the mixture was stirred for 24 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 19: 1) to give compound (T-14) (6.50 g; 60%).

Step 4 Compound (T-14) (6.50 g), triethylamine (3.77 ml) and THF (200 ml) were placed in a reactor and cooled to 0 ° C. Methacryloyl chloride (2.00 ml) was slowly added dropwise thereto, and the mixture was stirred for 4 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 1: 1) to give compound (T-15) (4.70 g; 63%).

Step 5 Compound (T-15) (4.70 g) and THF (100 ml) were placed in a reactor and cooled to 0 ° C. TBAF (1.00 M; THF solution; 10.3 ml) was slowly added thereto, and the mixture was stirred for 1 hour while returning to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 9: 1) to give compound (T-16) (1.50 g; 45%).

Step 6 Compound (T-16) (1.51 g; 55%) was obtained by the same method as in Step 4 of Synthesis Example 2, using compound (T-16) (1.50 g) as a raw material.

7th step Compound (1-4-2) (0.45 g; 45%) is obtained by the same method as in the 5th step of Synthesis Example 2 using the compound (T-17) (1.51 g) as a raw material. rice field.

The NMR analysis values of the obtained compound (1-4-2) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.25 (s, 1H), 6.09 (s, 1H), 5.82 (d, J = 1.1Hz, 1H), 5. 55 (s, 1H), 5.22-5.17 (m, 1H), 4.32-4.26 (m, 3H), 4.17-4.12 (m, 3H), 2.50 ( s, 1H), 2.03-1.89 (m, 5H), 1.83-1.58 (m, 9H), 1.41-1.08 (m, 11H), 0.96-0. 78 (m, 13H).

The physical characteristics of compound (1-4-2) were as follows.
Transition temperature: C 61.2 I.

[Synthesis Example 4]
Synthesis of compound (1-23-2)

Step 1 Compound (T-18) (20.0 g) and THF (200 ml) are placed in the reactor, cooled to −70 ° C. and lithium diisopropylamide (LDA) (1.10 M; THF solution; 68.0 ml). Was slowly added dropwise and stirred for 1 hour. Methyl chloroformate (7.00 g) was slowly added thereto, and the mixture was stirred for 4 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 9: 1) to give compound (T-19) (19.4 g; 82%).

Second step Lithium aluminum hydride (1.93 g) and THF (200 ml) were placed in a reactor and cooled to 0 ° C. A solution of compound (T-19) (19.4 g) in THF (100 ml) was slowly added thereto, and the mixture was stirred for 3 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 1: 1) to give compound (T-20) (6.0 g; 38%).

Step 3 Compound (T-20) (6.0 g), triethylamine (3.2 ml) and THF (100 ml) were placed in the reactor and cooled to 0 ° C. Methacryloyl chloride (1.8 ml) was slowly added thereto, and the mixture was stirred for 5 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution is concentrated under reduced pressure and the residue is purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 9: 1) to give compound (1-23-2) (2.5 g; 34%). rice field.

The NMR analysis values of the obtained compound (1-23-2) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.10 (s, 1H), 5.57 (d, J = 1.1Hz, 1H), 4.38 (dd, J = 11.4Hz) , J = 4.3Hz, 1H), 4.23 (dd, J = 11.3Hz, J = 6.7Hz, 1H), 3.71-3.68 (m, 1H), 3.63-3. 60 (m, 1H), 1.97 (s, 1H), 1.94 (s, 3H), 1.82-1.62 (m, 9H), 1.41-1.18 (m, 7H) , 1.14-0.79 (m, 16H).

The physical characteristics of compound (1-23-2) were as follows.
Transition temperature: C 68.4 S _A 89.3 I.

[Synthesis Example 5]
Synthesis of compound (1-4-3)

Step 1 Compound (T-7), 3,4-dihydro-2H-pyran (23.3 g) and pyridinium p-toluenesulfonate (PPTS) (5.80 g) were placed in a reactor and stirred at 50 ° C. for 10 hours. bottom. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate = 2: 1) to give compound (T-21) (39.5 g; 80%).

Second Step Compound (T-21) (39.5 g), THF (400 ml), and water (400 ml) were placed in a reactor and cooled to 0 ° C. Lithium hydroxide monohydrate (15.4 g) was added thereto, and the mixture was stirred for 12 hours while returning to room temperature. The reaction mixture was poured into water, 6N hydrochloric acid (60 ml) was slowly added to make it acidic, and then the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure to give compound (T-22) (32.6 g; 95%).

Step 3 Compound (1-23-2) (2.0 g), compound (T-22) (1.18 g), DMAP (0.32 g), and dichloromethane (100 ml) were placed in the reactor and brought to 0 ° C. Cooled. A solution of DCC (1.30 g) in dichloromethane (60 ml) was slowly added dropwise thereto, and the mixture was stirred for 12 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 19: 1) to give compound (T-23) (2.37 g; 82%).

Step 4 Compound (T-23) (2.37 g), pyridinium p-toluenesulfonate (PPTS) (0.54 g), THF (50 ml) and methanol (50 ml) were placed in the reactor at 50 ° C. for 5 hours. Stirred. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution is concentrated under reduced pressure and the residue is purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 9: 1) to give compound (1-4-3) (1.50 g; 75%). rice field.

The NMR analysis values of the obtained compound (1-4-3) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.24 (s, 1H), 6.09 (s, 1H), 5.84 (s, 1H), 5.57 (s, 1H) 4.33-4.27 (m, 4H), 4.20-4.16 (m, 2H), 2.34-2.31 (m, 1H), 1.97-1.90 (m, 4H) 1.82-1.67 (m, 8H), 1.43-1.39 (m, 1H), 1.31-1.18 (m, 6H), 1.15-0.75 ( m, 16H).

The physical characteristics of compound (1-4-3) were as follows.
Transition temperature: C 66.5 I.

[Synthesis Example 6]
Synthesis of compound (1-24-1)

Step 1 Compound (T-24) (30.0 g), ethanol (14.4 ml), potassium phosphate (53.6 g), copper iodide (1.60 g), ethyl acetoacetate (32.8 g) and dimethyl Sulfoxide (DMSO) (500 ml) was placed in the reactor and stirred at 80 ° C. for 6 hours. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 4: 1) to give compound (T-25) (19.5 g; 73%).

Second Step Compound (T-25) (19.5 g) was used as a raw material to obtain Compound (T-26) (16.2 g; 70%) by the same method as in the first step of Synthesis Example 4.

Third step Using the compound (T-26) (16.2 g) as a raw material, the compound (T-27) (6.0 g; 45%) was obtained by the same method as in the second step of Synthesis Example 4.

Step 4 Compound (T-27) (6.0 g) was used as a raw material, and compound (1-24-1) (2.3 g; 31%) was obtained by the same method as in Step 3 of Synthesis Example 4. rice field.

The NMR analysis values of the obtained compound (1-24-1) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.18-7.17 (m, 4H), 6.09 (s, 1H), 5.57 (s, 1H), 4.47- 4.38 (m, 2H), 3.91-3.85 (m, 2H), 3.19-3.14 (m, 1H), 2.44 (tt, J = 12.2Hz, J = 3) .0Hz, 1H), 1.93-1.86 (m, 8H), 1.48-1.38 (m, 2H), 1.34-1.19 (m, 9H), 1.07-0 .99 (m, 2H), 0.89 (t, J = 6.8Hz, 3H).

The physical characteristics of compound (1-24-1) were as follows.
Transition temperature: C 36.1 I.

[Synthesis Example 7]
Synthesis of compound (1-5-2)

First step Compound (T-28) (2.2 g; 76%) is obtained by using the compound (1-24-1) (2.0 g) as a raw material and the same method as in the third step of Synthesis Example 5. rice field.

Second step Compound (1-5-2) (1.3 g; 70%) is obtained by the same method as in the fourth step of Synthesis Example 5 using the compound (T-28) (2.2 g) as a raw material. rice field.

The NMR analysis values of the obtained compound (1-5-2) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.17-7.16 (m, 4H), 6.21 (s, 1H), 6.07 (s, 1H), 5.81 ( d, J = 1.0Hz, 1H), 5.55 (s, 1H), 4.46-4.39 (m, 4H), 4.27 (d, J = 6.2Hz, 2H), 3. 42-3.37 (m, 1H), 2.44 (tt, J = 12.2Hz, J = 3.1Hz, 1H), 2.22-2.21 (m, 1H), 1.95 (s) , 3H), 1.87-1.85 (m, 4H), 1.46-1.38 (m, 2H), 1.34-1.19 (m, 9H), 1.07-0.99 (M, 2H), 0.89 (t, J = 7.0Hz, 3H).

The physical characteristics of compound (1-5-2) were as follows.
Transition temperature: C 52.3 I.

[Synthesis Example 8]
Synthesis of compound (1-25-2)

First Step Compound (T-29) (30.0 g), triethyl phosphonoacetate (33.0 g) and toluene (500 ml) were placed in a reactor and cooled to 0 ° C. Sodium ethoxide (20% ethanol solution) (50.1 g) was slowly added dropwise thereto, and the mixture was stirred for 6 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 4: 1) to give compound (T-30) (32.8 g; 85%).

