CN112368260B - Compounds, liquid crystal compositions and liquid crystal display elements - Google Patents

Abstract

The invention provides a compound, a liquid crystal composition and a liquid crystal display elementIt has at least one of high chemical stability, high ability to orient liquid crystal molecules horizontally, high orientation property in a wide range of addition concentration, proper reactivity, and high solubility in a liquid crystal composition. The present invention provides a compound of formula (1) below. In the formula (1), a and b are independently 0, 1 or 2, and 0.ltoreq.a+b.ltoreq.3, ring A ¹ Ring A ² Ring A ³ Ring A ⁴ Independently, for example, 1, 4-cyclohexylene, Z ¹ 、Z ² 、Z ³ 、Z ⁴ Z is as follows ⁵ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, etc., sp ¹ Sp and Sp ² Independently a single bond or an alkylene group of 1 to 10 carbon atoms, etc., P ¹ P ² Independently a specific polymerizable group.

Description

Compound, liquid crystal composition and liquid crystal display element

Technical Field

The present invention relates to a compound, a liquid crystal composition and a liquid crystal display element. In particular, it relates to a polymerizable polar compound having an excellent light absorption structure in one molecule, a liquid crystal composition containing the compound and having positive or negative dielectric anisotropy, and a liquid crystal display element containing the composition.

Background Art

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

The liquid crystal display element contains a liquid crystal composition having a nematic phase. The composition has appropriate characteristics. By improving the characteristics of the composition, an AM element with good characteristics can be obtained. The relationship between the two characteristics is summarized in the following Table 1. The characteristics of the composition are further described based on commercially available AM elements. The temperature range of the nematic phase is related to the temperature range in which the element can be used. The preferred upper limit temperature of the nematic phase is above about 70°C, and the preferred lower limit temperature of the nematic phase is below about -10°C. The viscosity of the composition is related to the response time of the element. In order to display dynamic images with the element, it is preferred that the response time is short. The ideal response time is shorter than 1 millisecond. Therefore, it is preferred that the viscosity of the composition is small. More preferably, the viscosity is small at a low temperature.

Table 1. Composition and characteristics of AM devices

1) The time for injecting the composition into the liquid crystal display element can be shortened

The optical anisotropy of the composition is related to the contrast of the element. Depending on the mode of the element, the optical anisotropy needs to be large or small, that is, the optical anisotropy is appropriate. The product (Δn×d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the element is designed to maximize the contrast. The appropriate value of the product depends on the type of operating mode. In an element of a mode such as TN, the value is about 0.45μm. In an element of a VA mode, the value is in the range of about 0.30μm to about 0.40μm, and in an element of an IPS mode or FFS mode, the value is in the range of about 0.20μm to about 0.30μm. In these cases, a composition having a large optical anisotropy is preferred for an element with a small cell gap. A large dielectric anisotropy in the composition contributes to a low threshold voltage, a small power consumption and a large contrast in the element. Therefore, a large positive or negative dielectric anisotropy is preferred. A large specific resistance in the composition contributes to a large voltage holding ratio and a large contrast in the element. Therefore, it is preferred that the composition has a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase in the initial stage. It is preferred that the composition has a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase after long-term use. The stability of the composition to ultraviolet rays and heat is related to the life of the element. When the stability is high, the life of the element is long. This characteristic is preferred for AM elements used in liquid crystal projectors, liquid crystal televisions, etc.

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

A composition having positive or negative dielectric anisotropy is used in a polymer sustained alignment (PSA) type AM element. In a polymer sustained alignment (PSA) type liquid crystal display element, a liquid crystal composition containing a polymer is used. First, a composition to which a small amount of a polymerizable compound is added is injected into the element. Then, while a voltage is applied between the substrates of the element, ultraviolet light is irradiated on the composition. The polymerizable compound is polymerized to form a network structure of the polymer in the composition. In the composition, the orientation of the liquid crystal molecules can be controlled by the polymer, so the response time of the element is shortened and the afterimage of the image is improved. Elements having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA can expect this effect of the polymer.

The following method has been reported: instead of an alignment film such as polyimide, a low molecular compound having a cinnamate group, a low molecular compound having a polyvinyl cinnamate, a chalcone structure, a low molecular compound having an azobenzene structure, or a dendritic polymer is used to control the orientation of liquid crystal (Patent Document 1, Patent Document 2, or Patent Document 3). In the method of Patent Document 1, Patent Document 2, or Patent Document 3, first, the low molecular compound or polymer is dissolved in a liquid crystal composition as an additive. Then, a thin film containing the low molecular compound or polymer is generated on a substrate by phase separation of the additive. Finally, the substrate is irradiated with linear polarization at a temperature higher than the upper limit temperature of the liquid crystal composition. When the low molecular compound or polymer is dimerized or isomerized by the linear polarization, its molecules are arranged in a certain direction. In the method, by selecting the type of low molecular compound or polymer, a horizontal alignment mode element such as IPS or FFS and a vertical alignment mode element such as VA can be manufactured. In the method, it is important that the low molecular weight compound or polymer is easily dissolved at a temperature higher than the upper limit temperature of the liquid crystal composition, and when the temperature is restored to room temperature, the compound is easily phase-separated from the liquid crystal composition. However, it is difficult to ensure the compatibility of the low molecular weight compound or polymer with the liquid crystal composition.

So far, regarding liquid crystal display elements without an alignment film, as compounds capable of horizontally aligning liquid crystal molecules, Patent Document 2 describes compound (S-1) ([Chemical 2] in paragraph 0034 of the specification), and Patent Document 3 describes compound (S-2) (compound [14] in P176 of the specification). However, these compounds require high-energy light irradiation in order to horizontally align the liquid crystal molecules with sufficient alignment properties, and there are concerns about increased manufacturing time due to long-term light irradiation or damage to the liquid crystal caused by it, and improvements are desired.

Prior art literature

Patent Literature

Patent Document 1: International Publication No. 2015/146369

Patent Document 2: International Publication No. 2017/057162

Patent Document 3: International Publication No. 2017/102068

Summary of the invention

Problem to be solved by the invention

The first problem of the present invention is to provide a compound having at least one of the following characteristics: high chemical stability, high ability to orient liquid crystal molecules horizontally, high orientation in a wide range of added concentrations, appropriate reactivity, and high solubility in liquid crystal compositions, and it is expected that the voltage holding ratio when used in liquid crystal display elements is large. The second problem is to provide a liquid crystal composition, which contains the compound, and satisfies at least one of the following characteristics: high upper limit temperature of the nematic phase, low lower limit temperature of the nematic phase, low viscosity, appropriate optical anisotropy, large positive or negative dielectric anisotropy, large specific resistance, high stability to ultraviolet rays, high stability to heat, and large elastic constant. The third problem is to provide a liquid crystal display element, which contains the composition, and when the polar compound is formed into a film in the element by irradiating the composition with ultraviolet rays, the film has at least one characteristic of appropriate hardness, low permeability of contact components, high weather resistance, and appropriate volume resistance value, and the liquid crystal display element has at least one characteristic of a wide temperature range in which the element can be used, a short response time, a high voltage holding ratio, a low threshold voltage, a large contrast, and a long life.

Technical means of solving problems

The present inventors have found that the compound represented by the following formula (1) can solve the above-mentioned problems, and have completed the invention.

(The symbols in the formula will be described later)

Effects of the Invention

The first advantage of the present invention is to provide a compound having at least one of high chemical stability, high ability to orient liquid crystal molecules horizontally, high orientation in a wide range of added concentrations, appropriate reactivity and high solubility in liquid crystal compositions, and it is expected that the voltage holding ratio when used for liquid crystal display elements is large. The second advantage is to provide a liquid crystal composition, which contains the compound, and satisfies at least one of the characteristics of high upper limit temperature of the nematic phase, low lower limit temperature of the nematic phase, low viscosity, appropriate optical anisotropy, large positive or negative dielectric anisotropy, large specific resistance, high stability to ultraviolet rays, high stability to heat, and large elastic constant. The third advantage is to provide a liquid crystal display element, which contains the composition, and when the polar compound is formed into a film in the element by irradiating ultraviolet rays to the composition, the film has at least one characteristic of appropriate hardness, low permeability of contact components, high weather resistance, and appropriate volume resistance value, and the liquid crystal display element has at least one characteristic of a wide temperature range in which the element can be used, a short response time, a high voltage holding ratio, a low threshold voltage, a large contrast, and a long life. By using a liquid crystal composition containing the compound of the present invention, a step of forming an alignment film is no longer necessary, and thus a liquid crystal display element having a reduced production cost can be obtained.

DETAILED DESCRIPTION

The usage of the terms in the specification is as follows. Sometimes the terms "liquid crystal composition" and "liquid crystal display element" are referred to as "composition" and "element", respectively. "Liquid crystal display element" is a general term for liquid crystal display panels and liquid crystal display modules. "Liquid crystal compound" is a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and a general term for compounds that do not have a liquid crystal phase but are mixed into a composition for the purpose of adjusting the temperature range, viscosity, dielectric anisotropy and other properties of the nematic phase. The compound has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod-like. "Polymerizable compound" is a compound added for the purpose of generating a polymer in a composition. "Polar compound" helps the liquid crystal molecules to align by interacting with the substrate surface through polar groups.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. The proportion (content) of the liquid crystal compound is expressed as a weight percentage (wt%) based on the weight of the liquid crystal composition. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are added to the liquid crystal composition as needed. Similar to the proportion of the liquid crystal compound, the proportion (addition amount) of the additive is expressed as a weight percentage (wt%) based on the weight of the liquid crystal composition. Sometimes parts per million (ppm) by weight is also used. The proportion of the polymerization initiator and the polymerization inhibitor is expressed as an exception based on the weight of the polymerizable compound.

The compound represented by formula (1) is sometimes referred to as "compound (1)". Compound (1) refers to one compound, a mixture of two compounds, or a mixture of three or more compounds represented by formula (1). The above rule also applies to at least one compound selected from the group of compounds represented by formula (2). Symbols such as B ¹ , C ¹ , and F surrounded by a hexagon correspond to ring B ¹ , ring C ¹ , and ring F, respectively. The hexagon represents a six-membered ring such as a cyclohexane ring or a benzene ring, or a condensed ring such as a naphthalene ring. The oblique line across the hexagon indicates that any hydrogen on the ring can be substituted by a group such as -Sp ¹ -P ^1. Subscripts such as e indicate the number of substituted groups. When the subscript is 0, there is no such substitution.

The symbol of the terminal group R ¹¹ is used in a plurality of component compounds. In these compounds, the two groups represented by any two R ¹¹ may be the same or different. For example, there is a case where R ¹¹ of compound (2) is ethyl and R ¹¹ of compound (3) is ethyl. There is also a case where R ¹¹ of compound (2) is ethyl and R ¹¹ of compound (3) is propyl. The above rules also apply to symbols of other terminal groups, rings, bonding groups, etc. In formula (8), when i is 2, there are two rings D ^1. In the above compound, the two groups represented by the two rings D ¹ may be the same or different. The above rules also apply to any two rings D ¹ when i is greater than 2. The above rules also apply to symbols of other rings, bonding groups, etc.

The expression "at least one 'A'" means that the number of 'A's is arbitrary. Regarding the expression "at least one 'A' may be substituted by 'B'", when the number of 'A' is one, the position of 'A' is arbitrary, and when the number of 'A' is two or more, the positions of these 'A's can also be selected without limitation. The above rule also applies to the expression "at least one 'A' is substituted by 'B'". The expression "at least one A may be substituted by B, C or D" means that it includes the case where at least one A is substituted by B, the case where at least one A is substituted by C and the case where at least one A is substituted by D, and further includes the case where multiple A is substituted by at least two of B, C and D. For example, the alkyl group in which at least one -CH ₂ - (or -CH ₂ CH ₂ -) may be substituted by -O- (or -CH＝CH-) includes alkyl, alkenyl, alkoxy, alkoxyalkyl, alkoxyalkenyl and alkenoxyalkyl. Furthermore, the case where two consecutive -CH ₂ - are substituted by -O- to become -OO- is not preferred. In an alkyl group, for example, it is not preferable that the -CH ₂ - in the methyl portion (-CH ₂ -H) is replaced by -O- to become -OH.

Halogen refers to fluorine, chlorine, bromine or iodine. Preferred halogens are fluorine or chlorine. Further preferred halogens are fluorine. Alkyl groups are straight-chain or branched, and do not include cyclic alkyl groups. Generally speaking, straight-chain alkyl groups are better than branched alkyl groups. These situations are also the same for terminal groups such as alkoxy and alkenyl. Regarding the stereo configuration related to 1,4-cyclohexylene, in order to increase the upper limit temperature of the nematic phase, the trans configuration is better than the cis configuration. 2-Fluoro-1,4-phenylene refers to the following two divalent groups. In the chemical formula, fluorine can be to the left (L) or to the right (R). The above rule also applies to asymmetric divalent groups such as tetrahydropyran-2,5-diyl generated by removing two hydrogens from the ring.

The present invention includes the following items and the like.

[1] A compound represented by the formula (1).

In formula (1),

a and b are independently 0, 1 or 2, and 0≦a+b≦3,

Ring ^A1 , Ring ^A2 , Ring ^A3 and Ring ^A4 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, 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, the group represented by (A-1) or the group represented by (A-2), in which at least one hydrogen in these rings may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, an alkenyloxy group having 2 to 11 carbon atoms, -Sp ¹ -P ¹ or -Sp ² -P ² , in which at least one hydrogen in these groups may be substituted by fluorine or chlorine, when a is 2, the two rings A ¹ may be different, when b is 2, the two rings A ⁴ may be different, and in (A-2), c is 2, 3 or 4. wherein at least one of ring A ¹ , ring A ² , ring A ³ or ring A ⁴ is naphthalene-2,6-diyl, phenanthrene-2,7-diyl, the group represented by (A-1) or the group represented by (A-2);

Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ - may be substituted by -O-, -CO-, -COO-, -OCO- or -OCOO-, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted by a halogen. Wherein, at least one of Z ² , Z ³ or Z ⁴ is -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO- or -COCH=CH-, when a is 2, the two Z ¹ may be different, and when b is 2, the two Z ⁵ may be different;

Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ - may be substituted by -O-, -CO-, -COO-, -OCO- or -OCOO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-. In these groups, at least one hydrogen may be substituted by a halogen. When there are multiple Sp ¹ or Sp ² in the structure, they may be different.

^P1 and ^P2 are independently a group represented by any one of formula (1b) to formula (1h), and when a plurality of ^P1 or ^P2 exist in the structure, they may be different from each other;

In formula (1b) to formula (1h),

M ¹ , M ² , M ³ and M ⁴ 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 atom is substituted by halogen;

R ² is hydrogen, halogen, or an alkyl group having 1 to 5 carbon atoms, in which at least one hydrogen group may be substituted by a halogen, and at least one -CH ₂ - group may be substituted by -O-;

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently hydrogen or alkyl having 1 to 15 carbon atoms, in which at least one -CH ₂ - may be substituted by -O- or -S-, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, and in these groups at least one hydrogen may be substituted by halogen.

