TWI752287B - Compound, liquid crystal composition, and liquid crystal display element - Google Patents

Abstract

R¹ 為氫或可經取代的烷基；環A¹ ～環A² 為可經取代的伸環丙基、伸環丁基、伸環戊基、伸環己基、伸環庚基、伸環己烯基、伸苯基、萘二基、十氫萘二基、四氫萘二基、四氫吡喃二基、二噁烷二基、嘧啶二基或吡啶二基；a為0～4；Z¹ 為單鍵或可經取代的伸烷基；Sp¹ ～Sp⁵ 為單鍵或可經取代的伸烷基；M¹ ～M⁴ 為H、F、Cl、可經取代的烷基；R² 為氫或可經取代的碳數1～5的烷基；X¹ 為-OH、-NH₂ 、-OR³ 、-N(R³ )₂ 、-COOH、-SH或-Si(R³ )₃ 。The present invention relates to a compound, a liquid crystal composition and a liquid crystal display element, the compound is represented by the formula (1),

R ¹ is hydrogen or a substituted alkyl group; Ring A ¹ to Ring A ² are substituted cycloextended propyl, cyclobutyl, cyclopentylene, cyclohexylene, cycloheptyl, cycloextended Hexenyl, phenylene, naphthalenediyl, decahydronaphthalenediyl, tetrahydronaphthalenediyl, tetrahydropyrandiyl, dioxanediyl, pyrimidinediyl or pyridinediyl; a is 0-4 ; Z ¹ is a single bond or a substituted alkylene; Sp ¹ -Sp ⁵ are a single bond or a substituted alkylene; M ¹ -M ⁴ are H, F, Cl, a substituted alkyl ; R ² is hydrogen or a substituted alkyl group having 1 to 5 carbon atoms; X ¹ is -OH, -NH ₂ , -OR ³ , -N(R ³ ) ₂ , -COOH, -SH or -Si( R ³ ) ₃ .

Description

Compound, liquid crystal composition and liquid crystal display element

The present invention relates to a compound, a liquid crystal composition and a liquid crystal display element. More specifically, the present invention relates to a compound having both polar groups such as -OH groups and a plurality of polymerizable groups such as methacryloyloxy groups, and liquid crystals including the compound and having positive or negative dielectric anisotropy A composition and a liquid crystal display element comprising the composition or a part of cured product thereof.

If liquid crystal display elements are classified based on the operation mode of liquid crystal molecules, they can be 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), fringe field (fringe field) switching, FFS), field-induced photo-reactive alignment (FPA) and other modes. In addition, based on the driving method of the element, it can be classified into a passive matrix (PM) and an active matrix (AM). PM is classified into static, multiplex, etc., AM is classified into thin film transistor (TFT), metal insulator metal (MIM), and the like. Further, TFTs can be classified into amorphous silicon and polycrystal silicon. The latter are classified into high temperature type and low temperature type according to the manufacturing steps. Classification based on light sources can be classified into a reflective type using natural light, a transmissive type using backlight, and a transflective type using both natural light and backlight.

A liquid crystal composition having a nematic phase has suitable properties. By improving the properties of the composition, an AM device having good properties can be obtained. The relationship between the characteristics of the composition and the characteristics of the AM device is summarized in Table 1 below.

1）可縮短於液晶顯示元件中注入組成物的時間[Table 1]

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

The properties of the composition will be further described based on a commercially available AM device. The temperature range of the nematic phase (the temperature range in which the nematic phase is present) is associated with the temperature range over which the element can be used. The preferable upper limit temperature of the nematic phase is about 70°C or higher, and the preferable lower limit temperature of the nematic phase is about -10°C or lower. The viscosity of the composition correlates with the response time of the element. In order to display a dynamic image by the element, it is preferable that the response time is short. The ideal is a response time of less than 1 millisecond. Therefore, it is preferable that the viscosity of the composition is low, and further, it is more preferable that the viscosity of the composition is low even at low temperature.

The optical anisotropy of the composition correlates with the contrast of the element. Depending on the mode of the element, the optical anisotropy needs to be large or the optical anisotropy is 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 ratio. The appropriate value of the product depends on the type of operation mode. In devices such as TN mode, the value is about 0.45 μm. In the VA mode element, the value is in the range of about 0.30 μm to about 0.40 μm, and in the IPS mode or FFS mode element, the value is in the range of about 0.20 μm to about 0.30 μm. In these cases, a composition having a large optical anisotropy is preferable for an element with a small cell gap. The large dielectric anisotropy in the composition contributes to low threshold voltage, small power consumption and large contrast in the element. Thus, 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 ratio in the element. Therefore, it is preferable to use a composition having 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. A composition having 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 is preferred. The stability of the composition to UV light and heat correlates with the life of the element. When the stability is high, the life of the element is long. Such characteristics are preferable for AM elements used in liquid crystal projectors, liquid crystal televisions, and the like.

In a polymer sustained alignment (PSA) type liquid crystal display element, a polymer-containing liquid crystal composition is used. First, a composition to which a small amount of a polymerizable compound is added is injected into the element. Here, a polymerizable compound having a plurality of polymerizable groups is usually used. Next, the composition was irradiated with ultraviolet rays while applying a voltage between the substrates sandwiching the element. The polymerizable compound is polymerized to generate a polymer network structure in the composition. When the composition is used, the alignment of the liquid crystal molecules can be controlled by the polymer, so that the response time of the element is shortened, and the afterimage of the image is improved. Such effects of polymers can be expected for elements with modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

In general liquid crystal display elements, the vertical alignment of liquid crystal molecules can be achieved by a polyimide alignment film. On the other hand, as a liquid crystal display element without an alignment film, a mode in which a polar compound is added to a liquid crystal composition to align liquid crystal molecules is proposed. First, a composition containing a small amount of polar compound and a small amount of polymerizable compound is injected into the element. As the polymerizable compound, a polymerizable compound having a plurality of polymerizable groups is usually used. Here, the liquid crystal molecules are aligned by the action of the polar compound. Next, the composition was irradiated with ultraviolet rays while applying a voltage between the substrates sandwiching the element. Here, the polymerizable compound is polymerized to stabilize the alignment of the liquid crystal molecules. If this composition is used, the alignment of the liquid crystal molecules can be controlled by the polar compound and the polymer, so that the response time of the device is shortened, and the afterimage of the image is improved. Furthermore, an element without an alignment film does not need a step of forming an alignment film. Since the alignment film does not exist, the resistance of the element does not decrease due to the interaction between the alignment film and the composition. Elements having modes such as TN, ECB, OCB, IPS, VA, FFS, FPA, etc., can be expected to utilize this effect of the combination of polar compounds and polymers.

In liquid crystal display elements without an alignment film, a polymerizable polar compound has been synthesized as a compound having both the function of a polar compound and the function of a polymerizable compound (for example, Patent Document 1 and Patent Document 2). Patent Document 1 describes a polymerizable compound (S-1) having a plurality of polar groups and a plurality of polymerizable groups.

[現有技術文獻] [專利文獻][hua 1]

[Prior Art Document] [Patent Document]

[Patent Document 1] International Publication No. 2017/047177 [Patent Document 2] International Publication No. 2016/129490

[Problem to be Solved by the Invention] An embodiment of the present invention provides a compound having at least one of high chemical stability, high ability to align liquid crystal molecules, and high polymerization reactivity by ultraviolet irradiation, Furthermore, it has a high solubility in a liquid crystal composition. One embodiment of the present invention provides a liquid crystal composition comprising the compound, which fully satisfies the requirements of high upper limit temperature of nematic phase, low minimum temperature of nematic phase, low viscosity, suitable optical anisotropy, positive or negative At least one of characteristics such as high dielectric anisotropy, high specific resistance, high stability to ultraviolet rays, high thermal stability, high elastic constant, and high voltage retention when used in liquid crystal display elements. An embodiment of the present invention provides a liquid crystal display element, which has a wide usable temperature range, short response time, high transmittance, high voltage holding ratio, low threshold voltage, high contrast ratio, long life, and good vertical alignment. at least one of the characteristics.