Second step Compound (T-30) (32.8 g), toluene (300 ml), IPA (300 ml) and Pd / C (0.55 g) were placed in a reactor and stirred under a hydrogen atmosphere for 12 hours. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 4: 1). Further purification by recrystallization from heptane gave compound (T-31) (16.8 g; 51%).

Third step Using the compound (T-31) (16.8 g) as a raw material, the compound (T-32) (14.1 g; 71%) was obtained by the same method as in the first step of Synthesis Example 4.

Fourth Step Compound (T-33) (6.0 g; 52%) was obtained by using the compound (T-32) (14.1 g) as a raw material in the same manner as in the second step of Synthesis Example 4.

Fifth step Using the compound (T-33) (6.0 g) as a raw material, the compound (1-25-2) (2.3 g; 32%) was obtained by the same method as in the third step of Synthesis Example 4. rice field.

The NMR analysis values of the obtained compound (1-25-2) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.14-7.10 (m, 4H), 6.12 (s, 1H), 5.59 (s, 1H), 4.43- 4.40 (m, 1H), 4.28-4.25 (m, 1H), 3.75-3.64 (m, 2H), 2.55 (t, J = 7.6Hz, 2H), 2.47-2.42 (m, 1H), 2.14 (s, 1H), 1.96-1.91 (m, 7H), 1.74-1.69 (m, 1H), 1. 62-1.22 (m, 11H), 0.88 (t, J = 6.8Hz, 3H).

The physical characteristics of compound (1-25-2) were as follows.
Transition temperature: C <-50.0 I.

[Synthesis Example 9]
Synthesis of compound (1-6-1)

First step Compound (T-34) (1.9 g; 68%) is obtained by using the compound (1-25-1) (2.0 g) as a raw material and the same method as in the third step of Synthesis Example 5. rice field.

Second step Using the compound (T-34) (1.9 g) as a raw material, the compound (1-6-1) (1.2 g; 75%) was obtained by the same method as in the fourth step of Synthesis Example 5. rice field.

The NMR analysis values of the obtained compound (1-6-1) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.13-7.10 (m, 4H), 6.27 (s, 1H), 6.11 (s, 1H), 5.86 ( s, 1H), 5.58 (s, 1H), 4.40-4.32 (m, 4H), 4.25-4.20 (m, 2H), 2.56 (t, J = 7. 6Hz, 2H), 2.45 (tt, J = 12.1Hz, J = 2.9Hz, 1H), 2.35-2.32 (m, 1H), 2.04-1.91 (m, 7H) ), 1.62-1.26 (m, 12H), 0.88 (t, J = 6.8Hz, 3H).

The physical characteristics of compound (1-6-1) were as follows.
Transition temperature: C 35.8 I.

[Synthesis Example 10]
Synthesis of compound (1-23-3)

Step 1 2- (1,3-Dioxane-2-yl) ethyltriphenylphosphonium bromide (103.7 g) and THF (500 ml) were placed in the reactor, cooled to -30 ° C and potassium t-butoxide (25). .4 g) was added, and the mixture was stirred for 1 hour. A solution of compound (T-35) (50.0 g) in THF (300 ml) was slowly added dropwise thereto, and the mixture was stirred for 6 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 1: 1) to give compound (T-36) (63.0 g; 92%).

Second step Compound (T-36) (63.0 g), toluene (500 ml), IPA (500 ml) and Pd / C (0.55 g) were placed in a reactor and stirred under a hydrogen atmosphere for 16 hours. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 1: 1) to give compound (T-37) (60.1 g; 95%).

Step 3 Compound (T-37) (60.1 g), formic acid (75.8 g), and toluene (1000 ml) were placed in the reactor and stirred at 100 ° C. for 6 hours. The insoluble material was filtered off, neutralized with an aqueous sodium hydrogen carbonate solution, and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography with toluene to give compound (T-38) (45.0 g; 89%).

Step 4 Compound (T-38) (45.0 g), potassium peroxymonosulfate (OXONE) (108.3 g) and DMF (1000 ml) were placed in a reactor and stirred at room temperature for 8 hours.
After filtering the insoluble material, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to give compound (T-39) (28.5 g; 60%).

Fifth Step Compound (T-39) (28.5 g), sulfuric acid (0.5 ml) and methanol (500 ml) were placed in a reactor and stirred at 60 ° C. for 5 hours. The insoluble material was filtered off, concentrated, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-40) (22.3 g; 75%).

6th Step Compound (T-40) (22.3g) was used as a raw material, and the compound (T-41) (18.3g; 70%) was obtained by the same method as in the 1st step of Synthesis Example 4.

7th step Compound (T-42) (5.9 g; 38%) was obtained by using the compound (T-41) (18.3 g) as a raw material in the same manner as in the second step of Synthesis Example 4.

Step 8 Compound (T-42) (5.9 g) was used as a raw material, and compound (1-23-3) (2.4 g; 34%) was obtained by the same method as in Step 3 of Synthesis Example 4. rice field.

The NMR analysis values of the obtained compound (1-23-3) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.11 (s, 1H), 5.81 (s, 1H), 4.31-4.28 (m, 1H), 4.17- 4.14 (m, 1H), 3.63-3.58 (m, 1H), 3.54-3.49 (m, 1H), 1.98-1.95 (m, 4H), 1. 84-1.69 (m, 9H), 1.41-1.18 (m, 10H), 1.15-1.06 (m, 4H), 1.02-0.80 (m, 13H).

The physical characteristics of compound (1-23-3) were as follows.
Transition temperature: C 33.6 S _A 101 I.

[Synthesis Example 11]
Synthesis of compound (1-4-4)

First step Compound (T-43) (2.1 g; 74%) is obtained by the same method as in the third step of Synthesis Example 5, using compound (1-23-3) (2.0 g) as a raw material. rice field.

Second step Compound (1-4-4) (1.3 g; 72%) is obtained by the same method as in the fourth step of Synthesis Example 5 using the compound (T-43) (2.1 g) as a raw material. rice field.

The NMR analysis values of the obtained compound (1-4-4) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.25 (s, 1H), 6.10 (s, 1H), 5.85 (d, J = 1.1Hz, 1H), 5. 57 (s, 1H), 4.33 (d, J = 6.5Hz, 2H), 4.24-4.11 (m, 4H), 2.28 (t, J = 6.6Hz, 1H), 2.09-2.03 (m, 1H), 1.94 (s, 3H), 1.75-1.67 (m, 8H), 1.44-1.39 (m, 2H), 1. 32-1.18 (m, 8H), 1.15-1.06 (m, 4H), 1.02-0.79 (m, 13H).

The physical characteristics of compound (1-4-4) were as follows.
Transition temperature: C 71.4 I.

[Synthesis Example 12]
Synthesis of compound (1-42-1)

Step 1 Compound (T-20) (2.0 g), compound (T-22) (2.63 g), DMAP (0.78 g), and dichloromethane (100 ml) were placed in a reactor and cooled to 0 ° C. .. A solution of DCC (2.92 g) in dichloromethane (60 ml) was slowly added dropwise thereto, and the mixture was stirred for 12 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 9: 1) to give compound (T-44) (2.83 g; 68%).

Step 2 Compound (T-44) (2.83 g), pyridinium p-toluenesulfonate (PPTS) (1.09 g), THF (50 ml) and methanol (50 ml) were placed in the reactor at 50 ° C. for 8 hours. Stirred. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution is concentrated under reduced pressure and the residue is purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 1: 1) to give compound (1-42-1) (1.47 g; 70%). rice field.

The NMR analysis values of the obtained compound (1-42-1) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.24 (s, 2H), 5.82 (s, 2H), 4.35-4.31 (m, 6H), 4.22- 4.19 (m, 2H), 2.36 (s, 2H), 1.97-1.91 (s, 1H), 1.82-1.63 (m, 8H), 1.43-1. 18 (m, 7H), 1.15-0.79 (m, 16H).

The physical characteristics of compound (1-42-1) were as follows.
Transition temperature: C 102 I.

[Synthesis Example 13]
Synthesis of compound (1-43-1)

First Step Compound (T-27) (2.0 g) was used as a raw material, and compound (T-45) (2.7 g; 64%) was obtained by the same method as in the first step of Synthesis Example 12.

Second step Compound (T-45) (2.7 g) was used as a raw material, and compound (1-43-1) (1.3 g; 65%) was obtained by the same method as in the second step of Synthesis Example 12. rice field.

The NMR analysis values of the obtained compound (1-43-1) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.20-7.16 (m, 4H), 6.26 (s, 2H), 5.83 (d, J = 0.8Hz, 2H) ), 4.46 (d, J = 6.6Hz, 4H), 4.28 (d, J = 6.3Hz, 4H), 3.44-3.39 (m, 1H), 2.44 (tt) , J = 12.2Hz, J = 3.1Hz, 1H), 2.16-2.13 (m, 2H), 1.87-1.85 (m, 4H), 1.46-1.19 ( m, 11H), 1.07-0.99 (m, 2H), 0.89 (t, J = 6.8Hz, 3H).