[2] The compound according to [1], wherein in formula (1),

a and b are independently 0, 1 or 2, and 0≦a+b≦2;

Ring ^A1 , Ring ^A2 , Ring ^A3 and Ring ^A4 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, 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, the group represented by (A-1) or the group represented by (A-2), in which at least one hydrogen in these rings may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, an alkenyloxy group having 2 to 11 carbon atoms, -Sp ¹ -P ¹ or -Sp ² -P ² , in which at least one hydrogen in these groups may be substituted by fluorine or chlorine, when a is 2, the two rings A ¹ may be different, when b is 2, the two rings A ⁴ may be different, and in (A-2), c is 2, 3 or 4. wherein at least one of ring A ¹ , ring A ² , ring A ³ or ring A ⁴ is naphthalene-2,6-diyl, phenanthrene-2,7-diyl, the group represented by (A-1) or the group represented by (A-2);

Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are independently a single bond, -(CH ₂ ) ₂ -, -CH＝CH-, -C≡C-, -COO-, -OCO-, -CF 2 O-, -OCF ₂ -, _{-CH 2 O-} , -OCH ₂ -, -CF＝CF-, -CH＝CHCOO-, -OCOCH＝CH-, -CH＝CHCO- or -COCH＝CH-, wherein at least one of Z ² , Z ³ or Z ⁴ is -COO-, -OCO-, -CH＝CHCOO-, -OCOCH＝CH-, -CH＝CH-, -CH＝CHCO- or -COCH＝CH-, and when a is 2, two Z ^1s may be different, and two Z ^5s may be different;

Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ - may be substituted by -O-, -COO- or -OCO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH-. In these groups, at least one hydrogen may be substituted by fluorine or chlorine. When there are multiple Sp ¹ or Sp ² in the structure, they may be different.

^P1 and ^P2 are independently a group represented by any one of formula (1b) to formula (1h), and when a plurality of ^P1 or ^P2 exist in the structure, they may be different from each other;

In formula (1b) to formula (1h),

M ¹ , M ² , M ³ and M ⁴ 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 atom is substituted by halogen;

R ² is hydrogen, halogen, or an alkyl group having 1 to 5 carbon atoms, in which at least one hydrogen group may be substituted by a halogen, and at least one -CH ₂ - group may be substituted by -O-;

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently hydrogen or alkyl having 1 to 15 carbon atoms, in which at least one -CH ₂ - may be substituted by -O- or -S-, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, and in these groups at least one hydrogen may be substituted by halogen.

[3] The compound according to [1] or [2], which is represented by any one of Formula (1-1) to Formula (1-3).

In formula (1-1) to formula (1-3),

Ring A ¹ , Ring A ² , Ring A ³ and Ring A ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, the group represented by (A-1) or the group represented by (A-2); in these rings, at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, an alkenyloxy group having 2 to 11 carbon atoms, -Sp ¹ -P ¹ or -Sp ² -P ² ; in these groups, at least one hydrogen may be substituted by fluorine or chlorine; when a is 2, the two rings A ¹ may be different; when b is 2, the two rings A ⁴ may be different; in (A-2), c is 2, 3 or 4. wherein at least one of ring A ¹ , ring A ² , ring A ³ or ring A ⁴ is naphthalene-2,6-diyl, phenanthrene-2,7-diyl, the group represented by (A-1) or the group represented by (A-2);

Z ² , Z ³ and Z ⁴ are independently a single bond, -(CH ₂ ) ₂ -, -CH＝CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -CF＝CF-, -CH＝CHCOO-, -OCOCH＝CH-, -CH＝CHCO- or -COCH＝CH-, wherein at least one of Z ² , Z ³ and Z ⁴ is -COO-, -OCO-, -CH＝CHCOO-, -OCOCH＝CH-, -CH＝CH-, -CH＝CHCO- or -COCH＝CH-;

Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ - may be substituted by -O-, -COO-, -OCOO- or -OCO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH-. In these groups, at least one hydrogen may be substituted by fluorine or chlorine. When there are multiple Sp ¹ or Sp ² in the structure, they may be different.

^P1 and ^P2 are independently a group represented by any one of formula (1b) to formula (1h), and when a plurality of ^P1 or ^P2 exist in the structure, they may be different from each other;

In formula (1b) to formula (1h),

M ¹ , M ² , M ³ and M ⁴ 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 atom is substituted by halogen;

R ² is hydrogen, halogen, or an alkyl group having 1 to 5 carbon atoms, in which at least one hydrogen group may be substituted by a halogen, and at least one -CH ₂ - group may be substituted by -O-;

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently hydrogen or alkyl having 1 to 15 carbon atoms, in which at least one -CH ₂ - may be substituted by -O- or -S-, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, and in these groups at least one hydrogen may be substituted by halogen.

[4] The compound according to [3], wherein in Formula (1-1), Formula (1-2) and Formula (1-3),

Ring A ¹ , Ring A ² , Ring A ³ and Ring A ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, a group represented by (A-1) or a group represented by (A-2), and at least one hydrogen in these rings may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, an alkenyloxy group having 2 to 11 carbon atoms, -Sp ¹ -P ¹ or -Sp ² -P ² , and in (A-2), c is 2, 3 or 4. Among them, at least one of Ring A ¹ , Ring A ² , Ring A ³ or Ring A ⁴ is naphthalene-2,6-diyl, phenanthrene-2,7-diyl, a group represented by (A-1) or a group represented by (A-2);

Z ² , Z ³ and Z ⁴ are independently a single bond, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C-, -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CHCO- or -COCH=CH-, wherein at least one of Z ² , Z ³ and Z ⁴ is -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO- or -COCH=CH-;

Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ - may be substituted by -O-, -COO-, -OCOO- or -OCO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH-. When there are multiple Sp ¹ or Sp ² in the structure, they may be different.

^P1 and ^P2 are independently a group represented by any one of formula (1b), formula (1c), formula (1d) or formula (1e), and when a plurality of ^P1 or ^P2 exist in the structure, they may be different;

In formula (1b) to formula (1e),

M ¹ , M ² , M ³ and M ⁴ 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 atom is substituted by halogen;

R ² is hydrogen, halogen or an alkyl group having 1 to 5 carbon atoms, in which at least one hydrogen group may be substituted by a halogen, and at least one -CH ₂ - group may be substituted by -O-;

R ³ , R ⁴ , R ⁵ and R ⁶ are independently hydrogen or alkyl having 1 to 15 carbon atoms, in which at least one -CH ₂ - may be substituted by -O- or -S-, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, and in these groups at least one hydrogen may be substituted by halogen.

[5] The compound according to [3], wherein in Formula (1-1), Formula (1-2) and Formula (1-3),

Ring A ¹ , Ring A ² , Ring A ³ and Ring A ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, a group represented by (A-1) or a group represented by (A-2), at least one hydrogen in these rings may be substituted by fluorine, chlorine, methyl or ethyl, and in (A-2), c is 2, 3 or 4. Among them, at least one of Ring A ¹ , Ring A ² , Ring A ³ or Ring A ⁴ is naphthalene-2,6-diyl, phenanthrene-2,7-diyl, a group represented by (A-1) or a group represented by (A-2);

Z ² , Z ³ and Z ⁴ are independently a single bond, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C-, -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CHCO- or -COCH=CH-, wherein at least one of Z ² , Z ³ and Z ⁴ is -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO- or -COCH=CH-;

Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ - may be substituted by -O-, -COO-, -OCOO- or -OCO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH-. When there are multiple Sp ¹ or Sp ² in the structure, they may be different.

^P1 and ^P2 are independently a group represented by formula (1b-1), formula (1b-2), formula (1b-3), formula (1b-4), formula (1b-5), formula (1c-1), formula (1d-1), formula (1d-2) or formula (1e-1).

[6] The compound according to [3], wherein in the compound represented by Formula (1-1), Formula (1-2) or Formula (1-3), any one of Z ² , Z ³ or Z ⁴ is -COO- or -OCO-.

[7] The compound according to any one of [1] to [6], which is represented by the formula (1-A).

P ¹ -Sp ¹ -Y-Sp ² -P ² (1-A)

^P1 and ^P2 are independently a group represented by formula (1b-1), formula (1b-2), formula (1b-3), formula (1b-4), formula (1b-5), formula (1c-1), formula (1d-1), formula (1d-2) or formula (1e-1);

Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ - may be substituted by -O-, -COO-, -OCOO- or -OCO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH-;

Y is a group represented by any one of the formulae (MES-1-01) to (MES-1-10), and in these groups, at least one hydrogen atom may be substituted by fluorine, chlorine, methyl or ethyl.

[8] The compound according to [7], wherein in the compound represented by formula (1-A), Sp ¹ and Sp ² are independently alkylene groups having 1 to 10 carbon atoms, in which at least one -CH ₂ - group may be substituted by -O-, -COO-, -OCOO- or -OCO-, and at least one -(CH ₂ ) ₂ - group may be substituted by -CH=CH-.

[9] A liquid crystal composition comprising at least one compound according to any one of [1] to [8].

[10] The liquid crystal composition according to [9], further comprising at least one compound selected from the group of compounds represented by formula (2) to formula (4).

In formula (2) to formula (4),

R ¹¹ and R ¹² are independently alkyl groups having 1 to 10 carbon atoms or alkenyl groups having 2 to 10 carbon atoms, in which at least one -CH ₂ - group may be substituted by -O-, and at least one hydrogen group may be substituted by fluorine;

Ring B ¹ , Ring B ² , Ring B ³ and Ring B ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene or pyrimidine-2,5-diyl;

Z ¹¹ , Z ¹² and Z ¹³ are independently a single bond, -CH ₂ CH ₂ -, -CH＝CH-, -C≡C- or -COO-.

[11] The liquid crystal composition according to [9] or [10], further comprising at least one compound selected from the group of compounds represented by formula (5) to formula (7).

In formula (5) to formula (7),

R ¹³ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, in which at least one -CH ₂ - group may be substituted by -O-, and at least one hydrogen group may be substituted by fluorine;

X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ or -OCF ₂ CHFCF ₃ ;

Ring C ¹ , Ring C ² and Ring C ³ are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen radical may be substituted by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl;

Z ¹⁴ , Z ¹⁵ and Z ¹⁶ are independently a single bond, -CH ₂ CH ₂ -, -CH═CH-, -C≡C-, -COO-, -CF ₂ O-, -OCF ₂ -, -CH 2 O-, -CF═CF-, -CH═CF- or -( _{CH 2 ) 4} -;

L ¹¹ and L ¹² are independently hydrogen or fluorine.

[12] The liquid crystal composition according to any one of [9] to [11], further comprising at least one compound represented by formula (8).

In formula (8),

R ¹⁴ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, in which at least one -CH ₂ - group may be substituted by -O-, and at least one hydrogen group may be substituted by fluorine;

^X12 is -C≡N or -C≡CC≡N;

Ring ^D1 is 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be substituted by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl;

Z ¹⁷ is a single bond, -CH ₂ CH ₂ -, -C≡C-, -COO-, -CF ₂ O-, -OCF ₂ - or -CH ₂ O-;

L ¹³ and L ¹⁴ are independently hydrogen or fluorine;

i is 1, 2, 3 or 4.

[13] The liquid crystal composition according to any one of [9] to [12], further comprising at least one compound selected from the group of compounds represented by formula (9) to formula (15).

In formula (9) to formula (15),

R ¹⁵ and R ¹⁶ are independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, in which at least one -CH ₂ - group may be substituted by -O-, and at least one hydrogen group may be substituted by fluorine;

R ¹⁷ is hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, wherein at least one -CH ₂ - in the alkyl group and the alkenyl group may be substituted by -O-, and at least one hydrogen group may be substituted by fluorine;

Ring E ¹ , Ring E ² , Ring E ³ and Ring E ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene in which at least one hydrogen radical may be substituted by fluorine, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6-diyl;

Ring ^E5 and Ring ^E6 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6-diyl;

Z ¹⁸ , Z ¹⁹ , Z ²⁰ and Z ²¹ are independently a single bond, -CH ₂ CH ₂ -, -COO-, -CH ₂ O-, -OCF ₂ - or -OCF ₂ CH ₂ CH ₂ -;

L ¹⁵ and L ¹⁶ are independently fluorine or chlorine;

S ¹¹ is hydrogen or methyl;

X is -CHF- or -CF ₂ -;

j, k, m, n, p, q, r and s are independently 0 or 1, the sum of k, m, n and p is 1 or 2, the sum of q, r and s is 0, 1, 2 or 3, and t is 1, 2 or 3.

[14] The liquid crystal composition according to any one of [9] to [13], comprising at least one polymerizable compound of the compound represented by formula (16).

In formula (16),

Ring F and Ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl or pyridin-2-yl, and in these rings, at least one hydrogen atom may be substituted by halogen, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is substituted by halogen;

Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, and in these rings, at least one hydrogen may be substituted by halogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is substituted by halogen;

Z ²² and Z ²³ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ - may be substituted by -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ CH ₂ - may be substituted by -CH＝CH-, -C(CH ₃ )＝CH-, -CH＝C(CH ₃ )- or -C(CH ₃ )＝C(CH ₃ )-, and in these groups, at least one hydrogen may be substituted by fluorine or chlorine;

P ¹¹ , P ¹² and P ¹³ are independently polymerizable groups selected from the group of groups represented by formula (P-1) to formula (P-5);

M ¹¹ , M ¹² and M ¹³ are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen atom is substituted by fluorine or chlorine;

Sp ¹¹ , Sp ¹² and Sp ¹³ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ - may be substituted by -O-, -COO-, -OCO- or -OCOO-, at least one -CH ₂ CH ₂ - may be substituted by -CH＝CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted by fluorine or chlorine;

u is 0, 1, or 2;

f, g and h are independently 0, 1, 2, 3 or 4, and the sum of f, g and h is 2 or more.

[15] The liquid crystal composition according to any one of [9] to [14], comprising at least one polymerizable compound selected from the group of compounds represented by Formula (16-1) to Formula (16-27).

In formula (16-1) to formula (16-27),

^P11 , ^P12 and ^P13 are independently polymerizable groups selected from the group represented by formula (P-1) to formula (P-3), wherein ^M11 , ^M12 and ^M13 are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen atom is substituted with a halogen;

Sp ¹¹ , Sp ¹² and Sp ¹³ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ - may be substituted by -O-, -COO-, -OCO- or -OCOO-, at least one -CH ₂ CH ₂ - may be substituted by -CH＝CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted by fluorine or chlorine.

[16] The liquid crystal composition according to any one of [9] to [15], which further contains at least one of a polymerizable compound other than formula (1) and formula (16), a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer and a defoaming agent.

[17] A liquid crystal display element comprising the liquid crystal composition according to any one of [9] to [16].

The present invention also includes the following items. (a) The liquid crystal composition further contains at least two additives such as a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, and a defoaming agent. (b) A polymerizable composition prepared by adding a polymerizable compound different from compound (1) or compound (16) to the liquid crystal composition. (c) A polymerizable composition prepared by adding compound (1) and compound (16) to the liquid crystal composition. (d) A liquid crystal composite prepared by polymerizing the polymerizable composition. (e) A polymer-stabilized alignment type element containing the liquid crystal composite. (f) A polymer-stabilized alignment type element made by using a polymerizable composition, wherein the polymerizable composition is prepared by adding compound (1) and compound (16), and a polymerizable compound different from compound (1) or compound (16) to the liquid crystal composition.

The form of compound (1), the synthesis of compound (1), a liquid crystal composition, and a liquid crystal display device are described in order.

1. Form of compound (1)

The compound (1) of the embodiment of the present invention is a polar compound having a mesogen part and a polymerizable group including at least one excellent light absorption structure. The compound (1) has a high light absorption property and a property of absorbing light in a relatively long wavelength region by having a structure such as phenanthrene, naphthalene, tolane, etc. in the molecule, and exhibits sufficient properties by short-time or low-energy light irradiation compared to compounds without these structures.