[Means for Solving the Problems] One embodiment of the present invention relates to a compound represented by formula (1), a liquid crystal composition containing the compound, and a composition containing the composition and/or at least a part of the composition obtained by polymerizing of polymer liquid crystal display elements.

[hua 2]

In formula (1), R ¹ is hydrogen or an alkyl group having 1 to 15 carbon atoms, in the alkyl group, at least one -CH ₂ - may be substituted by -O- or -S-, and at least one -(CH ₂ ) ₂ -Can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by fluorine or chlorine; Ring A ¹ and Ring A ^{2 are} independently 1,2-cycloextended propyl, 1,3-cyclohexylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-cyclohexenyl, 1,4-cyclohexylene Phenyl, 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 or pyridine-2,5-diyl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine , substituted with alkyl with 1 to 10 carbons, alkenyl with 2 to 10 carbons, alkoxy with 1 to 9 carbons or alkenyl with 2 to 9 carbons, in these groups, at least one hydrogen may be replaced by Fluorine or chlorine substitution; a is 0, 1, 2, 3 or 4; Z ¹ is a single bond or an alkylene group having 1 to 6 carbon atoms, in the alkylene group, at least one -CH ₂ - may be through -O- , -CO-, -COO-, -OCO- or -OCOO- substituted, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen Can be substituted by fluorine or chlorine; Sp ¹ , Sp ² , Sp ³ and Sp ^{4 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in the alkylene group, at least one -CH ₂ - can be replaced by -O -, -CO-, -COO-, -OCO- or -OCOO- substituted, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, among these groups, at least one Hydrogen can be substituted by fluorine or chlorine; Sp ⁵ is an alkylene group having 2 to 10 carbon atoms, in the alkylene group, at least one -CH ₂ - can be substituted by -O-; M ¹ , M ² , M ³ and M ^{4 is} independently hydrogen, fluorine, chlorine, alkyl with 1 to 5 carbons, or alkyl with 1 to 5 carbons in which at least one hydrogen is substituted by fluorine or chlorine; R ² is hydrogen or alkane with 1 to 5 carbons group, in the alkyl group, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, and in these groups, at least one hydrogen can be substituted by fluorine or chlorine; X ¹ is - OH, -NH ₂ , -OR ³ , -N(R ³ ) ₂ , -COOH, -SH or -Si(R ³ ) ₃ , -OR ³ , -N(R ³ ) ₂ and -Si(R ³ ) _{In 3} , R ³ is hydrogen or an alkyl group having 1 to 10 carbon atoms, in the alkyl group, at least one -CH ₂ - can be substituted by -O-, and at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH -Substituted, among these groups, at least one hydrogen can be substituted by fluorine or chlorine; where a is 1, ring A ¹ is 1,4-cyclohexylene, and ring A ² is 1,4-phenylene, When Z ¹ is a single bond, Sp ² , Sp ³ and Sp ⁴ are -CH ₂ -, Sp ⁵ is -(CH ₂ ) ₂ -, R ² is methyl, and X ¹ is -OH, Sp ¹ is not -CH _2- ; where a is 1, ring A ¹ is 1,4-phenylene, ring A ² is naphthalene-2,6-diyl, Z ¹ is a single bond, Sp ² , Sp ³ and Sp ⁴ are -CH ₂ -, Sp ⁵ is -(CH ₂ ) ₂ -, R ² is methyl, when X ¹ is -OH, Sp ¹ is not -CH ₂ -; when a is 3, the four rings are respectively ^{from the R 1 side} 1,4-phenylene, 2-ethyl-1,4-phenylene, 1,4-cyclohexylene and 1,4-cyclohexylene, Z ¹ is a single bond, Sp ² , Sp ³ and Sp ^{When 4} is -CH ₂ -, Sp ⁵ is -(CH ₂ ) ₂ -, R ² is methyl, and X ¹ is -OH, Sp ¹ is not -CH ₂ -.

One embodiment of the present invention includes the following items and the like.

Item 1. A compound represented by formula (1). [hua 4]

In formula (1), R ¹ is hydrogen or an alkyl group having 1 to 15 carbon atoms, in the alkyl group, at least one -CH ₂ - may be substituted by -O- or -S-, and at least one -(CH ₂ ) ₂ -Can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by fluorine or chlorine; Ring A ¹ and Ring A ^{2 are} independently 1,2-cycloextended propyl, 1,3-cyclohexylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-cyclohexenyl, 1,4-cyclohexylene Phenyl, 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 or pyridine-2,5-diyl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine , substituted with alkyl with 1 to 10 carbons, alkenyl with 2 to 10 carbons, alkoxy with 1 to 9 carbons or alkenyl with 2 to 9 carbons, in these groups, at least one hydrogen may be replaced by Fluorine or chlorine substitution; a is 0, 1, 2, 3 or 4; Z ¹ is a single bond or an alkylene group having 1 to 6 carbon atoms, in the alkylene group, at least one -CH ₂ - may be through -O- , -CO-, -COO-, -OCO- or -OCOO- substituted, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen Can be substituted by fluorine or chlorine; Sp ¹ , Sp ² , Sp ³ and Sp ^{4 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in the alkylene group, at least one -CH ₂ - can be replaced by -O -, -CO-, -COO-, -OCO- or -OCOO- substituted, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, among these groups, at least one Hydrogen can be substituted by fluorine or chlorine; Sp ⁵ is an alkylene group having 2 to 10 carbon atoms, in the alkylene group, at least one -CH ₂ - can be substituted by -O-; M ¹ , M ² , M ³ and M ^{4 is} independently hydrogen, fluorine, chlorine, alkyl with 1 to 5 carbons, or alkyl with 1 to 5 carbons in which at least one hydrogen is substituted by fluorine or chlorine; R ² is hydrogen or alkane with 1 to 5 carbons group, in the alkyl group, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, and in these groups, at least one hydrogen can be substituted by fluorine or chlorine; X ¹ is - OH, -NH ₂ , -OR ³ , -N(R ³ ) ₂ , -COOH, -SH or -Si(R ³ ) ₃ , -OR ³ , -N(R ³ ) ₂ and -Si(R ³ ) _{In 3} , R ³ is hydrogen or an alkyl group having 1 to 10 carbon atoms, in the alkyl group, at least one -CH ₂ - can be substituted by -O-, and at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH -Substituted, among these groups, at least one hydrogen can be substituted by fluorine or chlorine; where a is 1, ring A ¹ is 1,4-cyclohexylene, and ring A ² is 1,4-phenylene, When Z ¹ is a single bond, Sp ² , Sp ³ and Sp ⁴ are -CH ₂ -, Sp ⁵ is -(CH ₂ ) ₂ -, R ² is methyl, and X ¹ is -OH, Sp ¹ is not -CH _2- ; where a is 1, ring A ¹ is 1,4-phenylene, ring A ² is naphthalene-2,6-diyl, Z ¹ is a single bond, Sp ² , Sp ³ and Sp ⁴ are -CH ₂ -, Sp ⁵ is -(CH ₂ ) ₂ -, R ² is methyl, when X ¹ is -OH, Sp ¹ is not -CH ₂ -; when a is 3, the four rings are respectively ^{from the R 1 side} 1,4-phenylene, 2-ethyl-1,4-phenylene, 1,4-cyclohexylene and 1,4-cyclohexylene, Z ¹ is a single bond, Sp ² , Sp ³ and Sp ^{When 4} is -CH ₂ -, Sp ⁵ is -(CH ₂ ) ₂ -, R ² is methyl, and X ¹ is -OH, Sp ¹ is not -CH ₂ -.