The physical characteristics of compound (1-43-1) were as follows.
Transition temperature: C 65.8 I.

[Synthesis Example 14]
Synthesis of compound (1-44-1)

First Step Compound (T-33) (2.5 g; 59%) was obtained by the same method as in the first step of Synthesis Example 12, using compound (T-33) (2.0 g) as a raw material.

Second step Compound (1-44-1) (1.1 g; 60%) is obtained by the same method as in the second step of Synthesis Example 12, using compound (T-46) (2.7 g) as a raw material. rice field.

The NMR analysis values of the obtained compound (1-44-1) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.14-7.10 (m, 4H), 6.27 (s, 2H), 5.87 (d, J = 1.1Hz, 2H) ), 4.39-4.33 (m, 6H), 4.27-4.20 (m, 2H), 2.57-2.54 (m, 2H), 2.45 (tt, J = 12) .2Hz, J = 3.1Hz, 1H) 2.38-2.35 (m, 2H), 2.05-1.91 (m, 5H), 1.63-1.26 (m, 11H) , 0.88 (t, J = 6.8Hz, 3H).

The physical characteristics of compound (1-44-1) were as follows.
Transition temperature: C 65.6 I.

[Synthesis Example 15]
Synthesis of compound (1-42-2)

First Step Compound (T-42) (2.0 g) was used as a raw material, and compound (T-47) (2.7 g; 67%) was obtained by the same method as in the first step of Synthesis Example 12.

Second step Compound (1-42-2) (1.3 g; 64%) was obtained by the same method as in the second step of Synthesis Example 12, using compound (T-47) (2.7 g) as a raw material. rice field.

The NMR analysis values of the obtained compound (1-42-2) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.25 (s, 2H), 5.85 (d, J = 1.1Hz, 2H), 4.33 (d, J = 6.3Hz) , 4H), 4.25-4.22 (m, 2H), 4.18-4.14 (m, 2H), 2.30-2.28 (m, 2H), 2.11-2.06 (M, 1H), 1.75-1.67 (m, 8H), 1.44-1.39 (m, 2H), 1.32-0.79 (m, 25H).

The physical characteristics of compound (1-42-2) were as follows.
Transition temperature: C 85.7 S _A 125 I.

[Synthesis Example 16]
Synthesis of compound (1-24-2)

First Step Compound (T-24) (50.0 g) and THF (1000 ml) were placed in a reactor and cooled to −70 ° C. Isopropylmagnesium chloride-lithium chloride (1.3 M; THF solution; 130.0 ml) was slowly added dropwise and stirred for 1 hour. DMF (13.0 ml) was added dropwise thereto, and the mixture was stirred for 4 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 4: 1) to give compound (T-48) (34.5 g; 95%).

Second step Methoxymethyl-triphenylphosphonium chloride (54.9 g) and THF (1000 ml) were placed in a reactor and cooled to −30 ° C. Potassium t-butoxide (18.0 g) was added, and the mixture was stirred for 1 hour. A solution of compound (T-48) (34.5 g) in THF (500 ml) was added dropwise thereto, and the mixture was stirred for 5 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 1: 4) to give compound (T-49) (31.7 g; 83%).

Step 3 Compound (T-49) (31.7 g), formic acid (50.9 g), and toluene (1000 ml) were placed in the reactor and stirred at 100 ° C. for 6 hours. After filtering the insoluble material, the reaction mixture was poured into water, neutralized with aqueous sodium hydrogen carbonate, and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 4: 1) to give compound (T-50) (26.5 g; 88%).

Step 4 Compound (T-50) (26.5 g), triethyl phosphonoacetate (26.2 g) and toluene (500 ml) were placed in the reactor and cooled to 0 ° C. Sodium ethoxide (20% ethanol solution) (39.7 g) was slowly added dropwise thereto, and the mixture was stirred for 6 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 9: 1) to give compound (T-51) (30.6 g; 92%).

Step 5 Compound (T-51) (30.6 g), Pd / C (0.55 g), toluene (250 ml), and IPA (250 ml) were placed in the reactor and stirred under a hydrogen atmosphere for 12 hours. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 9: 1) to give compound (T-52) (29.2 g; 95%).

Step 6 Compound (T-52) (29.2 g) and THF (250 ml) were placed in the reactor and cooled to −70 ° C. Lithium diisopropylamide (LDA) (1.1 M; THF solution; 92.5 ml) was slowly added dropwise. The mixture was stirred for 1 hour, benzyl chloromethyl ether (16.0 g) was added dropwise thereto, and the mixture was stirred for 12 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 9: 1) to give compound (T-53) (31.5 g; 80%).

Step 7 Compound (T-53) (31.5 g), palladium hydroxide (0.28 g), toluene (250 ml), and IPA (250 ml) were placed in a reactor and stirred under a hydrogen atmosphere for 12 hours. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 4: 1) to give compound (T-54) (23.3 g; 92%).

Step 8 Compound (T-54) (23.3 g), 3,4-dihydro-2H-pyran (5.8 g), PPTS (pyridinium p-toluenesulfonate) (1.5 g), and dichloromethane (500 ml) Was placed in a reactor and stirred at room temperature for 8 hours. The reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 9: 1) to give compound (T-55) (25.4 g; 89%).

Step 9 Lithium aluminum hydride (LAH) (1.2 g) and THF (300 ml) were placed in a reactor and cooled to 0 ° C. A solution of compound (T-55) (25.4 g) in THF (100 ml) was slowly added dropwise thereto, and the mixture was stirred for 3 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 4: 1) to give compound (T-56) (19.2 g; 83%).

Step 10 Compound (T-56) (19.2 g), triethylamine (7.6 ml) and THF (200 ml) were placed in a reactor and cooled to 0 ° C. Methacryloyl chloride (5.3 ml) was slowly added thereto, and the mixture was stirred for 5 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 19: 1) to give compound (T-57) (17.9 g; 80%).

Step 11 Compound (T-57) (17.9 g), pyridinium p-toluenesulfonate (PPTS) (4.6 g), THF (200 ml) and methanol (200 ml) were placed in a reactor and placed at 50 ° C. for 6 hours. Stirred. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution is concentrated under reduced pressure and the residue is purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 9: 1) to give compound (1-24-2) (12.4 g; 84%). rice field.

The NMR analysis values of the obtained compound (1-24-2) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.13-7.09 (m, 4H), 6.10 (s, 1H), 5.57 (s, 1H), 4.33- 4.30 (m, 1H), 4.23-4.20 (m, 1H), 3.65-3.62 (m, 1H), 3.58-3.54 (m, 1H), 2. 66 (t, J = 8.0Hz, 2H), 2.45-2.39 (m, 1H), 1.94-1.81 (m, 8H), 1.74-1.60 (m, 2H) ), 1.46-
1.19 (m, 12H), 1.07-0.99 (m, 2H), 0.89 (t, J = 6.9Hz, 3H).

The physical characteristics of compound (1-24-2) were as follows.
Transition temperature: C-24.7 I.

[Synthesis Example 17]
Synthesis of compound (1-5-2)

First step Compound (T-58) (2.1 g; 74%) is obtained by using the compound (1-24-2) (2.0 g) as a raw material and the same method as in the third step of Synthesis Example 5. rice field.

Second step Using the compound (T-58) (2.1 g) as a raw material, the compound (1-5-2) (1.4 g; 78%) was obtained by the same method as in the fourth step of Synthesis Example 5. rice field.

The NMR analysis values of the obtained compound (1-5-2) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.14-7.08 (m, 4H), 6.24 (s, 1H), 6.10 (s, 1H), 5.85 ( s, 1H), 5.57 (s, 1H), 4.32 (d, J = 6.1Hz, 2H), 4.27-4.18 (m, 4H), 2.67 (t, J = 7.4Hz, 2H), 2.45-2.40 (m, 2H), 2.18-2.12 (m, 1H), 1.93 (s, 3H), 1.88-1.84 ( m, 4H), 1.77-1.72 (m, 2H), 1.46-1.38 (m, 2H), 1.34-1.19
(M, 9H), 1.07-0.99 (m, 2H), 0.89 (t, J = 6.8Hz, 3H).

The physical characteristics of compound (1-5-2) were as follows.
Transition temperature: C -30.2 S _A -26.3 I.

[Synthesis Example 18]
Synthesis of compound (1-25-2)

First step Methoxymethyl-triphenylphosphonium chloride (84.2 g) and THF (1000 ml) were placed in a reactor and cooled to −30 ° C. Potassium t-butoxide (27.6 g) was added, and the mixture was stirred for 1 hour. A solution of compound (T-29) (50.0 g) in THF (500 ml) was added dropwise thereto, and the mixture was stirred for 5 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 1: 4) to give compound (T-59) (46.3 g; 83%).