One of the uses of compound (1) is as an additive for a liquid crystal composition used in a liquid crystal display element. Compound (1) is added for the purpose of horizontally controlling the orientation of liquid crystal molecules. Such an additive is preferably chemically stable under conditions of being sealed in the element, has a high solubility in the liquid crystal composition, and has a large voltage holding ratio when used in a liquid crystal display element. Compound (1) satisfies such characteristics to a large extent.

Preferred examples of compound (1) are described below. Preferred examples of R ¹ , Z ¹ to Z ⁵ , A ¹ to A ⁴ , Sp ¹ , Sp ² , P ¹ , P ² , a and b in compound (1) are also applicable to the lower formula of compound (1). In compound (1), the properties can be arbitrarily adjusted by appropriately combining the types of these groups. Since there is no great difference in the properties of the compounds, compound (1) may contain isotopes such as ² H (deuterium) and ¹³ C in an amount larger than the natural abundance.

Ring ^A1 , Ring ^A2 , Ring ^A3 and Ring ^A4 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, 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, the group represented by (A-1) or the group represented by (A-2), in which at least one hydrogen in these rings may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, an alkenyloxy group having 2 to 11 carbon atoms, -Sp ¹ -P ¹ or -Sp ² -P ² , in which at least one hydrogen in these groups may be substituted by fluorine or chlorine, when a is 2, the two rings A ¹ may be different, when b is 2, the two rings A ⁴ may be different, and in (A-2), c is 2, 3 or 4. wherein at least one of ring A ¹ , ring A ² , ring A ³ or ring A ⁴ is naphthalene-2,6-diyl, phenanthrene-2,7-diyl, the group represented by (A-1) or the group represented by (A-2);

Preferred rings ^A1 , ^A2 , ^A3 and ^A4 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, perhydrocyclopenta[a]phenanthrene-3,17-diyl, 2,3,4,7,8,9,10 ,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, the group represented by (A-1) or the group represented by (A-2), preferably c is 1 or 2, at least one hydrogen in these rings may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms or an alkenyloxy group having 2 to 11 carbon atoms, and at least one hydrogen in these groups may be substituted by fluorine or chlorine. Further preferred are 1,4-cyclohexylene, 1,4-phenylene, 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, and at least one hydrogen in these rings may be substituted by fluorine or an alkyl group having 1 to 5 carbon atoms. Particularly preferred are 1,4-cyclohexylene, 1,4-phenylene or perhydrocyclopenta[a]phenanthrene-3,17-diyl. In these rings, at least one hydrogen may be substituted by fluorine, methyl or ethyl.

Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are independently a single bond or an alkylene group having 1 to 10 carbon atoms. In the alkylene group, at least one -CH ₂ - may be substituted by -O-, -CO-, -COO-, -OCO- or -OCOO-, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted by a halogen. At least one of Z ² , Z ³ or Z ⁴ is any one of -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO- or -COCH=CH-, and when a is 2, two Z ^1s may be different, and two Z ^5s may be different.

Preferred Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are independently 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-. More preferred are single bonds, -(CH ₂ ) ₂ - or -CH=CH-. Particularly preferred are single bonds.

Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms. In the alkylene group, at least one -CH ₂ - may be substituted by -O-, -CO-, -COO-, -OCO- or -OCOO-, at least one -(CH ₂ ) ₂ - may be substituted by -CH＝CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted by a halogen.

Preferred Sp ¹ and Sp ² are independently a single bond, an alkylene group having 1 to 6 carbon atoms, an alkylene group having 1 to 6 carbon atoms in which one -CH ₂ - is substituted with -O-, or -OCOO-. More preferred are an alkylene group having 1 to 6 carbon atoms or -OCOO-.

^P1 and ^P2 are independently a group represented by any one of formula (1b) to formula (1h).

Preferred ^P1 and ^P2 are independently a group represented by any one of (1b), (1c), (1d) and (1e).

Preferred M ¹ , M ² , M ³ and M ⁴ are independently hydrogen, fluorine, methyl, ethyl or trifluoromethyl, and more preferably hydrogen.

R ² is hydrogen, halogen or an alkyl group having 1 to 5 carbon atoms, in which at least one hydrogen group may be substituted by a halogen, and at least one -CH ₂ - group may be substituted by -O-.

^R2 is preferably hydrogen, fluorine, methyl, ethyl, methoxymethyl or trifluoromethyl, and more preferably hydrogen.

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently hydrogen or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. In the alkyl group, at least one -CH ₂ - may be substituted by -O- or -S-, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted by a halogen.

Preferred R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently hydrogen, a linear alkyl group having 1 to 10 carbon atoms, a linear alkenyl group having 2 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 6 carbon atoms. More preferred are hydrogen, a linear alkyl group having 2 to 6 carbon atoms, a linear alkenyl group having 2 to 6 carbon atoms, a linear alkoxy group having 1 to 5 carbon atoms or a cyclic alkyl group having 4 to 6 carbon atoms.

A further preferred group is a group represented by formula (1b-1), formula (1b-2), formula (1b-3), formula (1b-4), formula (1b-5), formula (1c-1), formula (1d-1), formula (1d-2) or formula (1e-1).

In formula (1b) to formula (1h), ^M1 and ^M2 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 atom is substituted with halogen.

a and b are independently 0, 1 or 2, and preferably 0≦a+b≦2.

Preferred examples of the compound (1) are formula (1-1) to formula (1-3).

In formula (1-1) to formula (1-3),

Ring A ¹ , Ring A ² , Ring A ³ and Ring A ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, the group represented by (A-1) or the group represented by (A-2); in these rings, at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, an alkenyloxy group having 2 to 11 carbon atoms, -Sp ¹ -P ¹ or -Sp ² -P ² ; in these groups, at least one hydrogen may be substituted by fluorine or chlorine; when a is 2, the two rings A ¹ may be different; when b is 2, the two rings A ⁴ may be different; in (A-2), c is 2, 3 or 4. wherein at least one of ring A ¹ , ring A ² , ring A ³ or ring A ⁴ is naphthalene-2,6-diyl, phenanthrene-2,7-diyl, the group represented by (A-1) or the group represented by (A-2);

In these rings, at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, an alkenyloxy group having 2 to 11 carbon atoms, -Sp ¹ -P ¹ or -Sp ² -P ^2. In these groups, at least one hydrogen may be substituted by fluorine or chlorine.

Z ² , Z ³ and Z ⁴ are independently a single bond, -(CH ₂ ) ₂ -, -CH＝CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -CF＝CF-, -CH＝CHCOO-, -OCOCH＝CH-, -CH＝CHCO- or -COCH＝CH-, wherein at least one of Z ² , Z ³ and Z ⁴ is -COO-, -OCO-, -CH＝CHCOO-, -OCOCH＝CH-, -CH＝CH-, -CH＝CHCO- or -COCH＝CH-;

Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ - may be substituted by -O-, -COO-, -OCOO- or -OCO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH-. In these groups, at least one hydrogen may be substituted by fluorine or chlorine. When there are multiple Sp ¹ or Sp ² in the structure, they may be different.

^P1 and ^P2 are independently a group represented by any one of formula (1b) to formula (1h), and when a plurality of ^P1 or ^P2 exist in the structure, they may be different from each other;

In formula (1b) to formula (1h),

M ¹ , M ² , M ³ and M ⁴ 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 atom is substituted by halogen;

R ² is hydrogen, halogen, or an alkyl group having 1 to 5 carbon atoms, in which at least one hydrogen group may be substituted by a halogen, and at least one -CH ₂ - group may be substituted by -O-;

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently hydrogen or alkyl having 1 to 15 carbon atoms, in which at least one -CH ₂ - may be substituted by -O- or -S-, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, and in these groups at least one hydrogen may be substituted by halogen.

In the compound represented by Formula (1-1), Formula (1-2) or Formula (1-3), any one of Z ² , Z ³ and Z ⁴ is preferably -COO- or -OCO-.

In the compound represented by formula (1-1), formula (1-2) or formula (1-3), any one of Z ² , Z ³ and Z ⁴ is preferably -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CH-, -CH=CHCO- or -COCH=CH-.

The compound (1) is preferably a compound represented by the formula (1-A).

P ¹ -Sp ¹ -Y-Sp ² -P ² (1-A)

^P1 and ^P2 are independently a group represented by formula (1b-1), formula (1b-2), formula (1b-3), formula (1b-4), formula (1b-5), formula (1c-1), formula (1d-1), formula (1d-2) or formula (1e-1);

Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ - may be substituted by -O-, -COO-, -OCOO- or -OCO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH-;

Y is a group represented by any one of the formulae (MES-1-01) to (MES-1-10), and in these groups, at least one hydrogen atom may be substituted by fluorine, chlorine, methyl or ethyl.

In addition, specific examples of the compound (1) will be described in the examples given below.

Formula (2) to Formula (15) show the component compounds of the liquid crystal composition. Compounds (2) to (4) have small dielectric anisotropy. Compounds (5) to (7) have positive and large dielectric anisotropy. Compound (8) has a cyano group and therefore has a positive and larger dielectric anisotropy. Compounds (9) to (16) have negative and large dielectric anisotropy. Specific examples of these compounds will be described later.

In compound (16), P ¹¹ , P ¹² and P ¹³ are independently polymerizable groups.

Preferred ^P11 , ^P12 and ^P13 are polymerizable groups selected from the group represented by formula (P-1) to formula (P-5). Further preferred ^P11 , ^P12 and ^P13 are group (P-1), group (P-2) or group (P-3). Particularly preferred group (P-1) is -OCO-CH=CH ₂ or -OCO-C(CH ₃ )=CH _2. The wavy lines of group (P-1) to group (P-5) indicate bonding sites.

In the groups (P-1) to (P-5), M ¹¹ , M ¹² and M ¹³ are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen atom is substituted with a halogen atom.

In order to improve the reactivity, M ¹¹ , M ¹² and M ¹³ are preferably hydrogen or methyl. More preferably, M ¹¹ is methyl, and more preferably, M ¹² and M ¹³ are hydrogen.

Sp ¹¹ , Sp ¹² and Sp ¹³ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ - may be substituted by -O-, -COO-, -OCO- or -OCOO-, at least one -CH ₂ CH ₂ - may be substituted by -CH＝CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted by fluorine or chlorine.

Preferably, Sp ¹¹ , Sp ¹² and Sp ¹³ are single bonds.

Ring F and Ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl or pyridin-2-yl, and in these rings, at least one hydrogen may be substituted by halogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is substituted by halogen.

Preferred rings F and I are phenyl. Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, and at least one hydrogen in these rings may be substituted by halogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is substituted by halogen. Particularly preferred ring G is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ²² and Z ²³ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ - may be substituted by -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ CH ₂ - may be substituted by -CH＝CH-, -C(CH ₃ )＝CH-, -CH＝C(CH ₃ )- or -C(CH ₃ )＝C(CH ₃ )-, and in these groups, at least one hydrogen may be substituted by fluorine or chlorine.

Preferred Z ²² and Z ²³ are a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-. Further preferred Z ²² and Z ²³ are a single bond.

u is 0, 1, or 2.

Preferably, u is 0 or 1. f, g and h are independently 0, 1, 2, 3 or 4, and the sum of f, g and h is 1 or more. Preferably, f, g or h is 1 or 2.

2. Synthesis of compound (1)

The synthesis method of compound (1) is described. Compound (1) can be synthesized by appropriately combining the methods of organic synthetic chemistry. Compounds for which the synthesis method is not described are synthesized by methods described in books such as "Organic Syntheses" (John Wiley & Sons, Inc), "Organic Reactions" (John Wiley & Sons, Inc), "Comprehensive Organic Synthesis" (Pergamon Press), and "New Experimental Chemistry Lectures" (Maruzen).

2-1. Formation of bonding group Z ¹ , bonding group Z ² , bonding group Z ³ , bonding group Z ⁴ and bonding group Z ⁵

An example of a method for generating a bonding group in compound (1) is described in the following scheme. In the scheme, MSG ¹ (or MSG ² ) is a monovalent organic group having at least one ring. The monovalent organic groups represented by a plurality of MSG ¹ (or MSG ² ) may be the same or different. Compounds (1A) to (1J) correspond to compound (1) or intermediates of compound (1).

(I) Formation of single bond

Compound (1A) is synthesized by reacting arylboronic acid (21) with compound (22) in the presence of carbonate and tetrakis(triphenylphosphine)palladium catalyst. Compound (1A) can also be synthesized by reacting compound (23) with n-butyllithium, followed by reaction with zinc chloride, and then reacting with compound (22) in the presence of dichlorobis(triphenylphosphine)palladium catalyst.

(II) Formation of -COO- and -OCO-

Compound (23) is reacted with n-butyl lithium and then with carbon dioxide to obtain carboxylic acid (24). Carboxylic acid (24) and phenol (25) derived from compound (21) are dehydrated in the presence of 1,3-dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine (DMAP) to synthesize compound (1B) having -COO-. Compounds having -OCO- are also synthesized using the above method.

(III) Formation of -CF ₂ O- and -OCF ₂ -

Compound (1B) is sulfided with Lawesson's reagent to obtain compound (26). Compound (1C) having -CF ₂ O- is synthesized by fluorinating compound (26) with hydrogen fluoride pyridine complex and N-bromosuccinimide (NBS). See M. Kuroboshi et al., "Chem. Lett.", 1992, No. 827. Compound (1C) can also be synthesized by fluorinating compound (26) with (diethylamino)sulfur trifluoride (DAST). See WH Bunnelle et al., "J. Org. Chem.", 1990, No. 55, p. 768. Compounds having -OCF ₂ - are also synthesized by the above method.

(IV) Formation of -CH＝CH-

Compound (22) is reacted with n-butyl lithium, and then reacted with N,N-dimethylformamide (DMF) to obtain aldehyde (27). Phosphonium salt (28) is reacted with potassium tert-butoxide to produce phosphorus ylide, and the phosphorus ylide is reacted with aldehyde (27) to synthesize compound (1D). Cis isomer is generated due to the reaction conditions, and the cis isomer is isomerized to trans isomer by known methods as needed.

(V) Formation of -CH ₂ CH ₂ -

Compound (1E) is synthesized by hydrogenating compound (1D) in the presence of a palladium-carbon catalyst.

(VI) Generation of -C≡C-

Compound (23) is reacted with 2-methyl-3-butyn-2-ol in the presence of dichloropalladium and copper iodide catalysts, followed by deprotection under alkaline conditions to obtain compound (29). Compound (29) is reacted with compound (22) in the presence of dichlorobis(triphenylphosphine)palladium and copper halide catalysts to synthesize compound (1F).

(VII) Formation of -CH ₂ O- and -OCH ₂ -

Compound (27) is reduced with sodium borohydride to obtain compound (30). Compound (31) is obtained by bromination with hydrobromic acid. Compound (25) and compound (31) are reacted in the presence of potassium carbonate to synthesize compound (1G). Compounds having -OCH ₂ - are also synthesized by the above method.

(VIII) Formation of -CF＝CF-

Compound (23) is treated with n-butyllithium and then reacted with tetrafluoroethylene to obtain Compound (32). Compound (22) is treated with n-butyllithium and then reacted with Compound (32) to synthesize Compound (1H).

(VIV) Formation of -CH=CHCO- and -COCH=CH-

Compound (1I) is synthesized by subjecting Compound (40) to an aldol condensation reaction with Compound (27) in the presence of NaOH.