Item 2. The compound according to Item 1, wherein in formula (1), Z ¹ is a single bond, -(CH ₂ ) ₂ -, -(CH ₂ ) ₄ -, -CH=CH-, -C≡C -, - COO -, - OCO -, - CF 2 O -, - OCF 2 -, - CH 2 O -, - OCH 2 - or -CF = CF-.

Item 3. The compound according to Item 1 or Item 2, wherein in formula (1), Ring A ¹ and Ring A ^{2 are} independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1 ,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in these rings, at least one hydrogen may be fluorine, chlorine, alkyl with 1 to 10 carbons, alkenyl with 2 to 10 carbons, alkane with 1 to 9 carbons substituted by an oxy group or an alkenyloxy group having 2 to 9 carbon atoms, and in these groups, at least one hydrogen may be substituted by fluorine or chlorine.

Item 4. The compound according to any one of Items 1 to 3, which is represented by any one of Formula (1-1) to Formula (1-4). [hua 5]

In formulas (1-1) to (1-4), R ¹ is an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, or an alkyl group having 2 to 15 carbon atoms. The alkenyloxy group of 14, in these groups, at least one hydrogen may be substituted by fluorine; Ring A ¹ , Ring A ² , Ring A ³ and Ring A ^{4 are} independently 1,4-cyclohexylene, 1,4-cyclohexylene cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl, the In these rings, at least one hydrogen may be substituted by fluorine, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons or alkenyloxy having 2 to 9 carbons, In these groups, at least one hydrogen may be substituted by fluorine; Z ¹ , Z ² and Z ^{3 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-; Sp ¹ , Sp ² , Sp ³ and Sp ^{4 are} independently a single bond or Alkylene with 1 to 7 carbon atoms, in the alkylene, at least one -CH ₂ - can be substituted by -O-, -COO- or -OCO-, and at least one -(CH ₂ ) ₂ - can be substituted by -CH =CH-substituted, in these groups, at least one hydrogen can be substituted by fluorine; Sp ⁵ is an alkylene group having 2 to 7 carbon atoms, and in the alkylene group, at least one -CH ₂ - can be substituted by -O-; M ¹ , M ² , M ³ and M ^{4 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 is substituted with fluorine; R ² is hydrogen or an alkyl group having a carbon number of 5 Alkyl of 1 to 5; X ¹ is -OH, -NH ₂ or -SH; In formula (1-2), ring A ¹ is 1,4-cyclohexylene, and ring A ² is 1,4-cyclohexylene Phenyl, Z ¹ is a single bond, Sp ² , Sp ³ and Sp ⁴ are -CH ₂ -, Sp ⁵ is -(CH ₂ ) ₂ -, R ² is methyl, and X ¹ is -OH, Sp ¹ is not is -CH ₂ -; in formula (1-2), ring A ¹ is 1,4-phenylene, ring A ² is naphthalene-2,6-diyl, Z ¹ is a single bond, Sp ² , Sp ^{When 3} and Sp ⁴ are -CH ₂ -, Sp ⁵ is -(CH ₂ ) ₂ -, R ² is methyl, and X ¹ is -OH, Sp ¹ is not -CH ₂ -; in formula (1-4) , where Ring A ¹ is 1,4-phenylene, Ring A ² is 2-ethyl-1,4-phenylene, Ring A ³ and Ring A ⁴ are both 1,4-cyclohexylene, Z ¹ , Z ² and Z ³ are single bonds, Sp ² , Sp ³ and Sp ⁴ are -CH ₂ -, Sp ⁵ is -(CH ₂ ) ₂ -, R ² is methyl, and when X ¹ is -OH, Sp ¹ Not -CH ₂ -.

Item 5. The compound according to any one of Items 1 to 4, which is represented by any one of Formula (1-5) to Formula (1-7). [hua 6]

In formula (1-5) to formula (1-7), R ¹ is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkoxy group having 1 to 9 carbon atoms; Ring A ¹ , Ring A ² , Ring A ³ and Ring A ^{4 are} independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrakis Hydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl, in these rings, at least one hydrogen can be through fluorine, alkyl with 1 to 5 carbons, 2 with carbons Alkenyl to 5 or alkoxy of carbon number 1 to 4 is substituted; Z ¹ , Z ² and Z ^{3 are} independently a single bond, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C- , -CH ₂ O- or -OCH ₂ -; Sp ¹ , Sp ² , Sp ³ and Sp ^{4 are} independently a single bond or an alkylene group having 1 to 5 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be substituted by -O-, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH-; R ² is an alkyl group with 1 to 3 carbon atoms; in formula (1-5), in ring A ¹ is 1,4-cyclohexylene, ring A ² is 1,4-phenylene, Z ¹ is a single bond, Sp ² , Sp ³ and Sp ⁴ are -CH ₂ -, and when R ² is methyl, Sp ¹ not -CH ₂ -; in formula (1-5), ring A ¹ is 1,4-phenylene, ring A ² is naphthalene-2,6-diyl, Z ¹ is a single bond, Sp ² , Sp ³ and Sp ⁴ are -CH ₂ -, and when R ² is methyl, Sp ¹ is not -CH ₂ -; In formula (1-7), in ring A ¹ is 1,4-phenylene, ring A ² is 2-ethyl-1,4-phenylene, Ring A ³ and Ring A ⁴ are both 1,4-cyclohexylene, Z ¹ , Z ² and Z ³ are single bonds, Sp ² , Sp ³ and When Sp ⁴ is -CH ₂ - and R ² is a methyl group, Sp ¹ is not -CH ₂ -.

Item 6. The compound according to any one of Items 1 to 5, which is represented by any one of Formula (1-8) to Formula (1-16). [hua 7]

In formula (1-8) to formula (1-16), R ¹ is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkoxy group having 1 to 9 carbon atoms; Z ¹ and Z ^{2 is} independently a single bond or -(CH ₂ ) ₂ -; Sp ¹ , Sp ² and Sp ^{3 are} independently a single bond or an alkylene group having 1 to 5 carbon atoms, in the alkylene group, at least one -CH ₂ - may be substituted by -O-; Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ^{6 are} independently hydrogen, fluorine, alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons or Alkoxy with 1 to 4 carbon atoms; In formula (1-9), when Z ¹ is a single bond, Sp ² and Sp ³ are -CH ₂ -, and Y ¹ and Y ² are hydrogen, Sp ¹ is not - CH ₂ -.

Item 7. The compound according to any one of Items 1 to 6, which is represented by any one of Formula (1-17) to Formula (1-23). [hua 8]

In formula (1-17) to formula (1-23), R ¹ is an alkyl group having 1 to 10 carbon atoms; Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ^{6 are} independently hydrogen, fluorine , methyl or ethyl, Sp ¹ is a single bond or an alkylene group having 1 to 5 carbon atoms, in the alkylene group, at least one -CH ₂ - can be substituted by -O-; In formula (1-18), When Y ¹ and Y ² are hydrogen, Sp ¹ is not -CH ₂ -.

Item 8. A liquid crystal composition comprising at least one of the compounds described in any one of Items 1 to 7.