Second Step Compound (T-59) (46.3 g), p-toluenesulfonic acid (PTSA) (3.2 g), and toluene (1000 ml) were placed in a reactor and stirred at 100 ° C. for 12 hours. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 1: 1) to give compound (T-60) (49.2 g; 95%).

Step 3 Compound (T-60) (49.2 g), formic acid (74.4 g), and toluene (1000 ml) were placed in the reactor and stirred at room temperature for 8 hours. After filtering the insoluble material, the reaction mixture was poured into water and neutralized with aqueous sodium hydrogen carbonate. The aqueous layer was extracted with toluene, the combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 1: 1) to give compound (T-61) (35.0 g; 84%).

Step 4 Methoxymethyl-triphenylphosphonium chloride (55.7 g) and THF (1000 ml) were placed in the reactor and cooled to −30 ° C. Potassium t-butoxide (18.2 g) was added, and the mixture was stirred for 1 hour. A solution of compound (T-61) (35.0 g) in THF (500 ml) was added dropwise thereto, and the mixture was stirred for 5 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 1: 4) to give compound (T-62) (36.5 g; 94%).

Step 5 Compound (T-62) (36.5 g), formic acid (58.6 g), and toluene (1000 ml) were placed in the reactor and stirred at 100 ° C. for 4 hours. After filtering the insoluble material, the reaction mixture was poured into water and neutralized with aqueous sodium hydrogen carbonate. The aqueous layer was extracted with toluene, the combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 1: 1) to give compound (T-63) (33.0 g; 95%).

6th step Compound (T-63) (38.2 g; 92%) was obtained by the same method as in the 4th step of Synthesis Example 16 using the compound (T-63) (33.0 g) as a raw material.

7th step Compound (T-65) (18.7 g; 48%) was obtained by using the compound (T-64) (38.2 g) as a raw material in the same manner as in the 5th step of Synthesis Example 16.

Eighth step Compound (T-66) (21.5 g; 85%) was obtained by using the compound (T-65) (18.7 g) as a raw material in the same manner as in the sixth step of Synthesis Example 16.

Step 9 Compound (T-66) (15.6 g; 90%) was obtained by the same method as in Step 7 of Synthesis Example 16 using compound (T-66) (21.5 g) as a raw material.

Step 10 Compound (T-68) (16.8 g; 88%) was obtained in the same manner as in Step 8 of Synthesis Example 16 using compound (T-67) (15.6 g) as a raw material.

11th Step Compound (T-69) (13.0g; 85%) was obtained by using the compound (T-68) (16.8g) as a raw material in the same manner as in the 9th step of Synthesis Example 16.

Step 12 Compound (T-69) (11.6 g; 77%) was obtained in the same manner as in Step 10 of Synthesis Example 16 using compound (T-69) (13.0 g) as a raw material.

Step 13 Compound (T-70) (11.6 g) was used as a raw material, and compound (1-25-2) (7.8 g; 82%) was obtained by the same method as in Step 11 of Synthesis Example 16. rice field.

The NMR analysis values of the obtained compound (1-25-2) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.11-7.08 (m, 4H), 6.11 (s, 1H), 5.57 (s, 1H), 4.31- 4.28 (m, 1H), 4.19-4.16 (m, 1H), 3.63-3.60 (m, 1H), 3.55-3.52 (m, 1H), 1. 95 (s, 3H), 1.89-1.81 (m, 5H), 1.62-1.56 (m, 2H), 1.47-1.28 (m, 12H), 1.09- 1.01 (m, 2H), 0.88 (t, J = 6.7Hz, 3H).

The physical characteristics of compound (1-25-2) were as follows.
Transition temperature: C <-50 I.

[Synthesis Example 19]
Synthesis of compound (1-6-2)

First step Compound (T-71) (3.2 g; 75%) is obtained by using the compound (1-25-2) (3.0 g) as a raw material and the same method as in the third step of Synthesis Example 5. rice field.

Second step Using the compound (T-71) (3.2 g) as a raw material, the compound (1-6-2) (1.9 g; 70%) was obtained by the same method as in the fourth step of Synthesis Example 5. rice field.

The NMR analysis values of the obtained compound (1-6-2) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.12-7.08 (m, 4H), 6.26 (s, 1H), 6.11 (s, 1H), 5.86 ( s, 1H), 5.58 (s, 1H), 4.34 (d, J = 6.5Hz, 2H), 4.26-4.14 (m, 4H), 2.55 (t, J = 7.8Hz, 2H), 2.45-2.40 (m, 1H), 2.34
(S, 1H), 2.13-2.08 (m, 1H), 1.95 (s, 3H), 1.90-1.84 (m, 4H), 1.63-1.56 (m) , 2H), 1.48-1.39 (m, 4H), 1.35-1.27 (m, 7H), 1.09-1.01 (m, 2H), 0.88 (t, J) = 6.8Hz, 3H).

The physical characteristics of compound (1-6-2) were as follows.
Transition temperature: C 35.9 I.

[Synthesis Example 20]
Synthesis of compound (1-281)

1st step
Using compound (T-72) (50.0 g) as a raw material, compound (T-73) (31.8 g; 70%) was obtained by the same method as in the first step of Synthesis Example 6.

Second Step Compound (T-73) (26.2 g; 72%) was obtained by the same method as in the second step of Synthesis Example 6 using the compound (T-73) (31.8 g) as a raw material.

Third step Using the compound (T-74) (26.2 g) as a raw material, the compound (T-75) (10.1 g; 46%) was obtained by the same method as in the third step of Synthesis Example 6.

Step 4 Compound (T-75) (10.1 g) was used as a raw material, and compound (1-281) (3.8 g; 32%) was obtained by the same method as in Step 4 of Synthesis Example 6. rice field.

The NMR analysis values of the obtained compound (1-281) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.18-7.16 (m, 4H), 6.09 (s, 1H), 5.57 (s, 1H), 4.47- 4.38 (m, 2H), 3.91-3.83 (m, 2H), 3.20-3.14 (m, 1H), 2.45-2.40 (m, 1H), 1. 97-1.72 (m, 12H), 1.42-0.82 (m, 22H).

The physical characteristics of compound (1-281) were as follows.
Transition temperature: C 46.3 I.

[Synthesis Example 21]
Synthesis of compound (1-9-1)

1st step
Using compound (1-281) (3.0 g) as a raw material, compound (T-76) (3.1 g; 75%) was obtained by the same method as in the third step of Synthesis Example 5.

Second step
Using compound (T-76) (3.1 g) as a raw material, compound (1-9.1) (1.9 g; 71%) was obtained by the same method as in the fourth step of Synthesis Example 5.

The NMR analysis values of the obtained compound (1-9-1) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.17 (s, 4H), 6.21 (s, 1H), 6.07 (s, 1H), 5.80 (s, 1H) 5,56 (s, 1H), 4.46-4.39 (m, 4H), 4.27 (d, J = 6.6Hz, 2H), 3.42-3.37 (m, 1H) , 2.45-2.39 (m, 1H), 2.12 (t, J = 6.6Hz, 1H), 1.91-1.72 (m, 11H), 1.46-0.95 ( m, 16H), 0.89-0.82 (m, 5H).

The physical characteristics of compound (1-9-1) were as follows.
Transition temperature: C 80.0 I.

[Synthesis Example 22]
Synthesis of compound (1-23-4)

1st step
Compound (T-77) (50.0 g), triethyl phosphonoacetate (48.3 g) and toluene (500 ml) were placed in the reactor and cooled to 0 ° C. Sodium ethoxide (20% ethanol solution) (73.3 g) was slowly added dropwise thereto, and the mixture was stirred for 6 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 9: 1) to give compound (T-78) (60.7 g; 97%).

Second Step Compound (T-78) (60.7 g), Pd / C (0.51 g), toluene (500 ml), and IPA (50 ml) were placed in a reactor and stirred under a hydrogen atmosphere for 12 hours. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 9: 1) and further purified by recrystallization from Solmix to compound (T-79) ( 33.6 g; 55%) was obtained.

Third Step Compound (T-79) (33.6 g) was used as a raw material to obtain Compound (T-80) (38.8 g; 86%) by the same method as in the sixth step of Synthesis Example 16.

Fourth Step Compound (T-80) (38.8 g) was used as a raw material to obtain Compound (T-81) (29.8 g; 95%) by the same method as in the seventh step of Synthesis Example 16.

Fifth step Using the compound (T-81) (29.8 g) as a raw material, the compound (T-82) (34.6 g; 95%) was obtained by the same method as in the eighth step of Synthesis Example 16.

6th Step Compound (T-83) (30.5 g; 97%) was obtained by using the compound (T-82) (34.6 g) as a raw material in the same manner as in the 9th step of Synthesis Example 16.

Step 7 Compound (T-83) (30.5 g) was used as a raw material to obtain compound (T-84) (26.6 g; 75%) by the same method as in Step 10 of Synthesis Example 16.

Eighth step Compound (1-23-4) (18.3 g; 83%) was obtained by using the compound (T-84) (26.6 g) as a raw material and the same method as in the eleventh step of Synthesis Example 16. rice field.