(X) Formation of -CH=CHCOO- and -OCOCH=CH-

Compound (1J) is synthesized by dehydrating cinnamic acid (41) and compound (25) in the presence of 1,3-dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine (DMAP).

2-2. Formation of Ring A ¹ , Ring A ² , Ring A ³ and Ring A ⁴

Regarding rings such as 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2-ethyl-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, perhydrocyclopenta[a]phenanthrene-3,17-diyl, 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, initiators are commercially available or methods for synthesizing the same are well known. The group represented by (A-1) and the group represented by (A-2) can be synthesized by referring to the formation of -C≡C-.

2-3. Formation of Linking Group ^Sp1 or Linking Group ^Sp2 and Polymerizing Group ^P1 or Polymerizing Group ^P2

Preferred examples of the polymerizable group ^P1 or the polymerizable group ^P2 are acryloyloxy (1b), maleimide (1c), itaconate (1d), vinyl ester (1e), oxirane (1g) or vinyloxy (1h).

The following is an example of a method for synthesizing a compound in which the polymerizable group is bonded to a ring via a linking group Sp ¹ or a linking group Sp ^2. First, an example in which the linking group Sp ¹ or the linking group Sp ² is a single bond is shown.

(1) Synthesis of compounds with single bonds

The synthesis method of the compound in which Sp ¹ or Sp ² is a single bond is as described in the following process. In the process, MSG ¹ is a monovalent organic group having at least one ring. Compounds (1S) to (1Z) are equivalent to compound (1). In the case where the polymerizable group is an acrylate derivative, it is synthesized by esterification of the corresponding acrylic acid with HO-MSG ^{1. The vinyloxy group is synthesized by etherification of HO-MSG 1 with} vinyl bromide. The oxyheterocyclopropyl group is synthesized by oxidation of the terminal double bond. The maleimide group is synthesized by the reaction of an amino group with maleic anhydride. Itaconate ester is synthesized by esterification of the corresponding itaconic acid with HO-MSG ^1. Vinyl ester is synthesized by transesterification of vinyl acetate with HOOC-MSG ¹ .

The above describes the synthesis method of the compound in which the linking group Sp ¹ or the linking group Sp ² is a single bond. The method of generating other linking groups can refer to the synthesis method of the linking group Z ¹ , the linking group Z ² , the linking group Z ³ , the linking group Z ⁴ and the linking group Z ⁵ for synthesis.

2-4. Synthesis Example

Examples of methods for synthesizing compound (1) are described below. In these compounds, MES is a mesogen group having at least one ring. P ¹ , M ¹ , M ² , Sp ¹ and Sp ² have the same definitions as described above.

Compound (51A) and Compound (51B) are commercially available or can be synthesized by a conventional organic synthesis method using a mesogen (MES) having an appropriate ring structure as an initiator.

In the case of synthesizing a compound in which MES and Sp ¹ are linked by an ether bond, compound (51A) can be used as an initiator and etherification can be performed using compound (52) and a base such as potassium hydroxide to obtain compound (53A). In addition, in the case of synthesizing a compound in which MES and Sp ¹ are linked by a single bond, compound (51B) can be used as an initiator and a metal catalyst such as palladium and a base can be used to perform a cross-coupling reaction to obtain compound (53B). Compound (53A) or compound (53B) is sometimes derived as needed to allow a protecting group such as trimethylsilyl (TMS) or tetrahydropyranyl (THP) to function.

Thereafter, compound (53A), compound (53B), compound (54A) or compound (54B) is etherified again in the presence of compound (55) and a base such as potassium hydroxide to obtain compound (57A) or compound (57B).

At this time, when a protecting group has been allowed to act in the previous stage, the protecting group is removed by a deprotection reaction.

Compound (1A) wherein ^P2 is a group represented by formula (1b-3) can be synthesized from compound (57) by the following method: Compound (57) is subjected to an esterification reaction in the presence of compound (58), DCC and DMAP to derive compound (1A).

3. Liquid crystal composition

The liquid crystal composition of an embodiment of the present invention comprises compound (1) as component A. Compound (1) can contribute to the control of the orientation of liquid crystal molecules by interacting with the substrate of the element in a non-covalent bonding manner. The composition preferably comprises compound (1) as component A, and further comprises a liquid crystal compound selected from component B, component C, component D and component E shown below. Component B is compound (2) to compound (4). Component C is compound (5) to compound (7). Component D is compound (8). Component E is compound (9) to compound (16). The composition may also comprise other liquid crystal compounds different from compounds (2) to compound (16). When preparing the composition, it is preferred to select component B, component C, component D and component E in consideration of the size of positive or negative dielectric anisotropy, etc. The composition with appropriately selected ingredients has a high upper limit temperature, a low lower limit temperature, a low viscosity, an appropriate optical anisotropy (i.e., a large optical anisotropy or a small optical anisotropy), a large positive or negative dielectric anisotropy, a large specific resistivity, stability to heat or ultraviolet rays, and an appropriate elastic constant (i.e., a large elastic constant or a small elastic constant).

In order to maintain high stability to ultraviolet rays, the preferred ratio of compound (1) is usually about 0.01% by weight or more based on the weight of the liquid crystal composition, and in order to dissolve in the liquid crystal composition, the preferred ratio of compound (1) is usually about 10% by weight or less. Based on the weight of the liquid crystal composition, a further preferred ratio is in the range of about 0.1% by weight to about 5% by weight. The most preferred ratio is in the range of about 0.5% by weight to about 3% by weight based on the weight of the liquid crystal composition.

Component B is a compound having two terminal groups of alkyl or the like. Preferred examples of component B include compounds (2-1) to (2-11), compounds (3-1) to (3-19), and compounds (4-1) to (4-7). In the compound of component B, R ¹¹ and R ¹² are independently alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, and in the alkyl or alkenyl group, at least one -CH ₂ - may be substituted by -O-, and at least one hydrogen may be substituted by fluorine.

Component B is a compound close to neutral because of its small absolute value of dielectric anisotropy. Compound (2) is mainly effective in reducing viscosity or adjusting optical anisotropy. Compound (3) and compound (4) are effective in expanding the temperature range of the nematic phase by increasing the upper limit temperature, or are effective in adjusting optical anisotropy.

As the content of component B increases, the dielectric anisotropy of the composition decreases, but the viscosity decreases. Therefore, as long as the required value of the threshold voltage of the element is met, the content is preferably more. In the case of preparing a composition for modes such as IPS and VA, the content of component B is preferably 30% by weight or more, and more preferably 40% by weight or more, based on the weight of the liquid crystal composition.

Component C is a compound (5) to a compound (7) having a halogen or fluorine-containing group at the right terminal. Preferred examples of component C include compounds (5-1) to (5-16), compounds (6-1) to (6-120), and compounds (7-1) to (7-63). In the compound of component C, R ¹³ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, wherein at least one -CH ₂ - in the alkyl group and the alkenyl group may be substituted by -O-, and at least one hydrogen may be substituted by fluorine; and X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ or -OCF ₂ CHFCF ₃ .

The dielectric anisotropy of component C is positive, and the stability to heat, light, etc. is very excellent, so it can be used to prepare compositions for modes such as IPS, FFS, and OCB. Based on the weight of the liquid crystal composition, the content of component C is suitably in the range of 1 wt % to 99 wt %, preferably in the range of 10 wt % to 97 wt %, and further preferably in the range of 40 wt % to 95 wt %. In the case where component C is added to a composition having a negative dielectric anisotropy, the content of component C is preferably 30 wt % or less based on the weight of the liquid crystal composition. By adding component C, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the element can be adjusted.

Component D is a compound (8) wherein the right terminal group is -C≡N or -C≡CC≡N. Preferred examples of component D include compounds (8-1) to (8-64). In the compound of component D, R ¹⁴ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, wherein at least one -CH ₂ - in the alkyl group or the alkenyl group may be substituted by -O-, and at least one hydrogen may be substituted by fluorine; and X ¹² is -C≡N or -C≡CC≡N.

The dielectric anisotropy of component D is positive and has a large value, so it can be mainly used to prepare the composition of the TN mode. By adding the component D, the dielectric anisotropy of the composition can be increased. Component D brings the effect of expanding the temperature range of the liquid crystal phase, adjusting the viscosity or adjusting the optical anisotropy. Component D is also useful for adjusting the voltage-transmittance curve of the element.

In the case of preparing a composition for a TN mode, the content of component D is suitably in the range of 1% to 99% by weight, preferably in the range of 10% to 97% by weight, and more preferably in the range of 40% to 95% by weight, based on the weight of the liquid crystal composition. In the case of adding component D to a composition having a negative dielectric anisotropy, the content of component D is preferably 30% by weight or less based on the weight of the liquid crystal composition. By adding component D, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the element can be adjusted.

Component E is compound (9) to compound (16). These compounds have a phenylene group substituted with two halogens in the lateral position, such as 2,3-difluoro-1,4-phenylene.

Preferred examples of component E include compounds (9-1) to (9-8), compounds (10-1) to (10-17), compounds (11-1), compounds (12-1) to (12-3), compounds (13-1) to (13-11), compounds (14-1) to (14-3), compounds (15-1) to (15-3), and compounds (16-1) to (16-3). In the compound of component E, ^R15 and ^R16 are independently alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, wherein at least one _-CH2- in the alkyl or alkenyl group may be substituted with -O-, and at least one hydrogen may be substituted with fluorine; and ^R17 is hydrogen, fluorine, alkyl having 1 to 10 carbon atoms or alkenyl having 2 to 10 carbon atoms, wherein at least one _-CH2- in the alkyl or alkenyl group may be substituted with -O-, and at least one hydrogen may be substituted with fluorine.

The dielectric anisotropy of component E is negative and large. Component E can be used to prepare compositions for modes such as IPS, VA, and PSA. As the content of component E is increased, the dielectric anisotropy of the composition is negative and increases, but the viscosity becomes larger. Therefore, as long as the required value of the threshold voltage of the element is met, the content is preferably less. If the dielectric anisotropy is considered to be about -5, in order to carry out sufficient voltage drive, the content of component E is preferably more than 40% by weight based on the weight of the liquid crystal composition.

Among component E, compound (9) is a bicyclic compound and thus has an effect mainly in reducing viscosity, adjusting optical anisotropy or increasing dielectric anisotropy. Compound (10) and compound (11) are tricyclic compounds and thus have an effect of increasing the upper limit temperature, increasing optical anisotropy or increasing dielectric anisotropy. Compounds (12) to (16) have an effect of increasing dielectric anisotropy.

In the case of preparing a composition for IPS, VA, PSA and other modes, the content of component E is preferably 40% by weight or more, and more preferably in the range of 50% by weight to 95% by weight, based on the weight of the liquid crystal composition. In the case of adding component E to a composition having positive dielectric anisotropy, the content of component E is preferably 30% by weight or less, based on the weight of the liquid crystal composition. By adding component E, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the element can be adjusted.

By appropriately combining the above-mentioned component B, component C, component D and component E, a liquid crystal composition satisfying at least one of the following characteristics can be prepared: high upper limit temperature, low lower limit temperature, low viscosity, appropriate optical anisotropy, large positive or negative dielectric anisotropy, large specific resistance, high stability to ultraviolet rays, high stability to heat, large elastic constant, etc. Liquid crystal compounds different from component B, component C, component D and component E may also be added as needed.

The liquid crystal composition is prepared by a known method. For example, the component compounds are mixed and then dissolved in each other by heating. Additives may also be added to the composition according to the application. Examples of additives are polymerizable compounds other than formula (1) and formula (16), polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, defoamers, etc. Such additives are well known to those skilled in the art and are described in the literature.

The polymerizable compound is added for the purpose of generating a polymer in the liquid crystal composition. Ultraviolet rays are irradiated while a voltage is applied between the electrodes, so that the polymerizable compound and the compound (1) are copolymerized, thereby generating a polymer in the liquid crystal composition. At this time, the compound (1) is fixed in a state where the polar group interacts with the surface of the glass (or metal oxide) substrate in a non-covalently bonded manner. As a result, the ability to control the orientation of the liquid crystal molecules is further improved, and the compound (1) will not leak into the liquid crystal composition. In addition, an appropriate pre-tilt angle is also obtained on the surface of the glass (or metal oxide) substrate, so a liquid crystal display element with a shortened response time and a large voltage holding ratio can be obtained.

Preferred examples of polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxirane, oxetane) and vinyl ketones. Further preferred examples are compounds having at least one acryloyloxy group and compounds having at least one methacryloyloxy group. Further preferred examples also include compounds having both acryloyloxy groups and methacryloyloxy groups.

Further preferred examples of polymerizable compounds are compounds (M-1) to (M-17). In compounds (M-1) to (M-17), R ²⁵ to R ³¹ are independently hydrogen or methyl; s, v and x are independently 0 or 1; t and u are independently integers from 1 to 10; L ²¹ to L ²⁶ are independently hydrogen or fluorine, and L ²⁷ and L ²⁸ are independently hydrogen, fluorine or methyl.

The polymerizable compound can be rapidly polymerized by adding a polymerization initiator. By optimizing the reaction temperature, the amount of the remaining polymerizable compound can be reduced. Examples of photoradical polymerization initiators are TPO, 1173 and 4265 in the Darocure series of BASF, and 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850 and 2959 in the Irgacure series.

Additional examples of the photoradical polymerization initiator include 4-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(4-butoxyphenylvinyl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzophenazine, a benzophenone/Michler's ketone mixture, a hexaarylbiimidazole/mercaptobenzimidazole mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, benzyl dimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, a 2,4-diethylxanthone/methyl p-dimethylaminobenzoate mixture, and a benzophenone/methyltriethanolamine mixture.

After adding a photo-radical polymerization initiator to the liquid crystal composition, ultraviolet rays are irradiated in an electric field, thereby polymerization can be carried out. However, unreacted polymerization initiator or decomposition products of the polymerization initiator may cause poor display such as afterimage of the image in the element. In order to prevent the above situation, photopolymerization can also be carried out without adding a polymerization initiator. The preferred wavelength of the irradiated light is in the range of 150nm to 500nm. Further preferred wavelength is in the range of 250nm to 450nm, and the most preferred wavelength is in the range of 300nm to 400nm.

When a compound (1) having an ester bond, a cinnamate bond, a chalcone skeleton or a stilbene skeleton is mixed into the composition, the main effects of the compound (1) as component A on the properties of the composition are as follows. The compound (1) is aligned in a certain direction at the molecular level when Fries rearrangement, photodimerization or cis-trans isomerization of double bonds occurs by polarization. Therefore, a film made of a polar compound aligns liquid crystal molecules in the same manner as an alignment film such as polyimide.

In the case of the compound (1) having an aromatic ester and a polymerizable group, the aromatic ester site is photodecomposed by irradiation with ultraviolet light to form a radical, thereby causing photo-Fries rearrangement.

In the photo-Fries rearrangement, when the polarization direction of the polarized ultraviolet light is the same as the long axis direction of the aromatic ester part, the photo-decomposition of the aromatic ester part occurs. After the photo-decomposition, re-bonding occurs and hydroxyl groups are generated in the molecule by tautomerization. It is believed that the interaction of the substrate interface occurs through the hydroxyl group, so that the polar compound has anisotropy and is easily adsorbed on the substrate interface side. In addition, since it has a polymerizable group, the compound (1) that reacts in the direction of the polarized light by polymerization is fixed without losing its directionality. The above properties can be used to prepare a film that can orient liquid crystal molecules. In order to prepare the above film, the ultraviolet light irradiated is preferably linearly polarized light. First, the compound (1) as a polar compound is added to the liquid crystal composition in a range of 0.1% to 10% by weight, and the composition is heated to dissolve the polar compound. The composition is injected into a device without an oriented film. Then, while the device is heated, the linearly polarized light is irradiated, thereby causing the polar compound to undergo photo-Fries rearrangement and polymerize.