Item 9. The liquid crystal composition according to Item 8, which contains at least one compound selected from the group of compounds represented by formula (2) to formula (4). [Chemical 9]

In formulas (2) to (4), R ¹¹ and R ^{12 are} independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in the alkyl and alkenyl groups, at least one -CH ₂ - may be substituted by -O-, in these groups, at least one hydrogen 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} independent Ground is a single bond, -COO-, -CH ₂ CH ₂ -, -CH=CH- or -C≡C-.

Item 10. The liquid crystal composition according to Item 8 or Item 9, which contains at least one compound selected from the group of compounds represented by formula (5) to formula (7). [Chemical 10]

In 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, and in the alkyl and alkenyl groups, at least one -CH ₂ - may be through -O -Substituted, in these groups, 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 and Ring C ^{3 are} independently 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1, 3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or 1,4-phenylene in which at least one hydrogen is substituted with fluorine; Z ¹⁴ , Z ¹⁵ and Z ^{16 are} independently single bonds , -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CH=CH-, -C≡C-, or -(CH ₂ ) ₄ -; L ¹¹ and L ^{12 are} independently hydrogen or fluorine.

Item 11. The liquid crystal composition according to any one of Items 8 to 10, which contains at least one compound selected from the group of compounds represented by formula (8). [Chemical 11]

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. Among the alkyl and alkenyl groups, at least one -CH ₂ - may be substituted by -O-, and these In the base, at least one hydrogen can be substituted by fluorine; X ¹² is -C≡N or -C≡CC≡N; Ring D ¹ is 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran -2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or 1,4-phenylene in which at least one hydrogen is substituted with fluorine; Z ¹⁷ is Single bond, -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ - or -C≡C-; L ¹³ and L ^{14 is} independently hydrogen or fluorine; i is 1, 2, 3, or 4.

Item 12. The liquid crystal composition according to any one of Items 8 to 11, which contains at least one compound selected from the group of compounds represented by Formula (11) to Formula (19). [Chemical 12]

In formulas (11) to (19), R ¹⁵ , R ¹⁶ and R ^{17 are} independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and among the alkyl and alkenyl groups, at least one -CH ₂ - can be substituted by -O-, among these groups, at least one hydrogen can be substituted by fluorine, and R ¹⁷ can also be hydrogen or fluorine; Ring E ¹ , Ring E ² , Ring E ³ and Ring E ^{4 are} independent 1,4-cyclohexylene, 1,4-cyclohexenyl, 1,4-phenylene, tetrahydropyran-2,5-diyl, decalin-2,6-diyl or 1,4-phenylene substituted with at least one hydrogen by fluorine; Ring E ⁵ and Ring E ^{6 are} independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene base, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6-diyl; Z ¹⁸ , Z ¹⁹ , Z ²⁰ and Z ^{21 are} independently a single bond, -COO-, -OCO-, _{-CH 2 O -, - OCH 2} -, - CF 2 O -, - OCF 2 -, - CH 2 CH 2 -, - CF 2 OCH 2 CH 2 - or _{-OCF 2 CH 2 CH 2 -;} L 15 and L ^{16 is} 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.

Item 13. The liquid crystal composition according to any one of Items 8 to 12, which contains at least one polymerizable compound represented by Formula (20) other than the compound represented by Formula (1). [Chemical 13]

In formula (20), ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxanyl Alkyl-2-yl, pyrimidin-2-yl or pyridin-2-yl, in these rings, at least one hydrogen can be replaced by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or at least one hydrogen One hydrogen is substituted by a halogen-substituted alkyl group having 1 to 12 carbon atoms; Ring G is 1,4-cyclohexylene, 1,4-cyclohexenyl, 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, phenanthrene-2,7-diyl, tetrahydropyran-2 ,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in these rings, at least one hydrogen can be passed through halogen , an alkyl group having 1 to 12 carbon atoms, an alkoxy group having a carbon number of 1 to 12, or an alkyl group having 1 to 12 carbon atoms substituted for at least one hydrogen by halogen; Z ²² and Z ^{23 are} independently a single bond or a carbon number The alkylene of 1 to 10, in the alkylene, at least one -CH ₂ - can be substituted by -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ CH ₂ - can be substituted by - CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ )- substituted, in these groups, at least one hydrogen may be substituted by Fluorine or chlorine substitution; P ¹¹ , P ¹² and P ^{13 are} independently polymerizable groups; Sp ¹¹ , Sp ¹² and Sp ^{13 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in the alkylene group, At least one -CH ₂ - can be substituted by -O-, -COO-, -OCO- or -OCOO-, at least one -CH ₂ CH ₂ - can be substituted by -CH=CH- or -C≡C-, these In the base, 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 1 or more .

Item 14. The liquid crystal composition according to Item 13, wherein in formula (20), P ¹¹ , P ^{12 ,} and P ^{13 are} independently polymers selected from the group consisting of polymers represented by formula (P-1) to formula (P-5). A base in a sex-based group. [Chemical 14]

In 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 at least one hydrogen substituted by halogen with a carbon number of 1 to 5 5 alkyl.

Item 15. The liquid crystal composition according to Item 13 or Item 14, wherein the polymerizable compound represented by formula (20) is selected from the group consisting of polymerizable compounds represented by formula (20-1) to formula (20-7). at least one compound of the group. [Chemical 15]

In formula (20-1) to formula (20-7), L ³¹ , L ³² , L ³³ , L ³⁴ , L ³⁵ , L ³⁶ , L ³⁷ and L ^{38 are} independently hydrogen, fluorine or methyl; Sp ¹¹ , Sp ¹² and Sp ^{13 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be via -O-, -COO-, -OCO- or -OCOO -Substituted, at least one -CH ₂ CH ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by fluorine or chlorine; P ¹¹ , P ¹² and P ^{13 are} independent Ground is a group selected from the group of polymerizable groups represented by formula (P-1) to formula (P-3). [Chemical 16]

In formula (P-1) to formula (P-3), M ¹¹ , M ¹² and M ^{13 are} independently hydrogen, fluorine, alkyl group having 1 to 5 carbon atoms, or at least one hydrogen substituted by halogen with carbon number 1 to 5 5 alkyl.

Item 16. The liquid crystal composition according to any one of Items 8 to 15, which contains a polymerizable compound, a polymerization initiator, a polymerization At least one of the group of inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, pigments, and antifoaming agents. [Chemical 17]

In formula (20), ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxanyl Alkyl-2-yl, pyrimidin-2-yl or pyridin-2-yl, in these rings, at least one hydrogen can be replaced by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or at least one hydrogen One hydrogen is substituted by a halogen-substituted alkyl group having 1 to 12 carbon atoms; Ring G is 1,4-cyclohexylene, 1,4-cyclohexenyl, 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, phenanthrene-2,7-diyl, tetrahydropyran-2 ,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in these rings, at least one hydrogen can be passed through halogen , an alkyl group having 1 to 12 carbon atoms, an alkoxy group having a carbon number of 1 to 12, or an alkyl group having 1 to 12 carbon atoms substituted for at least one hydrogen by halogen; Z ²² and Z ^{23 are} independently a single bond or a carbon number The alkylene of 1 to 10, in the alkylene, at least one -CH ₂ - can be substituted by -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ CH ₂ - can be substituted by - CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ )- substituted, in these groups, at least one hydrogen may be substituted by Fluorine or chlorine substitution; P ¹¹ , P ¹² and P ^{13 are} independently polymerizable groups; Sp ¹¹ , Sp ¹² and Sp ^{13 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in the alkylene group, At least one -CH ₂ - can be substituted by -O-, -COO-, -OCO- or -OCOO-, at least one -CH ₂ CH ₂ - can be substituted by -CH=CH- or -C≡C-, these In the base, 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 1 or more .