The NMR analysis values of the obtained compound (1-23-4) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.10 (s, 1H), 5.57 (s, 1H), 4.40-4.37 (m, 1H), 4.24- 4.20 (m, 1H), 3.69-3.61 (m, 2H), 1.9-1.94 (m, 4H), 1.78-1.58 (m, 9H), 1. 43-1.37 (m, 1H), 1.32-1.02 (m, 17H), 0.90-0.79 (m, 9H).

The physical characteristics of compound (1-23-4) were as follows.
Transition temperature: C 54.5 S _A 81.0 I.

[Synthesis Example 23]
Synthesis of compound (1-4-5)

1st step
Using compound (1-23-4) (3.0 g) as a raw material, compound (T-85) (3.3 g; 78%) was obtained by the same method as in the third step of Synthesis Example 5.

Second step
Using compound (T-85) (3.3 g) as a raw material, compound (1-4-5) (2.1 g; 75%) was obtained by the same method as in the fourth step of Synthesis Example 5.

The NMR analysis values of the obtained compound (1-4-5) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.24 (s, 1H), 6.09 (s, 1H), 5.84 (s, 1H), 5.56 (s, 1H) 4.33-4.28 (m, 4H), 4.20-4.16 (m, 2H), 2.28 (t, J = 6.6Hz, 1H), 1.97-1.91 ( m, 4H) 1.79-1.69 (m, 8H), 1.47-1.41 (m, 1H), 1.32-1.07 (m, 17H), 0.90-0. 82 (m, 9H).

The physical characteristics of compound (1-4-5) were as follows.
Transition temperature: C 64.0 I.

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

Table 3 Notation of compounds using symbols R- (A ₁ ) -Z ₁ -... Z _n- ( _An ) -R'

Example of element 1. A composition in which a compound having a polymerizable group and a polar group was added to the branched structure at the molecular terminal was injected into an element having no raw material alignment film. After irradiating with ultraviolet rays, the vertical orientation of the liquid crystal molecules in this device was examined. First, the raw materials will be described. The raw materials are from the composition (M1) to (M18), from the compound (PC-1) to (PC-28) having a polymerizable group and a polar group in the branched structure at the molecular terminal, and from the polymerizable compound (RM-1) (RM-1). RM-8), and are listed in this order.

[Composition M1]
3-HB (2F, 3F) -O2 (2-1) 10%
5-HB (2F, 3F) -O2 (2-1) 7%
2-BB (2F, 3F) -O2 (2-4) 7%
3-BB (2F, 3F) -O2 (2-4) 7%
3-B (2F, 3F) B (2F, 3F) -O2 (2-5) 3%
2-HHB (2F, 3F) -O2 (2-6) 5%
3-HHB (2F, 3F) -O2 (2-6) 10%
2-HBB (2F, 3F) -O2 (2-10) 8%
3-HBB (2F, 3F) -O2 (2-10) 10%
2-HH-3 (3-1) 14%
3-HB-O1 (3-2) 5%
3-HHB-1 (3-5) 3%
3-HHB-O1 (3-5) 3%
3-HHB-3 (3-5) 4%
2-BB (F) B-3 (3-8) 4%
NI = 73.2 ° C; Tc <-20 ° C; Δn = 0.113; Δε = -4.0; Vth = 2.18V; η = 22.6 mPa · s.

[Composition M2]
3-HB (2F, 3F) -O4 (2-1) 6%
3-H2B (2F, 3F) -O2 (2-2) 8%
3-H1OB (2F, 3F) -O2 (2-3) 4%
3-BB (2F, 3F) -O2 (2-4) 7%
2-HHB (2F, 3F) -O2 (2-6) 7%
3-HHB (2F, 3F) -O2 (2-6) 7%
3-HH2B (2F, 3F) -O2 (2-7) 7%
5-HH2B (2F, 3F) -O2 (2-7) 4%
2-HBB (2F, 3F) -O2 (2-10) 5%
3-HBB (2F, 3F) -O2 (2-10) 5%
4-HBB (2F, 3F) -O2 (2-10) 6%
2-HH-3 (3-1) 12%
1-BB-5 (3-3) 12%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 3%
3-HBB-2 (3-6) 3%
NI = 82.8 ° C; Tc <-30 ° C; Δn = 0.118; Δε = -4.4; Vth = 2.13V; η = 22.5 mPa · s.

[Composition M3]
3-HB (2F, 3F) -O2 (2-1) 7%
5-HB (2F, 3F) -O2 (2-1) 7%
3-BB (2F, 3F) -O2 (2-4) 8%
3-HHB (2F, 3F) -O2 (2-6) 5%
5-HHB (2F, 3F) -O2 (2-6) 4%
3-HH1OB (2F, 3F) -O2 (2-8) 4%
2-BB (2F, 3F) B-3 (2-9) 5%
2-HBB (2F, 3F) -O2 (2-10) 3%
3-HBB (2F, 3F) -O2 (2-10) 8%
4-HBB (2F, 3F) -O2 (2-10) 5%
5-HBB (2F, 3F) -O2 (2-10) 8%
3-HH-V (3-1) 27%
3-HH-V1 (3-1) 6%
V-HHB-1 (3-5) 3%
NI = 78.1 ° C.; Tc <-30 ° C.; Δn = 0.107; Δε = -3.2; Vth = 2.02V; η = 15.9 mPa · s.

[Composition M4]
3-HB (2F, 3F) -O2 (2-1) 10%
5-HB (2F, 3F) -O2 (2-1) 10%
3-H2B (2F, 3F) -O2 (2-2) 8%
5-H2B (2F, 3F) -O2 (2-2) 8%
2-HBB (2F, 3F) -O2 (2-10) 6%
3-HBB (2F, 3F) -O2 (2-10) 8%
4-HBB (2F, 3F) -O2 (2-10) 7%
5-HBB (2F, 3F) -O2 (2-10) 7%
3-HDhB (2F, 3F) -O2 (2-16) 5%
3-HH-4 (3-1) 14%
V-HHB-1 (3-5) 10%
3-HBB-2 (3-6) 7%
NI = 88.5 ° C; Tc <-30 ° C; Δn = 0.108; Δε = -3.8; Vth = 2.25V; η = 24.6mPa · s;

[Composition M5]
3-HB (2F, 3F) -O2 (2-1) 7%
3-HB (2F, 3F) -O4 (2-1) 8%
3-H2B (2F, 3F) -O2 (2-2) 8%
3-BB (2F, 3F) -O2 (2-4) 10%
2-HHB (2F, 3F) -O2 (2-6) 4%
3-HHB (2F, 3F) -O2 (2-6) 7%
3-HHB (2F, 3F) -1 (2-6) 6%
2-HBB (2F, 3F) -O2 (2-10) 6%
3-HBB (2F, 3F) -O2 (2-10) 6%
4-HBB (2F, 3F) -O2 (2-10) 5%
5-HBB (2F, 3F) -O2 (2-10) 4%
3-HEB (2F, 3F) B (2F, 3F) -O2
(2-11) 3%
3-H1OCro (7F, 8F) -5 (2-14) 3%
3-HDhB (2F, 3F) -O2 (2-16) 5%
3-HH-O1 (3-1) 5%
1-BB-5 (3-3) 4%
V-HHB-1 (3-5) 4%
5-HB (F) BH-3 (3-12) 5%
NI = 81.1 ° C; Tc <-30 ° C; Δn = 0.119; Δε = −4.5; Vth = 1.69V; η = 31.4mPa · s.

[Composition M6]
3-HB (2F, 3F) -O4 (2-1) 15%
3-HBB (2F, 3F) -O2 (2-10) 8%
4-HBB (2F, 3F) -O2 (2-10) 5%
5-HBB (2F, 3F) -O2 (2-10) 7%
3-dhBB (2F, 3F) -O2 (2-17) 5%
3-chB (2F, 3F) -O2 (2-18) 7%
2-HchB (2F, 3F) -O2 (2-19) 8%
5-HH-V (3-1) 18%
7-HB-1 (3-2) 5%
V-HHB-1 (3-5) 7%
V2-HHB-1 (3-5) 7%
3-HBB (F) B-3 (3-13) 8%
NI = 98.8 ° C; Tc <-30 ° C; Δn = 0.111; Δε = -3.2; Vth = 2.47V; η = 23.9mPa · s.

[Composition M7]
3-H2B (2F, 3F) -O2 (2-2) 18%
5-H2B (2F, 3F) -O2 (2-2) 17%
3-HHB (2F, 3CL) -O2 (2-12) 5%
3-HBB (2F, 3CL) -O2 (2-13) 8%
5-HBB (2F, 3CL) -O2 (2-13) 7%
3-HDhB (2F, 3F) -O2 (2-16) 5%
3-HH-V (3-1) 11%
3-HH-VFF (3-1) 7%
F3-HH-V (3-1) 10%
3-HHEH-3 (3-4) 4%
3-HB (F) HH-2 (3-10) 4%
3-HHEBH-3 (3-11) 4%
NI = 77.5 ° C; Tc <-30 ° C; Δn = 0.084; Δε = -2.6; Vth = 2.43V; η = 22.8 mPa · s.