The polar compounds rearranged by photo-Fries are arranged in a certain direction, and the film formed after polymerization has the function of serving as a liquid crystal alignment film.

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

The optically active compound has the effect of preventing reverse twisting by inducing a helical structure in the liquid crystal molecule and imparting a desired twist angle. By adding an optically active compound, the helical pitch can be adjusted. Two or more optically active compounds may also be added for the purpose of adjusting the temperature dependence of the helical pitch. Preferred examples of the optically active compound include the following compounds (Op-1) to (Op-18). In compound (Op-18), ring J is 1,4-cyclohexylene or 1,4-phenylene, and R ²⁸ is an alkyl group having 1 to 10 carbon atoms.

In order to maintain a large voltage holding ratio, an antioxidant is effective. Preferred examples of antioxidants include: the following compounds (AO-1) and (AO-2); IRGANOX 415, IRGANOX 565, IRGANOX 1010, IRGANOX 1035, IRGANOX 3114 and IRGANOX 1098 (trade name: BASF). In order to prevent the upper limit temperature from decreasing, an ultraviolet absorber is effective. Preferred examples of ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, triazole derivatives, and the like. Specific examples include: the following compound (AO-3) and compound (AO-4); TINUVIN 329, TINUVIN P, TINUVIN 326, TINUVIN 234, TINUVIN 213, TINUVIN 400, TINUVIN 328 and TINUVIN 99-2 (trade name: BASF); and 1,4-diazabicyclo[2.2.2]octane (1,4-diazabicyclo[2.2.2]octane; triethylenediamine, DABCO).

In order to maintain a large voltage holding ratio, a light stabilizer such as an amine with steric hindrance is preferred. Preferred examples of light stabilizers include: the following compounds (AO-5) and (AO-6); TINUVIN 144, TINUVIN 765 and TINUVIN 770DF (trade name: BASF). In order to maintain a large voltage holding ratio, a heat stabilizer is also effective, and a preferred example is IRGAFOS 168 (trade name: BASF). In order to prevent foaming, a defoamer is effective. Preferred examples of defoamers are dimethyl silicone oil, methylphenyl silicone oil, etc.

In compound (AO-1), R ⁴⁰ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, -COOR ⁴¹ or -CH ₂ CH ₂ COOR ⁴¹ , wherein R ⁴¹ is an alkyl group having 1 to 20 carbon atoms. In compounds (AO-2) and (AO-5), R ^{42 is an alkyl group having 1 to 20 carbon atoms. In compound (AO-5), R 43 is} hydrogen, methyl or O ^· (oxy radical), ring G is 1,4-cyclohexylene or 1,4-phenylene, and z is 1, 2 or 3.

4. Liquid crystal display element

The liquid crystal composition can be used for liquid crystal display elements having operating modes such as PC, TN, STN, OCB, PSA, etc. and driven in an active matrix mode. The composition can also be used for liquid crystal display elements having operating modes such as PC, TN, STN, OCB, VA, IPS, etc. and driven in a passive matrix mode. These elements can also be applied to any type of reflective, transmissive, and semi-transmissive types.

The composition can also be used for nematic curve alignment phase (nematiccurvilinear aligned phase, NCAP) elements made by microencapsulating nematic liquid crystals, polymer dispersed liquid crystal display elements (polymer dispersed liquid crystal display, PDLCD) and polymer network liquid crystal display elements (polymer network liquid crystal display, PNLCD) made by forming three-dimensional mesh polymers in liquid crystals. When the amount of polymerizable compound added is about 10% by weight or less based on the weight of the liquid crystal composition, a liquid crystal display element of PSA mode can be made. Based on the weight of the liquid crystal composition, the preferred ratio of the polymerizable compound is in the range of about 0.1% by weight to about 2% by weight. Based on the weight of the liquid crystal composition, the preferred ratio is in the range of about 0.2% by weight to about 1.0% by weight. The element of PSA mode can be driven by a driving method such as an active matrix or a passive matrix. This element can also be applied to any type of reflective, transmissive, and semi-transmissive types. By increasing the amount of polymerizable compound added, a polymer dispersed (polymerdispersed) mode element can also be made.

In a polymer-stabilized orientation type element, the polymer contained in the composition orients the liquid crystal molecules. Compound (1) as a polar compound assists the liquid crystal molecules in aligning. That is, compound (1) can be used instead of an orientation film. An example of a method for manufacturing such an element is as follows.

A component having two substrates called an array substrate and a color filter substrate is prepared. The substrate does not have an alignment film. At least one of the substrates has an electrode layer. A liquid crystal composition is prepared by mixing liquid crystal compounds. A polymerizable compound and a compound (1) as a polar compound are added to the composition. Additives may be further added as needed. The composition is injected into the component. The component is irradiated with light. Preferably, ultraviolet light is used. The polymerizable compound is polymerized by light irradiation. A composition containing a polymer is generated by the polymerization, thereby producing a component having a PSA mode.

The method for manufacturing an element is described. The first step is to add a compound (1) as a polar compound to a liquid crystal composition, and to heat the composition at a temperature higher than the upper limit temperature to dissolve it. The second step is to inject the composition into a liquid crystal display element. The third step is to irradiate polarized ultraviolet light while heating the liquid crystal composition to a temperature higher than the upper limit temperature. The compound (1) as a polar compound produces any one of photo-Fries rearrangement, photo-dimerization or cis-trans isomerization of double bonds by linear polarization, and also polymerizes. The polymer of the compound (1) is formed on a substrate in the form of a thin film and fixed. The polymer is arranged in a certain direction at the molecular level, so that the film has the function of a liquid crystal alignment film. The method can be used to manufacture a liquid crystal display element that does not have an alignment film such as polyimide.

In the procedure, the compound (1) as a polar compound is biased to exist on the substrate because the polar group interacts with the substrate surface. The compound (1) aligns the liquid crystal molecules by irradiation with polarized ultraviolet rays, and the polymerizable compound is polymerized by ultraviolet rays, thereby generating a polymer that maintains the orientation. Through the effect of the polymer, the orientation of the liquid crystal molecules is further stabilized, so the response time of the element is shortened. The residual image of the image is the poor operation of the liquid crystal molecules, so the residual image is also improved by the effect of the polymer. In particular, the compound (1) of the embodiment of the present invention is a polymerizable polar compound, so the liquid crystal molecules are oriented and copolymerized with other polymerizable compounds. As a result, the polar compound will not leak into the liquid crystal composition, so a liquid crystal display element with a large voltage holding ratio can be obtained.

Example

The present invention is further described in detail by examples (including synthesis examples and use examples of elements). The present invention is not limited to these examples. The present invention includes a mixture of the composition of use example 1 and the composition of use example 2. The present invention also includes a mixture prepared by mixing at least two of the compositions of the use examples.

1. Examples of Compound (1)

Compound (1) was synthesized by the procedure shown in Example 1. Unless otherwise specified, the reaction was carried out under nitrogen. The synthesized compound was identified by nuclear magnetic resonance (NMR) analysis and other methods. The properties of compound (1), liquid crystal compound, composition, and device were measured by the following methods.

NMR analysis: DRX-500 manufactured by Bruker BioSpin was used for the measurement. In the measurement of ¹ H-NMR, the sample was dissolved in a deuterated solvent such as CDCl ₃ , and the measurement was performed at room temperature at 500 MHz and 16 cumulative times. Tetramethylsilane was used as an internal standard. In the measurement of ¹⁹ F-NMR, CFCl ₃ was used as an internal standard and the measurement was performed with a cumulative number of 24 times. In the description of the nuclear magnetic resonance spectrum, s refers to a singlet, d refers to a doublet, t refers to a triplet, q refers to a quartet, quin refers to a quintet, sex refers to a sextet, m refers to a multiplet, and br refers to a broad peak.

Gas chromatography analysis: During the measurement, a GC-2010 gas chromatograph manufactured by Shimadzu Corporation was used. The column was a capillary column DB-1 (length 60m, inner diameter 0.25mm, film thickness 0.25μm) manufactured by Agilent Technologies Inc. As a carrier gas, helium (1ml/min) was used. The temperature of the sample vaporization chamber was set to 300°C, and the temperature of the detector (flame ionization detector (FID)) was set to 300°C. The sample was dissolved in acetone and prepared in a manner to become a 1% by weight solution, and 1μl of the obtained solution was injected into the sample vaporization chamber. The recorder used was a GC Solution system manufactured by Shimadzu Corporation.

High Performance Liquid Chromatography (HPLC) analysis: During the measurement, Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used. The column was YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle diameter 5 μm) manufactured by YMC. The eluent was used by appropriately mixing acetonitrile and water. As a detector, an ultraviolet (UV) detector, a refractive index (RI) detector, a Corona (CORONA) detector, etc. are preferably used. When a UV detector is used, the detection wavelength is set to 254 nm. The sample is dissolved in acetonitrile and prepared in a manner to become a 0.1% by weight solution, and 1 μL of the solution is introduced into the sample chamber. As a recorder, C-R7A plus (C-R7Aplus) manufactured by Shimadzu Corporation is used.

UV-visible spectrometry: PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used for the measurement. The detection wavelength was set to 190 nm to 700 nm. The sample was dissolved in acetonitrile to prepare a 0.01 mmol/L solution and placed in a quartz cell (optical path length 1 cm) for measurement.

Measurement sample: When measuring the phase structure and transition temperature (clearing point, melting point, polymerization initiation temperature, etc.), the compound itself is used as a sample.

Measurement method: The characteristics were measured by the following methods. Most of these methods are methods described in the JEITA standard (JEITA ED-2521B) reviewed and formulated by the Japan Electronics and Information Technology Industries Association (JEITA), or modified methods thereof. The TN element used for the measurement does not have a thin film transistor (TFT) installed.

(1) Phase structure

The sample was placed on a hot plate (Mettler FP-52 hot stage) of a melting point measuring apparatus equipped with a polarizing microscope. The sample was heated at a rate of 3°C/min while observing the phase state and its change using a polarizing microscope to identify the type of phase.

(2) Transition temperature (℃)

During the measurement, a scanning calorimeter Diamond DSC system manufactured by Perkin Elmer or a high-sensitivity differential scanning calorimeter X-DSC7000 manufactured by SSI Nanotechnology is used. The sample is heated and cooled at a rate of 3°C/min, and the initiation point of the endothermic peak or the exothermic peak accompanying the phase change of the sample is obtained by extrapolation to determine the transition temperature. The melting point and polymerization initiation temperature of the compound are also measured using the device. Sometimes the temperature at which a compound changes from a solid to a liquid crystal phase such as a smectic phase or a nematic phase is referred to as the "lower limit temperature of the liquid crystal phase". Sometimes the temperature at which a compound changes from a liquid crystal phase to a liquid is referred to as the "clearing point".

Crystal is represented by C. When distinguishing the types of crystals, they are represented as C ₁ and C ₂ , respectively. Smectic phase is represented by S, and nematic phase is represented by N. In the smectic phase, when distinguishing between smectic A phase, smectic B phase, smectic C phase, or smectic F phase, they are represented as _SA , _SB , _SC , or _SF , respectively. Liquid (isotropic) is represented by I. The transition temperature is represented, for example, as "C 50.0N100.0I". This means that the temperature of transition from crystal to nematic phase is 50.0°C, and the temperature of transition from nematic phase to liquid is 100.0°C.

(3) Upper limit temperature of nematic phase (T _NI or NI; °C)

The sample is 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 at which a part of the sample changes from the nematic phase to an isotropic liquid is measured. The upper limit temperature of the nematic phase is sometimes referred to as the "upper limit temperature". When the sample is a mixture of compound (1) and mother liquid crystals, it is represented by the symbol _TNI . When the sample is a mixture of compound (1) and a compound such as component B, component C, component D, it is represented by the symbol NI.

(4) Lower limit temperature of nematic phase ( _TC ; °C)

After storing a sample having a nematic phase in a freezer at 0°C, -10°C, -20°C, -30°C, and -40°C for 10 days, the liquid crystal phase is observed. For example, when the sample maintains a nematic phase at -20°C and changes to a crystalline or smectic phase at -30°C, T _C is recorded as ≤ -20°C. The lower limit temperature of the nematic phase is sometimes simply referred to as the "lower limit temperature".

(5) Viscosity (bulk viscosity; η; measured at 20°C; mPa·s)

For the measurement, an E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used.

(6) Optical anisotropy (refractive index anisotropy; measured at 25°C; Δn)

The measurement is performed using light of 589 nm wavelength with an Abbe refractometer equipped with a polarizing plate on the eyepiece. After rubbing the surface of the main prism in one direction, the sample is dropped onto the main prism. The refractive index (n∥) is measured when the direction of polarization is parallel to the direction of rubbing. The refractive index (n⊥) is measured when the direction of polarization is perpendicular to the direction of rubbing. The value of optical anisotropy (Δn) is calculated by the formula Δn = n∥-n⊥.

(7) Specific resistance (ρ; measured at 25°C; Ωcm)

1.0 mL of sample is injected into a container equipped with electrodes. A DC voltage (10 V) is applied to the container, and the DC current is measured after 10 seconds. The specific resistance is calculated by the following formula: (Specific resistance) = {(voltage) × (capacitance of container)} / {(DC current) × (dielectric constant of vacuum)}.

The method for measuring the characteristics of a sample with positive dielectric anisotropy and a sample with negative dielectric anisotropy may be different. The method for measuring the characteristics of a sample with positive dielectric anisotropy is described in Items (8a) to (12a). The method for measuring the characteristics of a sample with negative dielectric anisotropy is described in Items (8b) to (12b).

(8a) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s)

Positive dielectric anisotropy: The measurement is based on the method described in "Molecular Crystals and Liquid Crystals" (Vol. 259, 37 (1995)) by M. Imai et al. A sample is placed in a TN element in which the twist angle is 0 degrees and the distance between two glass substrates (cell gap) is 5 μm. A voltage is applied to the element in steps of 0.5 V in the range of 16 V to 19.5 V. After no voltage is applied for 0.2 seconds, the voltage is repeatedly applied under the conditions of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by the application are measured. The value of rotational viscosity is obtained based on these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al. The value of dielectric anisotropy required for the calculation is obtained by the method described below using the element in which the rotational viscosity is measured.

(8b) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s)

Negative dielectric anisotropy: The measurement is based on the method described in "Molecular Crystals and Liquid Crystals" (Vol. 259, 37 (1995)) by M. Imai et al. A sample is placed in a VA element in which the interval (cell gap) between two glass substrates is 20 μm. Voltage is applied to the element in steps of 1 volt in the range of 39 volts to 50 volts. After no voltage is applied for 0.2 seconds, voltage is repeatedly applied under the conditions of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current (peak current) and peak time (peak time) of the transient current (transient current) generated by the application are measured. The value of rotational viscosity is obtained based on these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al. The dielectric anisotropy required for the calculation is the value measured using the following dielectric anisotropy item.

(9a) Dielectric anisotropy (Δε; measured at 25°C)

Positive dielectric anisotropy: A sample is placed in a TN device with a distance (cell gap) of 9 μm between two glass substrates and a twist angle of 80 degrees. A sine wave (10 V, 1 kHz) is applied to the device, and after 2 seconds, the dielectric constant (ε∥) of the liquid crystal molecules in the long axis direction is measured. A sine wave (0.5 V, 1 kHz) is applied to the device, and after 2 seconds, the dielectric constant (ε⊥) of the liquid crystal molecules in the short axis direction is measured. The value of dielectric anisotropy is calculated by the formula Δε＝ε∥-ε⊥.