Item 17. A liquid crystal display element containing at least a part selected from the liquid crystal composition described in any one of items 8 to 16 and the liquid crystal composition described in any one of items 8 to 16 to polymerize at least one of the group formed by the adult.

[Effects of the Invention] According to one embodiment of the present invention, a compound can be provided which has high chemical stability, high ability to align liquid crystal molecules, high polymerization reactivity due to ultraviolet irradiation, and has a large usefulness. At least one of the voltage holding ratios in liquid crystal display elements, and has high solubility in liquid crystal compositions. According to one embodiment of the present invention, there can be provided a liquid crystal composition comprising the compound, which fully satisfies the requirements of high upper limit temperature of nematic phase, low minimum temperature of nematic phase, low viscosity, suitable optical anisotropy, and positive Or at least one of the characteristics of large negative dielectric anisotropy, large specific resistance, high stability to ultraviolet rays, high stability to heat, and large elastic constant. According to an embodiment of the present invention, a liquid crystal display element can be provided, which has a wide usable temperature range, a short response time, a high transmittance, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, a long life, and a vertical At least one of characteristics such as good orientation.

How to use the terms in this specification is as follows. The terms "liquid crystal compound", "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "compound", "composition" and "element", respectively. "Liquid crystal compound" is a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and although it does not have a liquid crystal phase, it is used for the purpose of adjusting the physical properties of the composition such as upper limit temperature, lower limit temperature, viscosity, dielectric anisotropy, etc. The general term for the added compounds. The compound usually has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod-like. The "polymerizable compound" is a compound added for the purpose of producing a polymer in the composition. The liquid crystal compound having an alkenyl group is not a polymerizable compound in its meaning. "Polar group" -OH with the following non-covalent bonding interactions manner glass (or metal oxide) or the like the surface of a substrate, ^{_{etc., -NH 2, -OR 3, -N}} (R 3) 2, -COOH, -SH or -Si(R ³ ) ₃ and other groups. "Polar compounds" help liquid crystal molecules to align through the interaction of polar groups with the surface of the substrate. A "liquid crystal display element" is a general term for a liquid crystal display panel, a liquid crystal display module, and the like.

The liquid crystal composition is usually prepared by mixing a plurality of liquid crystal compounds. To this composition, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a Additives such as pigments and defoamers. The ratio (content) of the liquid crystal compound in the liquid crystal composition is represented by the weight percentage (% by weight) based on the weight of the liquid crystal composition not containing the additive even when an additive is added. The ratio (addition amount) of the additive in the liquid crystal composition is represented by the weight percentage (% by weight) based on the weight of the liquid crystal composition not containing the additive. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total weight of the liquid crystal compound. Parts per million (ppm) by weight are also sometimes used. The ratios of the polymerization initiator and the polymerization inhibitor in the liquid crystal composition are expressed based on the weight of the polymerizable compound exceptionally.

The "clearing point" is the transition temperature between the liquid crystal phase and the isotropic phase in the liquid crystal compound. The "lower limit temperature of the liquid crystal phase" is the transition temperature of the solid-liquid crystal phase (smectic phase, nematic phase) in the liquid crystal compound. The "upper limit temperature of the nematic phase" is the transition temperature between the nematic phase and the isotropic phase in the mixture of the liquid crystal compound and the mother liquid crystal or the liquid crystal composition, and may be simply referred to as the "upper limit temperature". The "lower limit temperature of the nematic phase" is sometimes simply referred to as the "lower limit temperature". The expression "increased dielectric anisotropy" or "large dielectric anisotropy" means that the absolute value of its value is increased or large. "Large voltage retention ratio" means that the device has a large voltage retention ratio not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and, after using the device for a long time, not only at room temperature, but also at It also has a large voltage holding ratio at a temperature close to the upper limit temperature. In a composition or element, characteristics may be investigated before and after a time-dependent change test (including an accelerated deterioration test). The expression "high solubility in a liquid crystal composition" means that the solubility is high with respect to any composition containing a liquid crystal compound at room temperature, but the composition can be used in the following examples as the composition The composition evaluated for solubility was set as a reference.

The compound represented by formula (1) may be abbreviated as "compound (1)" in some cases. Compound (1) refers to one compound represented by formula (1), a mixture of two compounds, or a mixture of three or more compounds. This rule also applies to at least one compound or the like selected from the group of compounds represented by formula (2). ^{Symbols such as A 1} , B ¹ , C ¹ surrounded by hexagons correspond to ring A ¹ , ring B ¹ , ring C ^{1 ,} etc., 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. A straight line crossing one side of the hexagon indicates that any hydrogen on the ring may be substituted by groups such as ^{-Sp 1} -P ^{1 .} Subscripts such as f, g, h indicate the number of substituted groups. When the subscript is 0, there is no such substitution. In the expression "Ring A and Ring C are independently X, Y or Z", since there are multiple subjects, "independently" is used. When the subject is "Ring A is", since the subject is single, "independently" is not used.

In the chemical formula, ^{the notation of the terminal group R 11} is used in various compounds, but the ^{groups represented by R 11} in these compounds may be the same or different. For example, R in the compound (2) in the case where ¹¹ is ethyl, R compound (3) ¹¹ can be ethyl, propyl and the like may also be other groups. This rule also applies to other tokens. In compound (8), when i is 2, two rings D ¹ exist. In this compound, ^{the two groups represented by the two rings D 1} may be the same or different. When i is greater than 2, it also applies to any two rings D ¹ . This rule also applies to other tokens.

The expression "at least one 'A'" means that the number of 'A's is arbitrary. The expression "at least one 'A' may be substituted by 'B'" includes the case where 'A' itself is not substituted by 'B', the case where one 'A' is substituted by 'B', the case where two or more 'A's are substituted by 'B' In the case of substitution with 'B', in these cases, the position of 'A' substituted with 'B' is arbitrary. The rule that the substitution position is arbitrary also applies to the expression "at least one 'A' is substituted with 'B'". The expression "at least one A may be substituted by B, C or D" is meant to include the case where A is unsubstituted, 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 case, and the case where multiple A's are substituted with at least two of B, C, and D. Among the alkyl groups in which at least one -CH ₂ - (or -CH ₂ CH ₂ -) can be substituted by -O- (or -CH=CH-), for example, including alkyl, alkenyl, alkoxy, alkoxyalkane group, alkoxyalkenyl, alkenyloxyalkyl. Furthermore, it is not preferable that two consecutive -CH ₂ - are substituted by -O- to become -OO-. In an alkyl group or the like, _{the case where -CH 2 - of the methyl moiety (-CH 2} -H) is substituted with -O- to become -OH is also unfavorable.

Sometimes "R ¹¹ and R ^{12 are} independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in the alkyl and alkenyl groups, at least one -CH ₂ - may be substituted by -O- , in these groups, at least one hydrogen may be substituted by fluorine". In this expression, "these bases" can be interpreted as literal. In this expression, "the groups" refer to alkyl groups, alkenyl groups, alkoxy groups, alkenyloxy groups, and the like. That is, "these bases" means all the bases described before the term "in these bases". This common sense interpretation also applies to other terms.