[Composition M8]
3-HB (2F, 3F) -O2 (2-1) 8%
3-H2B (2F, 3F) -O2 (2-2) 10%
3-BB (2F, 3F) -O2 (2-4) 10%
2O-BB (2F, 3F) -O2 (2-4) 3%
2-HHB (2F, 3F) -O2 (2-6) 4%
3-HHB (2F, 3F) -O2 (2-6) 7%
2-HHB (2F, 3F) -1 (2-6) 5%
2-BB (2F, 3F) B-3 (2-9) 6%
2-BB (2F, 3F) B-4 (2-9) 6%
2-HBB (2F, 3F) -O2 (2-10) 4%
3-HBB (2F, 3F) -O2 (2-10) 7%
3-HH1OCro (7F, 8F) -5 (2-15) 4%
3-HDhB (2F, 3F) -O2 (2-16) 6%
3-dhBB (2F, 3F) -O2 (2-17) 4%
3-HH-V (3-1) 11%
1-BB-5 (3-3) 5%
NI = 70.6 ° C; Tc <-20 ° C; Δn = 0.129; Δε = -4.3; Vth = 1.69V; η = 27.0 mPa · s.

[Composition M9]
3-HB (2F, 3F) -O4 (2-1) 14%
3-H1OB (2F, 3F) -O2 (2-3) 3%
3-BB (2F, 3F) -O2 (2-4) 10%
2-HHB (2F, 3F) -O2 (2-6) 7%
3-HHB (2F, 3F) -O2 (2-6) 7%
3-HH1OB (2F, 3F) -O2 (2-8) 6%
2-HBB (2F, 3F) -O2 (2-10) 4%
3-HBB (2F, 3F) -O2 (2-10) 6%
4-HBB (2F, 3F) -O2 (2-10) 4%
3-HH-V (3-1) 14%
1-BB-3 (3-3) 3%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 4%
V-HBB-2 (3-6) 4%
1-BB (F) B-2V (3-8) 6%
5-HBBH-1O1 (-) 4%
NI = 93.0 ° C; Tc <-30 ° C; Δn = 0.123; Δε = -4.0; Vth = 2.27V; η = 29.6 mPa · s.

[Composition M10]
3-HB (2F, 3F) -O4 (2-1) 6%
3-H2B (2F, 3F) -O2 (2-2) 8%
3-H1OB (2F, 3F) -O2 (2-3) 5%
3-BB (2F, 3F) -O2 (2-4) 10%
2-HHB (2F, 3F) -O2 (2-6) 7%
3-HHB (2F, 3F) -O2 (2-6) 7%
5-HHB (2F, 3F) -O2 (2-6) 7%
2-HBB (2F, 3F) -O2 (2-10) 4%
3-HBB (2F, 3F) -O2 (2-10) 7%
5-HBB (2F, 3F) -O2 (2-10) 6%
3-HH-V (3-1) 11%
1-BB-3 (3-3) 6%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 4%
3-HBB-2 (3-6) 4%
3-B (F) BB-2 (3-7) 4%
NI = 87.6 ° C; Tc <-30 ° C; Δn = 0.126; Δε = −4.5; Vth = 2.21V; η = 25.3 mPa · s.

[Composition M11]
3-HB (2F, 3F) -O4 (2-1) 6%
3-H2B (2F, 3F) -O2 (2-2) 8%
3-H1OB (2F, 3F) -O2 (2-3) 4%
3-BB (2F, 3F) -O2 (2-4) 7%
2-HHB (2F, 3F) -O2 (2-6) 6%
3-HHB (2F, 3F) -O2 (2-6) 10%
5-HHB (2F, 3F) -O2 (2-6) 8%
2-HBB (2F, 3F) -O2 (2-10) 5%
3-HBB (2F, 3F) -O2 (2-10) 7%
5-HBB (2F, 3F) -O2 (2-10) 5%
2-HH-3 (3-1) 12%
1-BB-3 (3-3) 6%
3-HHB-1 (3-5) 3%
3-HHB-O1 (3-5) 4%
3-HBB-2 (3-6) 6%
3-B (F) BB-2 (3-7) 3%
NI = 93.0 ° C; Tc <-20 ° C; Δn = 0.124; Δε = −4.5; Vth = 2.22V; η = 25.0 mPa · s.

[Composition M12]
3-HB (2F, 3F) -O2 (2-1) 7%
5-HB (2F, 3F) -O2 (2-1) 7%
3-BB (2F, 3F) -O2 (2-4) 8%
3-HHB (2F, 3F) -O2 (2-6) 4%
5-HHB (2F, 3F) -O2 (2-6) 5%
3-HH1OB (2F, 3F) -O2 (2-8) 5%
2-BB (2F, 3F) B-3 (2-9) 4%
2-HBB (2F, 3F) -O2 (2-10) 3%
3-HBB (2F, 3F) -O2 (2-10) 8%
4-HBB (2F, 3F) -O2 (2-10) 5%
5-HBB (2F, 3F) -O2 (2-10) 8%
3-HH-V (3-1) 33%
V-HHB-1 (3-5) 3%
NI = 76.4 ° C; Tc <-30 ° C; Δn = 0.104; Δε = -3.2; Vth = 2.06V; η = 15.6 mPa · s.

[Composition M13]
2-H1OB (2F, 3F) -O2 (2-3) 6%
3-H1OB (2F, 3F) -O2 (2-3) 4%
3-BB (2F, 3F) -O2 (2-4) 3%
2-HH1OB (2F, 3F) -O2 (2-8) 14%
2-HBB (2F, 3F) -O2 (2-10) 7%
3-HBB (2F, 3F) -O2 (2-10) 11%
5-HBB (2F, 3F) -O2 (2-10) 9%
2-HH-3 (3-1) 5%
3-HH-VFF (3-1) 30%
1-BB-3 (3-3) 5%
3-HHB-1 (3-5) 3%
3-HBB-2 (3-6) 3%
NI = 78.3 ° C; Tc <-20 ° C; Δn = 0.103; Δε = -3.2; Vth = 2.17V; η = 17.7mPa · s.

[Composition M14]
3-HB (2F, 3F) -O2 (2-1) 5%
5-HB (2F, 3F) -O2 (2-1) 7%
3-BB (2F, 3F) -O2 (2-4) 8%
3-HHB (2F, 3F) -O2 (2-6) 5%
5-HHB (2F, 3F) -O2 (2-6) 4%
3-HH1OB (2F, 3F) -O2 (2-8) 5%
2-BB (2F, 3F) B-3 (2-9) 4%
2-HBB (2F, 3F) -O2 (2-10) 3%
3-HBB (2F, 3F) -O2 (2-10) 9%
4-HBB (2F, 3F) -O2 (2-10) 4%
5-HBB (2F, 3F) -O2 (2-10) 8%
3-HH-V (3-1) 27%
3-HH-V1 (3-1) 6%
V-HHB-1 (3-5) 5%
NI = 81.2 ° C; Tc <-20 ° C; Δn = 0.107; Δε = -3.2; Vth = 2.11V; η = 15.5 mPa · s.

[Composition M15]
3-H2B (2F, 3F) -O2 (2-2) 7%
3-HHB (2F, 3F) -O2 (2-6) 8%
3-HH1OB (2F, 3F) -O2 (2-8) 5%
2-BB (2F, 3F) B-3 (2-9) 7%
2-BB (2F, 3F) B-4 (2-9) 7%
3-HDhB (2F, 3F) -O2 (2-16) 3%
5-HDhB (2F, 3F) -O2 (2-16) 4%
2-HchB (2F, 3F) -O2 (2-19) 8%
4-HH-V (3-1) 15%
3-HH-V1 (3-1) 6%
1-HH-2V1 (3-1) 6%
3-HH-2V1 (3-1) 4%
V2-BB-1 (3-3) 5%
1V2-BB-1 (3-3) 5%
3-HHB-1 (3-5) 6%
3-HB (F) BH-3 (3-12) 4%
NI = 88.7 ° C; Tc <-30 ° C; Δn = 0.115; Δε = -1.9; Vth = 2.82V; η = 17.3mPa · s.

[Composition M16]
V2-H2B (2F, 3F) -O2 (2-2) 8%
V2-H1OB (2F, 3F) -O4 (2-3) 4%
3-BB (2F, 3F) -O2 (2-4) 7%
2-HHB (2F, 3F) -O2 (2-6) 7%
3-HHB (2F, 3F) -O2 (2-6) 7%
3-HH2B (2F, 3F) -O2 (2-7) 7%
5-HH2B (2F, 3F) -O2 (2-7) 4%
V-HH2B (2F, 3F) -O2 (2-7) 6%
V2-HBB (2F, 3F) -O2 (2-10) 5%
V-HBB (2F, 3F) -O2 (2-10) 5%
V-HBB (2F, 3F) -O4 (2-10) 6%
2-HH-3 (3-1) 12%
1-BB-5 (3-3) 12%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 3%
3-HBB-2 (3-6) 3%
NI = 89.9 ° C; Tc <-20 ° C; Δn = 0.122; Δε = -4.2; Vth = 2.16V; η = 23.4 mPa · s.