(9b) Dielectric anisotropy (Δε; measured at 25°C)

Negative dielectric anisotropy: The value of dielectric anisotropy is calculated by the formula Δε=ε∥-ε⊥. The dielectric constant (ε∥ and ε⊥) is measured as follows.

1) Determination of dielectric constant (ε∥): Apply a solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) on a thoroughly cleaned glass substrate. After rotating the glass substrate using a rotator, heat it at 150°C for 1 hour. Place a sample in a VA element with a gap (cell gap) of 4 μm between two glass substrates, and seal the element with an adhesive that is cured by ultraviolet light. Apply a sine wave (0.5 V, 1 kHz) to the element, and after 2 seconds, measure the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecules.

2) Determination of dielectric constant (ε⊥): A polyimide solution was applied to a fully cleaned glass substrate. After the glass substrate was calcined, a rubbing treatment was performed on the resulting alignment film. A sample was placed in a TN element with a distance (cell gap) of 9 μm between two glass substrates and a twist angle of 80 degrees. A sine wave (0.5 V, 1 kHz) was applied to the element, and after 2 seconds, the dielectric constant (ε⊥) of the liquid crystal molecules in the short axis direction was measured.

(10a) Elastic constant (K; measured at 25°C; pN)

Positive dielectric anisotropy: The measurement was performed using an HP4284A LCR meter manufactured by Yokogawa-Hewlett Packard Co., Ltd. A sample was placed in a horizontally oriented element in which the interval (cell gap) between two glass substrates was 20 μm. A charge of 0 volts to 20 volts was applied to the element, and the electrostatic capacitance and applied voltage were measured. The measured electrostatic capacitance (C) and applied voltage (V) values were fitted using equations (2.98) and (2.101) on page 75 of the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), and the values of _K11 and _K33 were obtained from equation (2.99). Subsequently, in equation (3.18) on page 171, _K22 was calculated using the previously determined values of _K11 and _K33 . The elastic constant K is represented by the average value of _K11 , _K22, and _K33 determined in this way.

(10b) Elastic constants (K ₁₁ and K ₃₃ ; measured at 25°C; pN)

Negative dielectric anisotropy: EC-1 elastic constant measuring instrument manufactured by TOYO Technica Co., Ltd. was used for the measurement. The sample was placed in a vertically oriented element with a spacing (cell gap) of 20 μm between two glass substrates. A charge of 20 volts to 0 volts was applied to the element, and the electrostatic capacitance and applied voltage were measured. The values of electrostatic capacitance (C) and applied voltage (V) were fitted using equations (2.98) and (2.101) on page 75 of the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), and the value of the elastic constant was obtained from equation (2.100).

(11a) Threshold voltage (Vth; measured at 25°C; V)

Positive dielectric anisotropy: LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The sample was placed in a normally white mode TN element in which the distance between the two glass substrates (cell gap) was 0.45/Δn (μm) and the twist angle was 80 degrees. The voltage applied to the element (32Hz, rectangular wave) was increased stepwise from 0V to 10V in units of 0.02V. At this time, light was irradiated to the element from a vertical direction, and the amount of light passing through the element was measured. A voltage-transmittance curve was prepared in which the transmittance was 100% when the light amount reached the maximum and the transmittance was 0% when the light amount was the minimum. The threshold voltage is represented by the voltage when the transmittance reaches 90%.

(11b) Threshold voltage (Vth; measured at 25°C; V)

Negative dielectric anisotropy: An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. A sample was placed in a normally black mode VA element in which the distance between two glass substrates (cell gap) was 4 μm and the rubbing direction was antiparallel, and the element was sealed using an adhesive that was cured by ultraviolet light. The voltage applied to the element (60 Hz, rectangular wave) was increased stepwise from 0 V to 20 V in units of 0.02 V. At this time, light was irradiated to the element from a vertical direction, and the amount of light passing through the element was measured. A voltage-transmittance curve was prepared in which the transmittance was 100% when the light amount reached a maximum and the transmittance was 0% when the light amount reached a minimum. The threshold voltage is represented by the voltage when the transmittance becomes 10%.

(12a) Response time (τ; measured at 25°C; ms)

Positive dielectric anisotropy: LCD5100 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 5kHz. The sample was placed in a normally white mode TN element with a distance (cell gap) of 5.0μm between two glass substrates and a twist angle of 80 degrees. A rectangular wave (60Hz, 5V, 0.5 seconds) was applied to the element. At this time, light was irradiated to the element from a vertical direction, and the amount of light passing through the element was measured. The maximum light amount was considered to be 100% transmittance, and the minimum light amount was considered to be 0% transmittance. The rise time (τr: rise time; milliseconds) is the time required for the transmittance to change from 90% to 10%. The fall time (τf: falltime; milliseconds) is the time required for the transmittance to change from 10% to 90%. The response time is expressed as the sum of the rise time and fall time calculated in this way.

(12b) Response time (τ; measured at 25°C; ms)

Negative dielectric anisotropy: LCD5100 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 5kHz. The sample was placed in a normally black mode PVA element in which the distance between the two glass substrates (cell gap) was 3.2μm and the rubbing direction was antiparallel. The element was sealed with an adhesive that was cured by ultraviolet light. A voltage slightly exceeding the threshold voltage was applied to the element for 1 minute, and then a voltage of 5.6V was applied while irradiating 23.5mW/ ^cm2 of ultraviolet light for 8 minutes. A rectangular wave (60Hz, 10V, 0.5 seconds) was applied to the element. At this time, light was irradiated from the vertical direction to measure the amount of light passing through the element. When the amount of light reached the maximum, the transmittance was regarded as 100%, and when the amount of light reached the minimum, the transmittance was regarded as 0%. The response time is expressed as the time required for the transmittance to change from 90% to 10% (fall time; milliseconds).

raw material

Solmix (registered trademark) A-11 is a mixture of ethanol (85.5%), methanol (13.4%), and isopropanol (1.1%), and was obtained from Japan Alcohol Sales Co., Ltd.

[Synthesis Example 1]

Synthesis of compound (No.81)

Step 1

Compound (T-1) (3.2 g), potassium carbonate (0.61 g), compound (T-2) (4.1 g) and DMF (100 ml) were placed in a reactor and stirred at 60°C for 2 hours. The reaction mixture was injected into water, and the aqueous layer was extracted with ethyl acetate. The organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, ethyl acetate: toluene = 1:3) to obtain compound (T-3) (1.55 g; 33%). Furthermore, compound (T-1) and compound (T-2) are known substances, and the synthesis method can be easily obtained by those with general knowledge in the technical field.

Step 2

Compound (T-3) (1.55 g), compound (T-4) (1.69 g), DMAP (0.12 g) and dichloromethane (100 ml) were placed in a reactor and cooled to 0°C. DCC (1.14 g) was added thereto, the temperature was restored to room temperature and stirred for 12 hours. After filtering and separating the insoluble matter, the reaction mixture was injected into water, and the aqueous layer was extracted with dichloromethane. The organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, ethyl acetate: toluene = 1:4), and reprecipitated with heptane to obtain compound (No.81) (2.34 g; 80%). Furthermore, compound (T-4) is a known substance, and a person with ordinary knowledge in the art can easily obtain a synthesis method.

The NMR analysis values of the obtained compound (No. 81) are as follows.

¹ H-NMR: chemical shift δ (ppm; CDCl ₃ ): 8.61 (d, 1H), 8.55 (d, 2H), 8.21 (d, 2H), 7.70 (d, 1H), 7.68 (s, 1H), 7.67(s,1H), 7.48(dd,1H), 7.31(dd,1H), 7.27(d,1H), 6.98(d,2H), 6.43(dd,1H), 6.42(dd,1H), 6.18 (dd ,1H), 6.13(dd,1H), 5.85(dd,1H), 5.84(dd,1H), 4.60(t,2H), 4.37(t,2H), 4.18(t,2H), 4.04(t, 2H), 1.84(quint,2H), 1.72(quint,2H), 1.55(quint,2H), 1.46(quint,2H).

The physical properties of the compound (No. 81) are as follows.

Transition temperature (℃): C 82.5I Polymerization temperature (℃): 136.49

[Synthesis Example 2]

Synthesis of compound (No.165)

Step 1

4-Iodophenol (30.0 g), trimethylsilyl acetylene (16.1 g), copper iodide (1.3 g), Pd(PPh ₃ ) ₂ Cl ₂ (1.91 g), tetrahydrofuran (THF) (200 ml) and triethylamine (200 ml) were collected in a container and stirred overnight under a nitrogen atmosphere. THF (200 ml), MeOH (200 ml) and KF (15.8 g) were added thereto and stirred overnight under an air atmosphere. The reaction mixture was poured into water, extracted with toluene, washed with water, dried with anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a light brown solid. The solid was made into a solution and purified by silica gel column chromatography (volume ratio, ethyl acetate:toluene=1:4) to obtain compound (T-5) (12.7 g; 80%).

The following two steps can be synthesized by using compound (T-5) instead of compound (T-1) and compound (T-6) instead of compound (T-2) in the first and second steps of Synthesis Example 1 and performing the same operation. Compound (T-6) is a known substance, and a person with ordinary knowledge in the art can easily obtain a synthesis method.

The NMR analysis values of the obtained compound (No. 165) are as follows.

¹ H-NMR: chemical shift δ (ppm; CDCl ₃ ): 8.13 (d, 2H), 7.57 (d, 2H), 7.46 (d, 2H), 7.19 (d, 2H), 6.97 (d, 2H), 6.85(d,2H), 6.42(dd,1H), 6.41(dd,1H), 6.13(dd,1H), 6.11(dd,1H), 5.84(dd,1H), 5.82(dd,1H), 4.24 (t,2H), 4.18(t,2H), 4.05(t,2H), 4.01(t,2H), 1.91(t,2H), 1.90(t,2H), 1.84(quint,2H), 1.73( quint,2H), 1.57(quint,2H), 1.48(quint,2H).

The physical properties of the compound (No. 165) are as follows.

Transition temperature (℃): C 80.0I Polymerization temperature (℃): 230.8

[Synthesis Example 3]

Synthesis of compound (No.148)

Step 1

Compound (T-5) (3 g), triethylamine (2.6 g) and dichloromethane (100 ml) were placed in a reactor and cooled in an ice bath. Acryloyl chloride (1.16 g) was added dropwise, and the mixture was returned to room temperature and stirred overnight. The reaction mixture was filtered, the filtrate was concentrated, and the residue was purified by silica gel chromatography (volume ratio, ethyl acetate: toluene = 1:3) to obtain compound (T-7) (0.77 g; 21%).

Step 2

In the second step of Synthesis Example 1, Compound (No. 148) was synthesized by using Compound (T-7) instead of Compound (T-3) and performing the same operation.

The NMR analysis values of the obtained compound (No. 148) are as follows.

¹ H-NMR: chemical shift δ (ppm; CDCl ₃ ): 8.12(d,2H), 7.58(d,2H), 7.55(d,2H), 7.20(d,2H), 7.14(d,2H), 6.96(d,2H), 6.62(dd,1H), 6.41(dd,1H), 6.31(dd,1H), 6.13(dd,1H), 6.04(dd,1H), 5.82(dd,1H), 4.18 (t,2H), 4.05(t,2H), 1.84(quint,2H), 1.73(quint,2H), 1.53(quint,2H), 1.48(quint,2H).

The physical properties of the compound (No. 148) are as follows.

Transition temperature (℃): C 113.8IPolymerization temperature (℃): 259.1

[Synthesis Example 4]

Synthesis of compound (No.221)

Step 1

4-iodo-2-methylphenol (6 g), 1,4-diethynylbenzene (1.53 g), copper iodide (0.12 g), Pd(PPh ₃ ) ₂ Cl ₂ (0.90 g), THF (50 ml) and triethylamine (50 ml) were collected in a container and stirred overnight under a nitrogen atmosphere. The reaction mixture was poured into water, extracted with toluene, washed with water, dried with anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a light brown solid. The solid was made into a solution, purified by silica gel column chromatography (volume ratio, ethyl acetate: toluene = 1:3), and the obtained solution was dissolved in a mixed solution of MeOH (100 ml) and THF (100 ml). KF (7.7 g) was added thereto, and stirred overnight at room temperature. The obtained product was concentrated and purified by silica gel column chromatography (volume ratio, ethyl acetate:toluene=1:4) to obtain compound (T-8) (2.95 g; 68%).

The following two steps can be synthesized by using compound (T-8) instead of compound (T-1) in the first step and the second step of Synthesis Example 1 and performing the same operation.

The NMR analysis values of the obtained compound (No. 221) are as follows.

¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 8.15(d,2H), 7.48(s,4H), 7.45(s,1H), 7.42(d,1H), 7.35(d,1H), 7.34(s,1H), 7.13(d,1H), 6.98(d,2H), 6.78(d,1H), 6.45(dd,1H), 6.40(dd,1H) , 6.17(dd,1H), 6.13(dd,1H), 5.87(dd,1H), 5.82(dd,1H), 4.55(t,2H), 4.24(t,2H), 4.18(t,2H), 4.05(t,2H), 1.85(quint,2H), 1.73(quint,2H), 1.54(quint, 2H), 1.47(quint,2H).

The physical properties of the compound (No. 221) are as follows.

Transition temperature (℃): C 77.22N 95.28IPolymerization temperature (℃): 198.8

[Synthesis Example 5]

Synthesis of compound (No.16)

In Synthesis Example 1, Compound (T-10) was used instead of Compound (T-1), and Compound (T-9) was used instead of Compound (T-4), and the same operation was performed to synthesize Compound (No. 16). Compound (T-9) and Compound (T-10) are known substances, and the synthesis method can be easily obtained by a person with ordinary knowledge in the art.

The NMR analysis values of the obtained compound (No. 16) are as follows.

¹ H-NMR: chemical shift δ (ppm; CDCl ₃ ): 8.73 (s, 1H), 8.18 (dd, 1H), 7.90 (d, 1H), 7.82 (d, 1H), 7.53 (d, 2H), 7.46(s,1H), 7.43(dd,1H), 7.23(dd,1H), 7.22(d,1H), 7.19(s,1H), 7.00(d,2H), 6.46(dd,1H), 6.41 (dd,1H)、6 .19(dd,1H), 6.13(dd,1H), 5.87(dd,1H), 5.82(dd,1H), 4.55(t,2H), 4.27(t,2H), 4.19(t,2H), 4.13(t,2H), 1.90(quint,2H), 1.75(quint,2H), 1.58(quint,2H), 1.50(quint,2H).

The physical properties of the compound (No. 16) are as follows.

Transition temperature (℃): C 96.8N 154.3IPolymerization temperature (℃): 176.8

[Synthesis Example 6]

Synthesis of compound (No.158)

Step 1

4-iodophenol (30.0 g), potassium carbonate (38.0 g), compound (T-11) (17.0 g) and DMF (300 ml) were placed in a reactor and stirred at 100° C. for 10 hours. The reaction mixture was injected into water, and the aqueous layer was extracted with ethyl acetate. The organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, ethyl acetate: toluene = 1:3) to obtain compound (T-12) (35.0 g; 97%).