Halogen means fluorine, chlorine, bromine or iodine. Preferred halogens are fluorine or chlorine. A particularly preferred halogen is fluorine. In the liquid crystal compound, the alkyl group is linear or branched, and does not contain a cyclic alkyl group. In general, straight chain alkyl groups are preferred over branched alkyl groups. The same applies to terminal groups such as an alkoxy group and an alkenyl group. Regarding the stereo configuration associated with 1,4-cyclohexylene, the trans configuration is preferred to the cis configuration in order to increase the upper temperature limit of the nematic phase. The 2-fluoro-1,4-phenylene group refers to the following two divalent groups. In the chemical formula, fluorine can be left (L) or right (R). This rule also applies to left-right asymmetric divalent radicals, such as tetrahydropyran-2,5-diyl, formed by removing two hydrogens from the ring.

[hua 3]

One embodiment of the present invention also includes the following items. (a) The liquid crystal composition, which further contains a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a pigment, an antifoaming agent, and the like At least two of the additives. (b) A polymerizable composition prepared by adding a polymerizable compound different from compound (1) or compound (20) to the liquid crystal composition. (c) A polymerizable composition prepared by adding compound (1) and compound (20) to the liquid crystal composition. (d) A liquid crystal composite prepared by polymerizing the polymerizable composition. (e) A polymer-stabilized alignment-type element comprising the liquid crystal composite. (f) A polymer-stabilized alignment-type element prepared by using a polymerizable composition by adding compound (1) and compound (20) to the liquid crystal composition ), and a polymerizable compound different from compound (1) or compound (20).

The aspect of the compound (1), the synthesis of the compound (1), the liquid crystal composition, and the liquid crystal display element will be described in this order.

1. State sample of compound (1) The compound (1) according to one embodiment of the invention is characterized by having a mesogen moiety including at least one ring, one polar group, and two or more polymerizable groups, and further characterized by ^{The spacer (Sp 1} below) bonded to the ring is branched, at least one has a polymerizable group and a polar group, and the other has at least a polymerizable group, and is especially characterized in that the terminal is substituted with an ethoxy group through the spacer (below). The aforementioned Sp ⁴ ) is bonded to the polymerizable group. Compound (1) is useful because a polar group interacts with a substrate surface such as glass (or metal oxide) in a non-covalent bond manner. One of the applications is an additive for a liquid crystal composition used in a liquid crystal display element, and in this application, the compound (1) is added for the purpose of controlling the alignment of liquid crystal molecules. This kind of additive is preferably chemically stable under the condition of being sealed in the element, has a high ability to align liquid crystal molecules, and has a large solubility in the liquid crystal composition. In this case, a liquid crystal display element having a large voltage holding ratio can be obtained. The compound (1) sufficiently satisfies such characteristics to a considerable extent, which cannot be achieved with the conventional compound, and the solubility in the liquid crystal composition is extremely large. Compared with the case, a device excellent in alignment and long-term stability can be easily obtained.

Preferred examples of compound (1) will be described. Preferred examples of symbols such as R ¹ , A ¹ , and Sp ¹ in compound (1) are also applicable to the lower formula of compound (1), for example, formula (1-1). In the 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, the compound (1) may also contain ^{isotopes such as 2} H (deuterium), ¹³ C and the like in a larger amount than the naturally occurring ratio.

[Chemical 18]

R ¹ is hydrogen or an alkyl group having 1 to 15 carbon atoms, in the alkyl group, at least one -CH ₂ - can be substituted by -O- or -S-, and at least one -(CH ₂ ) ₂ - can be substituted by -CH= CH- or -C≡C-substituted, in these groups, at least one hydrogen may be substituted by fluorine or chlorine.

Preferred R ¹ is an alkyl group with 1 to 15 carbons, an alkenyl group with 2 to 15 carbons, an alkoxy group with 1 to 14 carbons or an alkenyloxy group with 2 to 14 carbons, among these groups, at least One hydrogen can be replaced by fluorine. Particularly preferred R ¹ is an alkyl group having 1 to 10 carbons, an alkenyl group having 2 to 10 carbons, or an alkoxy group having 1 to 9 carbons. Particularly preferred R ¹ is an alkyl group having 1 to 10 carbons.

The compound in which R ¹ is an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 14 carbon atoms tends to have high chemical stability. A ^{compound in which R 1} is an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or an alkenyloxy group having 2 to 14 carbon atoms tends to have a high solubility in the liquid crystal composition. The compound in which R ¹ is an alkyl group having 1 to 15 carbon atoms tends to have a high ability to align liquid crystal molecules.

Ring A ¹ and Ring A ^{2 are} independently 1,2-cycloextended propyl, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cyclopentylene Cycloheptyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, decalin-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 or pyridine-2 ,5-diyl, in these rings, at least one hydrogen can be fluorine, chlorine, alkyl with 1 to 10 carbons, alkenyl with 2 to 10 carbons, alkoxy with 1 to 9 carbons or carbon number 2 to 9 are substituted with alkenyloxy, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine.

Preferred ring A ¹ and ring A ² are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran -2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in which at least one hydrogen may be Substituted by fluorine, chlorine, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons or alkenyloxy having 2 to 9 carbons, among these groups, at least One hydrogen can be replaced by fluorine or chlorine.

More preferable ring A ¹ and ring A ² are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran -2,5-diyl or 1,3-dioxane-2,5-diyl, in these rings, at least one hydrogen may be fluorine, alkyl having 1 to 10 carbons, alkyl having 2 to 10 carbons Alkenyl, alkoxy having 1 to 9 carbons or alkenyloxy having 2 to 9 carbons are substituted, and in these groups, at least one hydrogen may be substituted with fluorine.

Particularly preferred ring A ¹ and ring A ² are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran -2,5-diyl or 1,3-dioxane-2,5-diyl, in these rings, at least one hydrogen may be fluorine, alkyl having 1 to 5 carbons, alkyl having 2 to 5 carbons Alkenyl or alkoxy having 1 to 4 carbon atoms is substituted.

Particularly preferred ring A ¹ and ring A ² are 1,4-cyclohexylene, 1,4-phenylene, 2-substituted 1,4-phenylene, 3-substituted 1,4-phenylene or 2 Substituted 1,4-phenylene at position and 3 positions, as the substituent, preferably hydrogen, fluorine, alkyl group having 1 to 5 carbon atoms, alkenyl group having 2 to 5 carbon atoms, or alkane having 1 to 4 carbon atoms Oxygen, more preferably hydrogen, fluorine, methyl or ethyl.

Ring A ¹ and Ring A ^{2 are} independently 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-phenylene, at least one hydrogen is substituted with fluorine 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is substituted with an alkyl group having 1 to 5 carbon atoms, decalin-2,6-diyl or tetrahydropyran-2,5 -Diyl compounds tend to have high chemical stability. Ring A ¹ and Ring A ^{2 are} independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is substituted with fluorine , At least one hydrogen is substituted with 1,4-phenylene substituted by an alkyl group of carbon number 1 to 5 or at least one hydrogen is substituted by an alkenyl group of carbon number 2 to 5. 1,4-phenylene compounds are present in the liquid crystal composition tends to have high solubility in substances. Ring A ¹ and Ring A ^{2 are} independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene compound in which at least one hydrogen is substituted with an alkyl group having 1 to 2 carbon atoms. The ability to align liquid crystal molecules tends to be high. Ring A ¹ and Ring A ^{2 are} independently 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is substituted with an alkyl group having 1 to 5 carbon atoms, and at least one hydrogen is substituted with an alkyl group having 1 to 4 carbon atoms. Alkoxy-substituted 1,4-phenylene, naphthalene-2,6-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl compounds exhibit polymerization by ultraviolet irradiation high sexual tendency.

a is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 1, 2 or 3, particularly preferably 1 or 2.