[Composition M17]
3-HB (2F, 3F) -O2 (2-1) 3%
V-HB (2F, 3F) -O2 (2-1) 3%
V2-HB (2F, 3F) -O2 (2-1) 5%
5-H2B (2F, 3F) -O2 (2-2) 5%
V2-BB (2F, 3F) -O2 (2-4) 3%
1V2-BB (2F, 3F) -O2 (2-4) 3%
3-HHB (2F, 3F) -O2 (2-6) 6%
V-HHB (2F, 3F) -O2 (2-6) 6%
V-HHB (2F, 3F) -O4 (2-6) 5%
V2-HHB (2F, 3F) -O2 (2-6) 4%
V2-BB (2F, 3F) B-1 (2-9) 4%
V2-HBB (2F, 3F) -O2 (2-10) 5%
V-HBB (2F, 3F) -O2 (2-10) 4%
V-HBB (2F, 3F) -O4 (2-10) 5%
V-HHB (2F, 3CL) -O2 (2-12) 3%
3-HH-V (3-1) 27%
3-HH-V1 (3-1) 6%
V-HHB-1 (3-5) 3%
NI = 77.1 ° C; Tc <-20 ° C; Δn = 0.101; Δε = −3.0; Vth = 2.04V; η = 13.9 mPa · s.

[Composition M18]
V-HB (2F, 3F) -O2 (2-1) 10%
V2-HB (2F, 3F) -O2 (2-1) 10%
2-H1OB (2F, 3F) -O2 (2-3) 3%
3-H1OB (2F, 3F) -O2 (2-3) 3%
2O-BB (2F, 3F) -O2 (2-4) 3%
V2-BB (2F, 3F) -O2 (2-4) 8%
V2-HHB (2F, 3F) -O2 (2-6) 5%
2-HBB (2F, 3F) -O2 (2-10) 3%
3-HBB (2F, 3F) -O2 (2-10) 3%
V-HBB (2F, 3F) -O2 (2-10) 6%
V-HBB (2F, 3F) -O4 (2-10) 8%
V-HHB (2F, 3CL) -O2 (2-12) 7%
3-HH-4 (3-1) 14%
V-HHB-1 (3-5) 10%
3-HBB-2 (3-6) 7%
NI = 75.9 ° C; Tc <-20 ° C; Δn = 0.114; Δε = -3.9; Vth = 2.20V; η = 24.7mPa · s.

[Composition M19]
3-HB (2F, 3F) -O2 (2-1) 12%
2-HH1OB (2F, 3F) -O2 (2-8) 10%
3-HH1OB (2F, 3F) -O2 (2-8) 9%
2OB (2F) B (2F, 3F) -O2 (2-22) 4%
2O-B (2F) B (2F, 3F) -O4 (2-22) 5%
2-HH-3 (3-1) 25%
3-HH-4 (3-1) 6%
1-BB-3 (3-3) 4%
3-HHB-1 (3-5) 9%
3-HBB-2 (3-6) 7%
5-B (F) BB-2 (3-7) 9%
NI = 74.2 ° C; Tc <-20 ° C; Δn = 0.103; Δε = -2.5; Vth = 2.36V; η = 18.4mPa · s.

[Composition M20]
3-H1OB (2F, 3F) -O2 (2-3) 10%
V-HHB (2F, 3F) -O2 (2-6) 5%
2-HH1OB (2F, 3F) -O2 (2-8) 4%
3-HBB (2F, 3F) -O2 (2-10) 5%
V-HBB (2F, 3F) -O2 (2-10) 9%
2OB (2F) B (2F, 3F) -O2 (2-22) 5%
2O-B (2F) B (2F, 3F) -O4 (2-22) 5%
2-HH-3 (3-1) 22%
3-HH-4 (3-1) 5%
3-HH-5 (3-1) 3%
3-HB-O2 (3-2) 10%
3-HHB-1 (3-5) 8%
3-HHB-3 (3-5) 4%
5-B (F) BB-2 (3-7) 5%
NI = 74.9 ° C; Tc <-20 ° C; Δn = 0.102; Δε = -2.8; Vth = 2.30V; η = 19.2mPa · s.

[Composition M21]
3-HB (2F, 3F) -O2 (2-1) 12%
5-HB (2F, 3F) -O2 (2-1) 8%
3-HH2B (2F, 3F) -O2 (2-7) 9%
3-HDhB (2F, 3F) -O2 (2-16) 9%
3-dhBB (2F, 3F) -O2 (2-17) 7%
2OB (2F) B (2F, 3F) -O2 (2-22) 5%
3-HH-V (3-1) 29%
2-HH-3 (3-1) 2%
V-HHB-1 (3-5) 5%
V-HBB-2 (3-6) 14%
NI = 76.5 ° C; Tc <-20 ° C; Δn = 0.098; Δε = −3.0; Vth = 2.15V; η = 16.2 mPa · s.

[Composition M22]
2-HHB (2F, 3F) -O2 (2-6) 3%
3-HHB (2F, 3F) -O2 (2-6) 6%
V-HHB (2F, 3F) -O1 (2-6) 4%
V-HHB (2F, 3F) -O2 (2-6) 10%
3-HH2B (2F, 3F) -O2 (2-7) 9%
2OB (2F) B (2F, 3F) -O2 (2-22) 7%
2OB (2F) B (2F, 3F) -O4 (2-22) 7%
3-HH-V (3-1) 20%
2-HH-3 (3-1) 10%
3-HH-4 (3-1) 6%
3-HB-O2 (3-2) 7%
1-BB-3 (3-3) 4%
5-B (F) BB-2 (3-7) 7%
NI = 75.3 ° C; Tc <-20 ° C; Δn = 0.102; Δε = -2.6; Vth = 2.41V; η = 17.5 mPa · s.

The following compounds (PC-1) to (PC-28) having a polymerizable group and a polar group in the branched structure at the molecular terminal were used as the first additive.

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

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

Examples 2 to 55 and Comparative Examples 1-2
An element having no alignment film was prepared by using a mixture of the composition and a compound having a polymerizable group and a polar group in the branched structure at the molecular terminal. The presence or absence of light leakage was observed by the same method as in Example 1. The results are summarized in Tables 4 and 5. In Example 18, a polymerizable compound (RM-1) was also added in a proportion of 0.5% by weight. In Comparative Example 1, the following polar compound (A-1) described in Patent Document 5 was selected for comparison. This compound is different from compound (1-1) because it does not have a branched structure from the end of the molecule.

表５ 液晶分子の垂直配向

Table 4 Vertical orientation of liquid crystal molecules

Table 5 Vertical orientation of liquid crystal molecules

As can be seen from Tables 4 and 5, in Examples 1 to 55, the types of compositions and first additives and the concentrations of polar compounds were changed, but no light leakage was observed. This result indicates that the vertical orientation is good even if the device does not have an alignment film, and the liquid crystal molecules are stably oriented. In Examples 18 and 40, the second additive, the polymerizable compound (RM-1), was further added, and similar results were obtained. On the other hand, in Comparative Examples 1 and 2, light leakage was observed. This result indicates that the vertical orientation was not good.

3. 3. Compatibility of Polar Compounds The stability of the mixture of the liquid crystal composition and the first additive obtained in the above example at room temperature was evaluated. After mixing, it was isotropicized at 100 ° C. and allowed to cool to 25 ° C. When the presence or absence of precipitation was confirmed after half a day at room temperature, no precipitation was confirmed in the mixture of Examples 1 to 55, and the compatibility of the first additive was good. On the other hand, precipitation was confirmed in the mixture of Comparative Examples 1 and 2, and the compatibility of the polar compound was poor.

From the above results, the polymer produced from the compound having a polymerizable group and a polar group in the branched structure at the molecular terminal plays an important role in the vertical orientation of the liquid crystal molecule, and the compatibility with the liquid crystal composition is also improved. You can see that. Such a tendency is the same even when the compounds shown in Synthesis Examples 1 to 23 other than the compounds (PC-1) to the compound (PC-28) shown in Tables 4 and 5 are used. Therefore, when the liquid crystal composition of the present invention is used, an AM device having characteristics such as a short response time, a large voltage retention rate, a low threshold voltage, a large contrast ratio, and a long life can be obtained. In addition, the high upper temperature of the nematic phase, the lower lower temperature of the nematic phase, small viscosity, proper optical anisotropy, negatively large permittivity anisotropy, large specific resistance, high stability to ultraviolet rays, high stability to heat. A liquid crystal display element having a liquid crystal composition satisfying at least one of the characteristics such as is obtained.

The liquid crystal composition of the present invention can control the orientation of liquid crystal molecules in an element having no alignment film, and can be used for liquid crystal projectors, liquid crystal monitors, liquid crystal televisions, and the like.

Claims (21)

It contains at least one polymerizable polar compound selected from the group of compounds represented by formulas (1-4) to (1-60) as the first additive and has a negative dielectric anisotropy. Liquid crystal composition having.