Step 2

Compound (T-12) (35.0 g), trimethylsilyl acetylene (15.6 g), copper iodide (2.5 g), Pd(PPh ₃ ) ₂ Cl ₂ (4.67 g) and triethylamine (200 ml) were collected in a container and stirred overnight. The reaction mixture was poured into water, extracted with toluene, washed with water, dried with anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a light brown solid. The solid was made into a solution, purified by silica gel column chromatography (volume ratio, ethyl acetate: toluene = 1:4), and the obtained solution was dissolved in a mixed solution of methanol (100 ml) and THF (100 ml). KF (7.7 g) was added thereto, and stirred at room temperature overnight. The obtained solution was concentrated and purified by silica gel column chromatography (volume ratio, ethyl acetate: toluene = 1:4) to obtain compound (T-13) (17.9 g; 83%).

Step 3

Compound (T-13) (32.5 g), acrylic acid (20.0 g), DMAP (2.7 g) and dichloromethane (500 ml) were placed in a reactor and cooled to 0°C. DCC (48.1 g) was added thereto, the mixture was returned to room temperature and stirred for 12 hours. After filtering and separating the insoluble matter, the reaction mixture was injected into water, and the aqueous layer was extracted with dichloromethane. The organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene) to obtain compound (T-14) (45 g; 93%).

Step 4

Compound (T-14) (24.0 g), trimethylsilyl acetylene (54.5 g), copper iodide (2.11 g), Pd(PPh ₃ ) ₂ Cl ₂ (3.89 g), THF (200 ml) and triethylamine (200 ml) were collected in a container and stirred overnight under oxygen. The reaction mixture was poured into water, extracted with toluene, washed with water, dried with anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a light brown solid. The solid was made into a solution, purified by silica gel column chromatography (volume ratio, ethyl acetate: toluene = 1:4), and the obtained solution was dissolved in a mixed solution of methanol (100 ml) and THF (100 ml). KF (7.7 g) was added thereto, and stirred overnight at room temperature. The obtained solution was concentrated and purified by silica gel column chromatography (volume ratio, ethyl acetate: toluene = 1:4) to obtain compound (T-15) (12.6 g; 66%).

Step 5

4-iodo-2-methylphenol (50.0 g), compound (T-16) (65.5 g), DMAP (5.2 g) and dichloromethane (1000 ml) were placed in a reactor and cooled to 0°C. DCC (46.2 g) was added thereto, the mixture was returned to room temperature and stirred for 12 hours. After filtering and separating the insoluble matter, the reaction mixture was injected into water, and the aqueous layer was extracted with dichloromethane. The organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, ethyl acetate: toluene = 1:9) to obtain compound (T-17) (86 g; 79%).

Step 6

Compound (T-17) (4.9 g), compound (T-15) (2.2 g), copper iodide (0.05 g), Pd(PPh ₃ ) ₂ Cl ₂ (0.18 g), THF (200 ml) and triethylamine (200 ml) were collected in a container and stirred overnight. The reaction mixture was poured into water, extracted with toluene, washed with water, dried with anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a light brown solid. The solid was made into a solution and purified by silica gel column chromatography (volume ratio, ethyl acetate:toluene=1:9) to obtain compound (No.158) (21 g; 64.5%).

The NMR analysis values of the obtained compound (No. 158) are as follows.

¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 8.13 (d, 2H), 7.49 (d, 2H), 7.44 (s, 1H), 7.40 (d, 1H), 7.11 (d, 1H), 6.98(d,2H), 6.88(d,2H), 6.43(dd,2H), 6.15(dd,2H), 5.85(dd,2H), 4.52(t,2H), 4.23(t,2H), 4.18 (t,2H), 4.05(t,2H), 2.21(s,3H), 1.84(quint,2H), 1.73(quint,2H), 1.55(quint,2H), 1.47(quint,2H).

The physical properties of the compound (No. 158) are as follows.

Transition temperature (℃): C 77.9N 82.5IPolymerization temperature (℃): 231.86

The following compounds (No. 1) to (No. 224) can be synthesized according to the synthesis methods described in the synthesis examples.

2. Examples of component usage

The compounds in the use examples are represented by symbols based on the definitions in Table 2 below. In Table 2, the stereo configuration associated with 1,4-cyclohexylene is the trans configuration. The numbers in the brackets after the symbols correspond to the numbers of the compounds. The symbol (-) refers to other liquid crystal compounds. The ratio (percentage) of the liquid crystal compounds is the weight percentage (wt%) based on the weight of the liquid crystal composition. Finally, the characteristic values of the liquid crystal composition are summarized.

Table 2 Expression of compounds using symbols

R-(A ₁ )-Z ₁ -·····-Z _n -(A _n )-R'

1. Raw materials

A composition to which a polar compound is added is injected into a device without an alignment film. After irradiation with linear polarized light, the orientation of the liquid crystal molecules in the device is confirmed. First, the raw materials are described. The raw materials are appropriately selected from compositions such as composition (M1) to composition (M41) and polar compounds such as compound (No.1) to compound (No.224). The composition is as follows.

[Composition (M1)]

NI=73.2℃; Tc<-20℃; Δn=0.113; Δε=-4.0; Vth=2.18V; η=22.6mPa·s.

[Composition (M2)]

NI＝82.8℃; Tc<-30℃; Δn＝0.118; Δε＝-4.4; Vth＝2.13V; η＝22.5mPa·s.

[Composition (M3)]

NI=78.1℃; Tc<-30℃; Δn=0.107; Δε=-3.2; Vth=2.02V; η=15.9mPa·s.

[Composition (M4)]

NI＝88.5℃; Tc<-30℃; Δn＝0.108; Δε＝-3.8; Vth＝2.25V; η＝24.6mPa·s; VHR-1＝99.1%; VHR-2＝98.2%; VHR-3＝ 97.8%.

[Composition (M5)]

NI=81.1℃; Tc<-30℃; Δn=0.119; Δε=-4.5; Vth=1.69V; η=31.4mPa·s.

[Composition (M6)]

NI＝98.8℃; Tc<-30℃; Δn＝0.111; Δε＝-3.2; Vth＝2.47V; η＝23.9mPa·s.

[Composition (M7)]

NI＝77.5℃; Tc<-30℃; Δn＝0.084; Δε＝-2.6; Vth＝2.43V; η＝22.8mPa·s.

[Composition (M8)]

NI＝70.6℃; Tc<-20℃; Δn＝0.129; Δε＝-4.3; Vth＝1.69V; η＝27.0mPa·s.

[Composition (M9)]

NI=93.0℃; Tc<-30℃; Δn=0.123; Δε=-4.0; Vth=2.27V; η=29.6mPa·s.

[Composition (M10)]

NI＝87.6℃; Tc<-30℃; Δn＝0.126; Δε＝-4.5; Vth＝2.21V; η＝25.3mPa·s.

[Composition (M11)]

NI=93.0℃; Tc<-20℃; Δn=0.124; Δε=-4.5; Vth=2.22V; η=25.0mPa·s.

[Composition (M12)]

NI＝76.4℃; Tc<-30℃; Δn＝0.104; Δε＝-3.2; Vth＝2.06V; η＝15.6mPa·s.

[Composition (M13)]

NI＝78.3℃; Tc<-20℃; Δn＝0.103; Δε＝-3.2; Vth＝2.17V; η＝17.7mPa·s.

[Composition (M14)]

NI＝81.2℃; Tc<-20℃; Δn＝0.107; Δε＝-3.2; Vth＝2.11V; η＝15.5mPa·s.

[Composition (M15)]

NI＝88.7℃; Tc<-30℃; Δn＝0.115; Δε＝-1.9; Vth＝2.82V; η＝17.3mPa·s.

[Composition (M16)]

NI＝89.9℃; Tc<-20℃; Δn＝0.122; Δε＝-4.2; Vth＝2.16V; η＝23.4mPa·s.

[Composition (M17)]

NI=77.1℃; Tc<-20℃; Δn=0.101; Δε=-3.0; Vth=2.04V; η=13.9mPa·s.

[Composition (M18)]

NI=75.9℃; Tc<-20℃; Δn=0.114; Δε=-3.9; Vth=2.20V; η=24.7mPa·s.

[Composition (M19)]

NI＝80.8℃; Tc<-20℃; Δn＝0.108; Δε＝-3.8; Vth＝2.02V; η＝19.8mPa·s.

[Composition (M20)]

NI＝85.3℃; Tc<-20℃; Δn＝0.109; Δε＝-3.6; Vth＝2.06V; η＝20.9mPa·s.

[Composition (M21)]

NI＝87.5℃; Tc<-20℃; Δn＝0.100; Δε＝-3.4; Vth＝2.25V; η＝16.6mPa·s.

[Composition (M22)]

NI＝79.8℃; Tc<-30℃; Δn＝0.106; Δε＝8.5; Vth＝1.45V; η＝11.6mPa·s; γ1＝60.0mPa·s.

[Composition (M23)]

NI＝71.2℃; Tc<-20℃; Δn＝0.099; Δε＝6.1; Vth＝1.74V; η＝13.2mPa·s; γ1＝59.3mPa·s.

[Composition (M24)]

NI=78.5℃; Tc<-20℃; Δn=0.095; Δε=3.4; Vth=1.50V; eta=8.4mPa·s; γ1=54.2mPa·s.

[Composition (M25)]

NI＝90.3℃; Tc<-20℃; Δn＝0.089; Δε＝5.5; Vth＝1.65V; η＝13.6mPa·s; γ1＝60.1mPa·s.

[Composition (M26)]

NI=78.3℃; Tc<-20℃; Δn=0.107; Δε=7.0; Vth=1.55V; eta=11.6mPa·s; γ1=55.6mPa·s.

[Composition (M27)]

NI＝80.4℃; Tc<-20℃; Δn＝0.106; Δε＝5.8; Vth＝1.40V; η＝11.6mPa·s; γ1＝61.0mPa·s.

[Composition (M28)]

NI＝78.4℃; Tc<-20℃; Δn＝0.094; Δε＝5.6; Vth＝1.45V; η＝11.5mPa·s; γ1＝61.7mPa·s.

[Composition (M29)]

NI＝80.0℃; Tc<-20℃; Δn＝0.101; Δε＝4.6; Vth＝1.71V; η＝11.0mPa·s; γ1＝47.2mPa·s.

[Composition (M30)]

NI＝78.6℃; Tc<-20℃; Δn＝0.088; Δε＝5.6; Vth＝1.85V; η＝13.9mPa·s; γ1＝66.9mPa·s.

[Composition (M31)]

NI＝82.9℃; Tc<-20℃; Δn＝0.093; Δε＝6.9; Vth＝1.50V; η＝16.3mPa·s; γ1＝65.2mPa·s.

[Composition (M32)]

NI=79.6℃; Tc<-20℃; Δn=0.111; Δε=4.7; Vth=1.86V; eta=9.7mPa·s; γ1=49.9mPa·s.

[Composition (M33)]

NI=83.0℃; Tc<-20℃; Δn=0.086; Δε=3.8; Vth=1.94V; eta=7.5mPa·s; γ1=51.5mPa·s.

[Composition (M34)]

NI＝81.9℃; Tc<-20℃; Δn＝0.109; Δε＝4.8; Vth＝1.75V; η＝13.3mPa·s; γ1＝57.4mPa·s.

[Composition (M35)]

NI＝78.2℃; Tc<-20℃; Δn＝0.101; Δε＝6.7; Vth＝1.45V; η＝17.8mPa·s; γ1＝67.8mPa·s.

[Composition (M36)]

NI＝77.6℃; Tc<-20℃; Δn＝0.109; Δε＝10.6; Vth＝1.34V; η＝22.6mPa·s; γ1＝92.4mPa·s.

[Composition (M37)]

NI=85.2℃; Tc<-20℃; Δn=0.102; Δε=4.1; γ1=43.0mPa·s.

[Composition (M38)]

NI=85.8℃; Tc<-20℃; Δn=0.115; Δε=4.2; γ1=41.4mPa·s.

[Composition (M39)]

NI＝78.4℃; Tc<-20℃; Δn＝0.094; Δε＝5.6; Vth＝1.45V; η＝11.5mPa·s; γ1＝61.7mPa·s.

[Composition (M40)]

NI＝79.3℃; Tc<-20℃; Δn＝0.099; Δε＝5.0; Vth＝1.64V; η＝10.4mPa·s; γ1＝44.7mPa·s.

[Composition (M41)]

NI＝79.7℃; Tc<-20℃; Δn＝0.091; Δε＝5.7; Vth＝1.83V; η＝14.9mPa·s; γ1＝69.3mPa·s.

2. Orientation of liquid crystal molecules

Use Case 1 to Use Case 7

(Sample Preparation)

Compound (No. 148) as the first additive was added to composition (M1) at a ratio of 0.1 wt%, 0.3 wt%, 0.5 wt%, 1.0 wt%, 3.0 wt%, 5.0 wt%, and 10.0 wt%, and a compound (AO-1) in which R ⁴⁰ is an n-heptyl group was added as an antioxidant at a ratio of 150 ppm. The mixture was heated and stirred at 100°C, then returned to room temperature and left for one week. As a result, no crystals or the like were precipitated and the mixture was completely dissolved.

(Component production)

The mixture was injected into an IPS element without an alignment film at 90°C (above the upper limit temperature of the nematic phase). The IPS element was heated at 90°C and irradiated with polarized ultraviolet rays having peaks at wavelengths of 313nm, 335nm, and 365nm from the normal direction for a certain period of time to perform an alignment treatment, and the irradiation was continued until the alignment became good.

(Polarized UV irradiation conditions)

The illuminance at a wavelength of 313 nm was 3 mW/cm ² . The illuminance was measured using UIT-150 and UVD-S313 manufactured by Ushio Electric Co., Ltd.

The ultraviolet irradiation lamp used was USH-250BY manufactured by Ushio Electric Co., Ltd.

The exposure unit used was ML-251A/B manufactured by Ushio Electric Co., Ltd.

Polarized ultraviolet light was generated using a wire grid polarizing element (ProFlux UVT260A manufactured by Polatechno Co., Ltd.).

(Orientation confirmation method)

The element is placed parallel to the polarization axis of linear polarization and placed on a polarizing microscope in which the polarizing element and the analyzer are arranged orthogonally, and light is irradiated from below to observe whether there is light leakage. If light does not pass through the element, it is judged that the orientation is "good". If light is observed to pass through the element, it is judged that the orientation is "poor" and the irradiation is insufficient.

(Evaluation of Ease of Orientation)

The irradiation time was changed from 1 minute to 60 minutes, and the orientation was confirmed at each irradiation time. The irradiation was terminated at the time point when the orientation became good. The irradiation time until the orientation became good is summarized in the following Table 3.

Use Case 8 to Use Case 42

Using composition (M1), a compound (AO-1) in which R ⁴⁰ is an n-heptyl group was added as an antioxidant at a ratio of 150 ppm, and the first additive was mixed at the ratio shown in Table 3 below. Otherwise, the same operation as in Example 1 was performed. The irradiation time was measured by the same method as in Example 1. The results are summarized in Table 3 below.

Table 3

In Use Examples 1 to 42, the compositions used were changed to M2 to M41, and the same operation was performed. As a result, the irradiation time did not change significantly in any of the cases.

The same operation was performed by appropriately selecting the first additive from the composition (M1) to the composition (M41) and the compound (No. 1) to the compound (No. 224). As a result, in any of them, the irradiation time was within 15 minutes.