The compound in which a is 0 tends to have a high solubility in the liquid crystal composition. The compound in which a is 3 or 4 tends to have a high ability to align liquid crystal molecules. The compound in which a is 1 or 2 has a high solubility in a liquid crystal composition, a high ability to align liquid crystal molecules, and a tendency to have high polymerization reactivity by ultraviolet irradiation.

Z ¹ is a single bond or an alkylene group having 1 to 6 carbon atoms, and 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 - can be substituted by -CH=CH- or -C≡C-, and in these groups, at least one hydrogen can be substituted by fluorine or chlorine.

Preferred Z ¹ is a single bond, -(CH ₂ ) ₂ -, -(CH ₂ ) ₄ -, -CH=CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O- _{, -OCF 2 -, - CH 2} O -, - OCH 2 - or -CF = CF-. More preferably Z ¹ is a single bond, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ - or -CF=CF-. More preferably Z ¹ is a single bond, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C-, -CH ₂ O- or -OCH ₂ -, more preferably Z ¹ is a single bond or - (CH ₂ ) ₂ -, especially Z ¹ is a single bond.

A compound in which Z ¹ is a single bond tends to have high chemical stability. The compound in which Z ¹ is a single bond, -(CH ₂ ) ₂ -, -CF ₂ O- or -OCF ₂ - tends to have a high solubility in the liquid crystal composition. The compound in which Z ¹ is a single bond or -(CH ₂ ) ₂ - tends to have a high ability to align liquid crystal molecules. Compounds in which Z ¹ is a single bond, -CH=CH-, -C≡C-, -COO-, -OCO-, -CH ₂ O-, and -OCH ₂ - have high polymerization reactivity by ultraviolet irradiation. tendency.

Sp ¹ , Sp ² , Sp ³ and Sp ^{4 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be via -O-, -CO-, - COO-, -OCO- or -OCOO- substituted, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by fluorine or chlorine .

Preferred Sp ¹ , Sp ² , Sp ³ and Sp ^{4 are} independently a single bond or an alkylene group having 1 to 7 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be through -O-, -COO - or -OCO- substituted, at least one -(CH ₂ ) ₂ - may be substituted with -CH=CH-, and in these groups, at least one hydrogen may be substituted with fluorine.

Compounds in which Sp ¹ , Sp ² , Sp ³ and Sp ^{4 are} independently a single bond or an alkylene group having 1 to 7 carbon atoms tend to have high chemical stability. A ^{compound in which Sp 1} , Sp ² , Sp ³ and Sp ^{4 are} _{independently at least one -CH 2} --O-substituted group of an alkylene group having 1 to 7 carbon atoms or an alkylene group having 1 to 7 carbon atoms exists. The solubility in the liquid crystal composition tends to be large.

More preferably Sp ¹ , Sp ² , Sp ³ and Sp ^{4 are} independently a single bond or an alkylene group having 1 to 5 carbon atoms, in the alkylene group, at least one -CH ₂ - may be substituted by -O-, at least a - (CH _{2) 2} - may be substituted with -CH = CH-.

In terms of becoming a compound having more excellent solubility in liquid crystal compositions, it is particularly preferred that Sp ¹ is a single bond or an alkylene group having 1 to 5 carbon atoms, and in the alkylene group, at least one -CH ₂ -Can be substituted by -O-; Sp ² and Sp ^{3 are} independently a single bond or an alkylene group having 1 to 5 carbon atoms, in the alkylene group, at least one -CH ₂ - can be substituted by -O-, especially preferred is -CH ₂ -; Sp ⁴ is -CH ₂ -.

Sp ⁵ is an alkylene group having 2 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be substituted by -O-. Preferred Sp ⁵ is an alkylene group having 2 to 7 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be substituted by -O-. The compound in which Sp ⁵ is an alkylene group having 2 to 7 carbon atoms has high chemical stability and tends to be more excellent in solubility in a liquid crystal composition. Compounds in which Sp ⁵ _{is at least one -CH 2} --O- substituted group of a C2 to 7 alkylene group tend to have high solubility in the liquid crystal composition and high ability to align liquid crystal molecules. ^{Sp 5 is} particularly preferably -(CH ₂ ) ₂ - in terms of becoming a compound having more excellent solubility in the liquid crystal composition.

M ¹ , M ² , M ³ and M ^{4 are} independently hydrogen, fluorine, chlorine, 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 is substituted by fluorine or chlorine, preferably It is 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 is substituted by fluorine, and it is a compound having particularly high polymerization reactivity by ultraviolet irradiation. , more preferably hydrogen.

R ² is hydrogen or an alkyl group having 1 to 5 carbon atoms, in the alkyl group, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, and in these groups, at least one Hydrogen can be replaced by fluorine or chlorine. Preferred R ² is hydrogen or alkyl having 1 to 5 carbons. In terms of being a compound with more excellent solubility in liquid crystal compositions, high chemical stability, and high ability to align liquid crystal molecules, more preferable R ² is an alkyl group having 1 to 3 carbon atoms, and particularly preferable R 2 is an alkyl group having 1 to 3 carbon atoms. R ² is methyl.

X ¹ is -OH, -NH ₂ , -OR ³ , -N(R ³ ) ₂ , -COOH, -SH or -Si(R ³ ) ₃ . ^{Desirable X 1} is -OH, -NH ₂ or -SH, and particularly preferred X ¹ is -OH in terms of becoming a compound having more excellent solubility in the liquid crystal composition. Here, R ³ is hydrogen or an alkyl group having 1 to 10 carbon atoms, in the alkyl group, at least one -CH ₂ - may be substituted by -O-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH -Substituted, in these groups, at least one hydrogen may be replaced by fluorine or chlorine.

The compound in which X ¹ is -OH, -NH ₂ or -SH tends to have a high ability to align liquid crystal molecules. Compounds in which X ¹ is -OH tend to have high chemical stability, high ability to align liquid crystal molecules, and high solubility in liquid crystal compositions. By using these compounds, it is easy to obtain a liquid crystal display element with a high voltage holding ratio.

Furthermore, where a is 1, ring A ¹ is 1,4-cyclohexylene, ring A ² is 1,4-phenylene, Z ¹ is a single bond, and Sp ² , Sp ³ and Sp ⁴ are -CH ₂ -, Sp ⁵ is -(CH ₂ ) ₂ -, R ² is methyl, when X ¹ is -OH, Sp ¹ is not -CH ₂ -; when a is 1, ring A ¹ is 1,4-phenylene base, ring A ² is naphthalene-2,6-diyl, Z ¹ is a single bond, Sp ² , Sp ³ and Sp ⁴ are -CH ₂ -, Sp ⁵ is -(CH ₂ ) ₂ -, and R ² is methyl base, when X ¹ is -OH, Sp ¹ is not -CH ₂ -; when a is 3, the four rings are 1,4-phenylene, 2-ethyl-1,4-extended respectively ^{from the side of R 1} Phenyl, 1,4-cyclohexylene and 1,4-cyclohexylene, Z ¹ is a single bond, Sp ² , Sp ³ and Sp ⁴ are -CH ₂ -, Sp ⁵ is -(CH ₂ ) ₂ -, When R ² is methyl and X ¹ is -OH, Sp ¹ is not -CH ₂ -.

Examples of preferable compound (1) are compound (1-1) to compound (1-4) described in item 4. More preferable examples of the compound (1) are the compounds (1-5) to (1-7) described in item 5. Examples of particularly preferred compounds (1) are the compounds (1-8) to (1-16) described in item 6. Examples of the most preferable compound (1) are the compounds (1-17) to (1-23) described in item 7.