In equations (1-4) to (1-60),
R ¹ is an alkyl with 1 to 10 carbon atoms;
Z ^{1, Z 12,} and ^{Z 13} are independently a single bond, _-CH 2 CH ₂ -, or - _{(CH 2) 4} - a and;
Sp ¹² , Sp ¹³ , and Sp ¹⁴ are independently single-bonded or 1 to 5 carbon alkylenes, in which at least one -CH ₂ − may be replaced by -O-;
L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ , L ⁸ , L ⁹ , L ¹⁰ , L ¹¹ , and L ¹² are independently hydrogen, fluorine, methyl, or ethyl. can be;
l is 0, 1, 2, 3, 4, 5, or 6. Based on the weight of the liquid crystal composition, a ratio of the first additive is 10 wt% or less, the liquid crystal composition according to claim 1. The liquid crystal composition according to claim 1 or 2 , which contains at least one compound selected from the group of compounds represented by the formula (2) as a first component.

In formula (2), R ³ and R ⁴ are independently composed of an alkyl having 1 to 12 carbon atoms, an alkoxy having 1 to 12 carbon atoms, an alkenyl having 2 to 12 carbon atoms, or an alkenyloxy having 2 to 12 carbon atoms. Yes; Rings C and E are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4- at least one hydrogen replaced with fluorine or chlorine. Phenylene, or tetrahydropyran-2,5-diyl; ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro- 5-Methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl; Z ² and Z ³ are independent. Te single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or a is -OCO-; b is 1, 2, or 3,, c is 0 or It is 1, and the sum of b and c is 3 or less. The liquid crystal according to any one of claims 1 to 3 , which contains at least one compound selected from the group of compounds represented by formulas (2-1) to (2-22) as a first component. Composition.

In formulas (2-1) to (2-22), R ³ and R ⁴ are independently alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or It is an alkoxyoxy having 2 to 12 carbon atoms. The liquid crystal composition according to claim 3 or 4 , wherein the proportion of the first component is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition. The liquid crystal composition according to any one of claims 1 to 5 , which contains at least one compound selected from the group of compounds represented by the formula (3) as the second component.

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

In formulas (3-1) to (3-13), R ⁵ and R ⁶ are independently alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, or at least. An alkyl having 1 to 12 carbon atoms in which one hydrogen has been replaced with fluorine or chlorine, or an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen has been replaced with fluorine or chlorine. The liquid crystal composition according to any one of claims 6 or 7 , wherein the proportion of the second component is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition. The liquid crystal composition according to any one of claims 1 to 8 , which contains at least one polymerizable compound selected from the group of compounds represented by the formula (4) as the second additive.

In formula (4), ring J and ring P are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-. It is 2-yl or pyridine-2-yl, and in these rings at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least one hydrogen. It may be replaced with an alkyl having 1 to 12 carbon atoms replaced with fluorine or chlorine; ring K is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1, 2-Diyl, Naphthalene-1,3-Diyl, Naphthalene-1,4-Diyl, Naphthalene-1,5-Diyl, Naphthalene-1,6-Diyl, Naphthalene-1,7-Diyl, Naphthalene-1,8- Diyl, Naphthalene-2,3-Diyl, Naphthalene-2,6-Diyl, Naphthalene-2,7-Diyl, Tetrahydropyran-2,5-Diyl, 1,3-Dioxane-2,5-Diyl, Pyrimidine-2 , 5-Diyl, or pyridine-2,5-Diyl, in which at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least 1 One hydrogen may be replaced with an alkyl having 1 to 12 carbon atoms replaced with fluorine or chlorine; Z ⁵ and Z ⁶ are independently single-bonded or alkylenes having 1 to 10 carbon atoms, and this Z ⁵ And in Z ⁶ , at least one −CH ₂ − may be replaced by −O −, −CO−, −COO−, or −OCO−, and at least one −CH ₂ CH ₂₋ It may be replaced by CH = CH −, −C (CH ₃ ) = CH −, −CH = C (CH ₃ ) −, or −C (CH ₃ ) = C (CH ₃ ) −, and at least one hydrogen. ^{May be} replaced with fluorine or chlorine; P ¹ , P ² , and P ³ are polymerizable groups; Sp ³ , Sp ⁴ , and Sp 5 are independent from a single bond or 1 carbon. It is an alkylene of 10, and in Sp ³ , Sp ⁴ , and Sp ⁵ , at least one -CH _2- may be replaced with -O-, -COO-, -OCO-, or -OCOO-. And at least one -CH ₂ CH ₂ − may be replaced by −CH = CH − or −C≡C−, and at least one hydrogen may be replaced by fluorine or chlorine; q is 0, 1, or 2; j. , K, and p are independently 0, 1, 2, 3, or 4, and the sum of j, k, and p is greater than or equal to 1. Claimed that in formula (4), P ¹ , P ² , and P ³ are polymerizable groups independently selected from the group of groups represented by formula (P-1) to formula (P-5). Item 9. The liquid crystal composition according to Item 9.

In formulas (P-1) to (P-5), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine. It is an alkyl having 1 to 5 carbon atoms replaced with. The second additive is any one of claims 1 to 10 , wherein the second additive is at least one polymerizable compound selected from the group of compounds represented by formulas (4-1) to (4-29). Liquid crystal composition.

In formulas (4-1) to (4-29), P ¹ , P ² , and P ³ are independently from the group of groups represented by formulas (P-1) to (P-3). The polymerizable groups of choice, where M ¹ , M ² , and M ³ were independently replaced with hydrogen, fluorine, alkyl with 1 to 5 carbon atoms, or at least one hydrogen with fluorine or chlorine. Alkyl with 1 to 5 carbon atoms;

Sp ³ , Sp ⁴ , and Sp ⁵ are independently single bonds or alkylenes with 1 to 10 carbon atoms, and in these Sp ³ , Sp ⁴ , and Sp ⁵ , at least one -CH ₂ -is -O. -, -COO-, -OCO-, or -OCOO- may be replaced, and at least one -CH ₂ CH _2- may be replaced with -CH = CH- or -C≡C-. , At least one hydrogen may be replaced with fluorine or chlorine. The liquid crystal composition according to any one of claims 9 to 11 , wherein the proportion of the second additive is in the range of 0.03% by weight to 10% by weight based on the weight of the liquid crystal composition. The liquid crystal composition according to any one of claims 1 to 12 , which contains at least one polymerizable compound selected from the group of compounds represented by the formula (5) as a third additive.

In formula (5), ^R50 was hydrogen, halogen, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, and at least one hydrogen was 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 with fluorine or chlorine; R ⁵¹ is -OH, -NH ₂ , -OR ⁵³ , -N (R). ⁵³ ) A group represented by ₂ or -Si (R ⁵³ ) ₃ ^{, where R 53} is hydrogen or an alkyl having 1 to 5 carbon atoms, in which at least one -CH _2- May be replaced with −O−, at least one − (CH ₂ ) ₂ − may be replaced with −CH = CH−, and in these groups at least one hydrogen is replaced with fluorine. Ring A ⁵⁰ and Ring B ⁵⁰ may independently be 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1. , 3-Xylene, 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, pyridine- 2,5-Diyl, Fluoren-2,7-Diyl, Phenantren-2,7-Dyle, Anthracen-2,6-Diyl, Perhydrocyclopenta [a] Phenantren-3,17-Diyl, or 2,3 4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl, at least one in these rings. Hydrogen may be replaced with fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or alkyl with 1 to 12 carbons in which at least one hydrogen has been replaced with fluorine or chlorine; Z ⁵⁰ is a single bond,-(CH ₂ ) _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ O -, -OCH _2- , or -CF = CF-; Sp ⁵¹ And Sp ⁵² are independently single-bonded or 1 to 7 carbon alkylenes, in which at least one -CH ₂ − is replaced by -O-, -COO-, or -OCO-. Also, at least one −CH ₂ CH ₂ − may be replaced by −CH = CH −, and in these groups, at least one hydrogen may be replaced by fluorine; a ⁵⁰ is 0. 1, 2, 3, or 4. The liquid crystal composition according to claim 13 , wherein the proportion of the third additive is in the range of 0.3% by weight to 10% by weight based on the weight of the liquid crystal composition. A liquid crystal display device containing the liquid crystal composition according to any one of claims 1 to 14. The liquid crystal display element according to claim 15, 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 drive method of the liquid crystal display element is an active matrix method. A polymer-supported oriented liquid crystal display element containing the liquid crystal composition according to any one of claims 1 to 14 and polymerized with a polymerizable compound in the liquid crystal composition. A liquid crystal display element having no alignment film and containing the liquid crystal composition according to any one of claims 1 to 14, wherein the polymerizable compound in the liquid crystal composition is polymerized. Use of the liquid crystal composition according to any one of claims 1 to 14 in a liquid crystal display element. Use of the liquid crystal composition according to any one of claims 1 to 14 in a polymer-supported oriented liquid crystal display device. Use of the liquid crystal composition according to any one of claims 1 to 14 in a liquid crystal display device having no alignment film.