Comparative Example 1 to Comparative Example 21

Compound (A-1-1-1), compound (S-1) described in Patent Document 3, and compound (S-2) described in Patent Document 2 were used as the first additive and mixed into composition (M1) in the ratio shown in Table 4 below, and the irradiation time was evaluated by the same operation as in the use example. As a result, compared with the compounds of the embodiments of the present invention, in any compound, when the longest irradiation time in the use example was 10 minutes, good orientation could not be obtained, and it was confirmed that the irradiation time for good orientation was more than 30 minutes. In addition, the same evaluation was performed using compositions (M2) to (M41), and the results were all the same tendency as when composition (M1) was used.

Table 4

In the use example, although the composition or the type and amount of the compound (1) as a polar compound were changed, there was no dissolved residue or precipitation, and no light leakage of the element was observed during irradiation within 15 minutes. The results show that even if there is no alignment film such as polyimide in the element, the orientation is good, and all liquid crystal molecules are arranged in a certain direction. On the other hand, in the comparative example, if the irradiation is within 30 minutes, light leakage of the element is observed, and the orientation is not good. Therefore, as long as the compound (1) of the embodiment of the present invention is used, it can be used for short-time or low-energy light irradiation, thereby reducing the shortening of the tact time and the damage to the mother liquid crystal caused by light irradiation. In addition, as long as the liquid crystal composition of the embodiment of the present invention is used, a liquid crystal display element having at least one characteristic of a wide temperature range in which the element can be used, a short response time, a high voltage holding ratio, a low threshold voltage, a large contrast, and a long life can be obtained. Furthermore, a liquid crystal display element can be obtained having a liquid crystal composition that satisfies at least one of the following properties: a high upper limit temperature of the nematic phase, a low lower limit temperature of the nematic phase, a low viscosity, a suitable optical anisotropy, a large negative dielectric anisotropy, a large specific resistivity, a high stability to ultraviolet rays, and a high stability to heat.

Industrial Applicability

The liquid crystal composition according to the embodiment of the present invention can be used in a liquid crystal monitor, a liquid crystal television, and the like.

Claims (15)

1. A compound represented by formula (1-1) or formula (1-3);

in the formula (1-1) and the formula (1-3),

ring A ¹ Ring A ² Ring A ³ Ring A ⁴ Independently 1, 4-cyclohexylene, 1, 4-phenylene, naphthalene-2, 6-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, the group represented by (a-1), or the group represented by (a-2), at least one hydrogen in these rings being substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, or an alkenyloxy group having 2 to 11 carbon atoms, at least one hydrogen in these groups being substituted by fluorine or chlorine, (a-2), c is 2, 3, or 4; wherein ring A ¹ Ring A ² Ring A ³ Or ring A ⁴ At least one of which is phenanthrene-2, 7-diyl, (A-1) or (A-2);

Z ² 、Z ³ z is as follows ⁴ Independently a single bond, - (CH) ₂ ) ₂ -、-CH＝CH-、-C≡C-、-COO-、-OCO-、-CF ₂ O-、-OCF ₂ -、-CH ₂ O-、-OCH ₂ -, -cf=cf-, -ch=chcoo-, -ococh=ch-, -ch=chco-, or-coch=ch-, wherein Z ² 、Z ³ Z is as follows ⁴ At least one of them is-COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO-, or-COCH=CH-;

Sp ¹ sp and Sp ² Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -may be substituted by-O-, -COO-, -OCOO-or-OCO-, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-, of which groups at least one hydrogen may be substituted by fluorine or chlorine;

P ¹ p ² Independently a group represented by any one of the formulae (1 b) to (1 h);

in the formulas (1 b) to (1 h),

M ¹ 、M ² 、M ³ m and M ⁴ Independently hydrogen, halogen, alkyl of 1 to 5 carbon atoms or alkyl of 1 to 5 carbon atoms with at least one hydrogen substituted with halogen;

R ² is hydrogen, halogen, alkyl of 1 to 5 carbon atoms, at least one hydrogen of which may be substituted by halogen, at least one-CH ₂ -may be substituted by-O-;

R ³ 、R ⁴ 、R ⁵ 、R ⁶ r is R ⁷ Independently hydrogen or C1-15 alkyl, at least one of said alkyl groups being-CH ₂ -may be substituted by-O-or-S-, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by halogen.

2. The compound according to claim 1, wherein in the formula (1-1) and the formula (1-3),

ring A ¹ Ring A ² Ring A ³ Ring A ⁴ Independently 1, 4-cyclohexylene, 1, 4-phenylene, naphthalene-2, 6-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, the group represented by (a-1) or the group represented by (a-2), wherein at least one hydrogen in these rings may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms or an alkenyloxy group having 2 to 11 carbon atoms, (a-2) wherein c is 2, 3 or 4; wherein ring A ¹ Ring A ² Ring A ³ Or ring A ⁴ At least one of which is phenanthrene-2, 7-diyl, (A-1) or (A-2);

Z ² 、Z ³ z is as follows ⁴ Independently a single bond, - (CH) ₂ ) ₂ -, -CH=CH-, -C≡C-, -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CHCO-, or-COCH=CH-, wherein Z ² 、Z ³ Z is as follows ⁴ At least one of them is-COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO-, or-COCH=CH-;

Sp ¹ sp and Sp ² Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -may be substituted by-O-, -COO-, -OCOO-or-OCO-, at least one- (CH) ₂ ) ₂ -may be substituted with-ch=ch-;

P ¹ p ² Independently a group represented by any one of formula (1 b), formula (1 c), formula (1 d) or formula (1 e);

in the formulas (1 b) to (1 e),

M ¹ 、M ² 、M ³ m and M ⁴ Independently and separatelyIs hydrogen, halogen, alkyl of 1 to 5 carbon atoms or alkyl of 1 to 5 carbon atoms with at least one hydrogen substituted by halogen;

R ² is hydrogen, halogen or C1-5 alkyl, wherein at least one hydrogen may be substituted by halogen, at least one-CH ₂ -may be substituted by-O-;

R ³ 、R ⁴ 、R ⁵ r is R ⁶ Independently hydrogen or C1-15 alkyl, at least one of said alkyl groups being-CH ₂ -may be substituted by-O-or-S-, at least one- (CH) ₂ ) ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by halogen.

3. The compound according to claim 1, wherein in the formula (1-1) and the formula (1-3),

ring A ¹ Ring A ² Ring A ³ Ring A ⁴ Independently 1, 4-cyclohexylene, 1, 4-phenylene, naphthalene-2, 6-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, the group represented by (a-1) or the group represented by (a-2), wherein at least one hydrogen in these rings may be substituted by fluorine, chlorine, methyl or ethyl, and wherein c is 2, 3 or 4; wherein ring A ¹ Ring A ² Ring A ³ Or ring A ⁴ At least one of which is phenanthrene-2, 7-diyl, (A-1) or (A-2);

Z ² 、Z ³ z is as follows ⁴ Independently a single bond, - (CH) ₂ ) ₂ -, -CH=CH-, -C≡C-, -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CHCO-, or-COCH=CH-, wherein Z ² 、Z ³ Z is as follows ⁴ At least one of them is-COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO-, or-COCH=CH-;

Sp ¹ sp and Sp ² Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -may be substituted by-O-, -COO-, -OCOO-or-OCO-, at least one- (CH) ₂ ) ₂ -may be substituted with-ch=ch-;

P ¹ p ² Independently a group represented by formula (1 b-1), formula (1 b-2), formula (1 b-3), formula (1 b-4), formula (1 b-5), formula (1 c-1), formula (1 d-2) or formula (1 e-1);

4. The compound according to claim 1, wherein Z in the compound represented by the formula (1-1) or the formula (1-3) ² 、Z ³ Or Z is ⁴ Either of them is-COO-or-OCO-.

5. A compound represented by the formula (1-a);

P ¹ —Sp ¹ -Y-Sp ² —P ² (1-A)

P ¹ p ² Independently a group represented by formula (1 b-1), formula (1 b-2), formula (1 b-3), formula (1 b-4), formula (1 b-5), formula (1 c-1), formula (1 d-2) or formula (1 e-1);

Sp ¹ sp and Sp ² Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -may be substituted by-O-, -COO-, -OCOO-or-OCO-, at least one- (CH) ₂ ) ₂ -may be substituted with-ch=ch-;

y is a group represented by any one of (MES-1-01) to (MES-1-06), in which at least one hydrogen may be substituted with fluorine, chlorine, methyl or ethyl;

6. the compound according to claim 5, wherein Sp is the compound represented by the formula (1-A) ¹ Sp and Sp ² Independently an alkylene group of 1 to 10 carbon atoms, at least one of the alkylene groups-CH ₂ -may be substituted by-O-, -COO-, -OCOO-or-OCO-, at least one- (CH) ₂ ) ₂ -may be substituted with-ch=ch-.

7. A liquid crystal composition containing at least one of the compounds according to any one of claims 1 to 6.

8. The liquid crystal composition according to claim 7, further comprising at least one compound selected from the group of compounds represented by formulas (2) to (4);

In the formulas (2) to (4),

R ¹¹ r is R ¹² Independently is an alkyl group of 1 to 10 carbon atoms or an alkenyl group of 2 to 10 carbon atoms, at least one of which-CH ₂ -may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

ring B ¹ Ring B ² Ring B ³ Ring B ⁴ Independently 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene or pyrimidine-2, 5-diyl;

Z ¹¹ 、Z ¹² z is as follows ¹³ Independently a single bond, -CH ₂ CH ₂ -, -CH=CH-, -C≡C-, or-COO-.

9. The liquid crystal composition according to claim 7 or 8, further comprising at least one compound selected from the group of compounds represented by formulas (5) to (7);

in the formulas (5) to (7),

R ¹³ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one of the alkyl and alkenyl groups being-CH ₂ -may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

X ¹¹ is fluorine, chlorine, -OCF ₃ 、-OCHF ₂ 、-CF ₃ 、-CHF ₂ 、-CH ₂ F、-OCF ₂ CHF ₂ or-OCF ₂ CHFCF ₃ ；

Ring C ¹ Ring C ² Ring C ³ Independently 1, 4-cyclohexylene, 1, 4-phenylene, which may be substituted with at least one hydrogen by fluorine, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl or pyrimidine-2, 5-diyl;

Z ¹⁴ 、Z ¹⁵ z is as follows ¹⁶ Independently a single bond, -CH ₂ CH ₂ -、-CH＝CH-、-C≡C-、-COO-、-CF ₂ O-、-OCF ₂ -、-CH ₂ O-, -cf=cf-, -ch=cf-, or- (CH) ₂ ) ₄ -；

L ¹¹ L and L ¹² Independently hydrogen or fluorine.

10. The liquid crystal composition according to claim 7 or 8, further comprising at least one compound of the compounds represented by formula (8);

In the formula (8), the amino acid sequence of the compound,

R ¹⁴ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one of the alkyl and alkenyl groups being-CH ₂ -may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

X ¹² is-C.ident.N or-C.ident.C-C.ident.N;

ring D ¹ Is 1, 4-cyclohexylene, at least one hydrogen may be fluorinatedSubstituted 1, 4-phenylene, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl or pyrimidine-2, 5-diyl;

Z ¹⁷ is a single bond, -CH ₂ CH ₂ -、-C≡C-、-COO-、-CF ₂ O-、-OCF ₂ -or-CH ₂ O-；

L ¹³ L and L ¹⁴ Independently hydrogen or fluorine;

i is 1, 2, 3 or 4.

11. The liquid crystal composition according to claim 7 or 8, further comprising at least one compound selected from the group of compounds represented by formulas (9) to (15);

in the formulas (9) to (15),

R ¹⁵ r is R ¹⁶ Independently is an alkyl group of 1 to 10 carbon atoms or an alkenyl group of 2 to 10 carbon atoms, at least one of which-CH ₂ -may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

R ¹⁷ is hydrogen, fluorine, C1-10 alkyl or C2-10 alkenyl, at least one of which is-CH ₂ -may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

ring E ¹ Ring E ² Ring E ³ Ring E ⁴ Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, which may be fluorine substituted for at least one hydrogen, tetrahydropyran-2, 5-diyl or decahydronaphthalene-2, 6-diyl;

Ring E ⁵ Ring E ⁶ Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, tetrahydropyran-2, 5-diyl or decahydronaphthalene-2, 6-diyl;

Z ¹⁸ 、Z ¹⁹ 、Z ²⁰ z is as follows ²¹ Independently a single bond, -CH ₂ CH ₂ -、-COO-、-CH ₂ O-、-OCF ₂ -or-OCF ₂ CH ₂ CH ₂ -；

L ¹⁵ L and L ¹⁶ Independently fluorine or chlorine;

S ¹¹ is hydrogen or methyl;

x is-CHF-or-CF ₂ -；

j. k, m, n, p, q, r and s are independently 0 or 1, the sum of k, m, n and p is 1 or 2, the sum of q, r and s is 0, 1,2 or 3, and t is 1,2 or 3.

12. The liquid crystal composition according to claim 7 or 8, which contains at least one polymerizable compound of the compound represented by formula (16);

in the formula (16), the amino acid sequence of the compound,

ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1, 3-dioxan-2-yl, pyrimidin-2-yl or pyridin-2-yl, in which rings at least one hydrogen may be substituted with halogen, alkyl of 1 to 12 carbon atoms or alkyl of 1 to 12 carbon atoms with at least one hydrogen substituted with halogen;

ring G is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl or pyridine-2, 5-diyl, and in these rings at least one hydrogen may be substituted by halogen, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms or at least one hydrogen is substituted by halogen;

Z ²² Z is as follows ²³ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -CO-, -COO-or-OCO-, at least one-CH ₂ CH ₂ Can be modified by-ch=ch-, -C (CH ₃ )＝CH-、-CH＝C(CH ₃ ) -or-C (CH) ₃ )＝C(CH ₃ ) -substitution, of which at least one hydrogen may be substituted by fluorine or chlorine;

P ¹¹ 、P ¹² p ¹³ Independently a polymerizable group selected from the group of groups represented by the formulas (P-1) to (P-5);

M ¹¹ 、M ¹² m and M ¹³ Independently hydrogen, fluorine, an alkyl group of 1 to 5 carbon atoms, or an alkyl group of 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine;

Sp ¹¹ 、Sp ¹² sp and Sp ¹³ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -COO-, -OCO-or-OCOO-, at least one-CH ₂ CH ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by fluorine or chlorine;

u is 0, 1 or 2;

f. g and h are independently 0, 1, 2, 3 or 4, and the sum of f, g and h is 2 or more.

13. The liquid crystal composition according to claim 7 or 8, which contains at least one polymerizable compound selected from the group of compounds represented by formulas (16-1) to (16-27);

in the formulae (16-1) to (16-27),

P ¹¹ 、P ¹² p ¹³ Independently a polymerizable group selected from the group consisting of groups represented by the formulas (P-1) to (P-3), where M ¹¹ 、M ¹² M and M ¹³ Independently hydrogen, fluorine, an alkyl group of 1 to 5 carbon atoms or an alkyl group of 1 to 5 carbon atoms in which at least one hydrogen is substituted with halogen;

Sp ¹¹ 、Sp ¹² sp and Sp ¹³ Independently a single bond or an alkylene group of 1 to 10 carbon atoms, of which at least one-CH ₂ -can be substituted by-O-, -COO-, -OCO-or-OCOO-, at least one-CH ₂ CH ₂ -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by fluorine or chlorine.

14. The liquid crystal composition according to claim 7 or 8, further comprising at least one of a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, a light stabilizer, a heat stabilizer, and a defoaming agent.

15. A liquid crystal display element comprising the liquid crystal composition according to any one of claims 7 to 14.