2. Synthesis of compound (1) The synthesis method of compound (1) will be described. Compound (1) can be synthesized by appropriately combining methods of organic synthetic chemistry. Compounds whose synthesis is not described can be synthesized by "Organic Syntheses" (John Wiley & Sons, Inc), "Organic Reactions" (John Wiley & Sons) Company (John Wiley & Sons, Inc)), "Comprehensive Organic Synthesis" (Pergamon Press), "New Experimental Chemistry Lectures" (Maruzen) and other books. synthesis.

2-1. Generation of Bonding Group An example of the method for generating the bonding group in compound (1) is as described in the following scheme. In this 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. Compound (1A) to compound (1G) correspond to compound (1) or an intermediate of compound (1).

[Chemical 19]

[hua 20]

[Chemical 21]

[Chemical 22]

[Chemical 23]

[Chemical 24]

(I) Formation of single bond Compound (1A) is synthesized by reacting the boronic acid compound (21) with the compound (22) in the presence of a carbonate and a tetrakis(triphenylphosphine)palladium catalyst. The compound (1A) can also be synthesized by reacting the compound (23) with n-butyllithium, and then reacting with zinc chloride in the presence of dichlorobis(triphenylphosphine)palladium catalyst. Compound (22) is allowed to react.

(II) Production of -COO- and -OCO- The carboxylic acid (24) is obtained by reacting the compound (23) with n-butyllithium and then with carbon dioxide. The carboxylic acid (24) is combined with the alcohol (25) derived from compound (21) in 1,3-dicyclohexylcarbodiimide (1,3-dicyclohexylcarbodiimide, DCC) and 4-dimethylamine Compound (1B) with -COO- was synthesized by dehydration in the presence of 4-dimethylaminopyridine (DMAP). Compounds having -OCO- were also synthesized by this method.

(III) _{Production of -CF 2} O- and -OCF ₂ - Compound ( 26 ) is obtained by sulfurizing compound ( 1B ) with Lawesson's reagent. Compound (1C) _{with -CF 2} O- was synthesized by fluorination of 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 fluorination of compound (26) using (diethylamino)sulphur trifluoride (DAST). See WH Bunnelle et al., J. Org. Chem., 1990, vol. 55, p. 768. Compounds with -OCF ₂ - can also be synthesized by this method.

(IV) Formation of -CH=CH- The compound (22) reacts with n-butyllithium, and then reacts with N,N-dimethylformamide (N,N-dimethylformamide, DMF) to obtain the aldehyde (27). The compound (1D) is synthesized by reacting the phosphonium salt (28) with potassium tert-butoxide to generate a phosphorus dipole (phosphorus ylide) and reacting the phosphorus dipole with the aldehyde (27). Since a cis-isomer is formed depending on the reaction conditions, the cis-isomer can be isomerized into a trans-isomer by a known method if necessary.

(V) _{Formation of -CH 2} CH ₂ - Compound (1E) is synthesized by hydrogenating compound (1D) in the presence of a palladium-carbon catalyst.

(VI)-C≡C- is formed in the presence of catalysts of dichloropalladium and copper iodide, and the compound (23) is reacted with 2-methyl-3-butyn-2-ol, and then reacted in an alkaline solution. Deprotection is carried out under conditions to obtain compound (29). Compound (1F) is synthesized by reacting compound (29) with compound (22) in the presence of a catalyst of dichlorobis(triphenylphosphine)palladium and copper halide.

(VII) _{Production of -CH 2} O- and -OCH ₂ - Compound (30) is obtained by reducing compound (27) with sodium borohydride. It is brominated with hydrobromic acid to obtain compound (31). Compound (1G) is synthesized by reacting compound (25) with compound (31) in the presence of potassium carbonate. Compounds having -OCH ₂ - can also be synthesized by this method.

(VIII) Production of -CF=CF- After the compound (23) is treated with n-butyllithium, the compound (32) is obtained by reacting tetrafluoroethylene. Compound (22) is treated with n-butyllithium, and then reacted with compound (32) to synthesize compound (1H).

2-2. ^{Formation of Ring A 1} and Ring A ² About 1,2-cyclopropylidene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1 ,4-cycloheptene, 1,4-cyclohexenyl, 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 and other rings, starting materials are commercially available, or synthetic methods are well known.

2-3. Synthesis Examples Examples of the method for synthesizing the compound (1) are as follows. Among these compounds, R ¹ , R ² , A ¹ , A ² , Z ¹ , Sp ¹ , Sp ² , Sp ³ and a have the same definitions as described in Item 1.

In formula (1), Sp ⁴ is -CH ₂ -, Sp ⁵ is -(CH ₂ ) ₂ -, M ¹ , M ² , M ³ and M ⁴ are hydrogen, X ¹ is -OH compound (1-51 ) can be synthesized by the following method. Compound (52) is obtained by reacting compound (51) with formaldehyde in the presence of 1,4-diazabicyclo[2.2.2]octane (1,4-diazabicyclo[2.2.2]octane, DABCO). Compound (53) is obtained by reacting compound (52) with trifluoromethanesulfonic anhydride (Tf _{2 O) and triethylamine, and then reacting with ethylene glycol.} Compound (54) is obtained by reacting compound (53) with 3,4-dihydro-2H-pyran in the presence of pyridinium p-toluenesulfonate (PPTS). Compound (55) is obtained by hydrolyzing compound (54) using lithium hydroxide. Compound (58) is obtained by reacting diol (56) synthesized by a known method with compound (57) in the presence of triethylamine. Compound (1-51) can be derived by reacting compound (58) with compound (55) in the presence of DCC and DMAP to obtain compound (59), followed by deprotection using PPTS.

[Chemical 25]

3. Liquid Crystal Composition 3-1. Component Compound The liquid crystal composition according to one embodiment of the present invention contains the compound (1) as the component A. The compound (1) can control the alignment of liquid crystal molecules by interacting with the substrate of the device in a non-covalent bonding manner. The composition preferably contains compound (1) as component A, and further contains at least one liquid crystal compound selected from the group consisting of component B, component C, component D, and component E described below. Component B is selected from compounds (2) to (4). Component C is selected from compounds (5) to (7) other than compounds (2) to (4). Ingredient D is compound (8). Component E is selected from compounds (11) to (19). The composition may also contain other liquid crystal compounds different from Compound (2) to Compound (8) and Compound (11) to Compound (19). When preparing the composition, it is preferable to select Component B, Component C, Component D, and Component E in consideration of the magnitude of positive or negative dielectric anisotropy and the like. The composition of properly selected components has a high upper limit temperature, low lower limit temperature, low viscosity, appropriate optical anisotropy (ie, large optical anisotropy or small optical anisotropy), large positive or negative optical anisotropy Dielectric anisotropy, large specific resistance, stability to heat or ultraviolet light, and appropriate elastic constant (ie, large elastic constant or small elastic constant).

Compound (1) is added to the composition for the purpose of controlling the alignment of liquid crystal molecules. The preferable ratio of the compound (1) to 100 wt % of the liquid crystal composition is 0.05 wt % or more in terms of easily aligning the liquid crystal molecules, and in terms of further preventing the display failure of the device, etc. Preferably it is 10 weight% or less. A more preferable ratio is in the range of 0.1 wt % to 7 wt %, an especially preferable ratio is in the range of 0.4 wt % to 5 wt %, and a particularly preferable ratio is in the range of 0.5 wt % to 5 wt %. These ratios also apply to compositions containing compound (20).

Component B is a compound whose two terminal groups are an alkyl group or the like. Component B has a small dielectric anisotropy. Preferred examples of component B include compound (2-1) to compound (2-11), compound (3-1) to compound (3-19), and compound (4-1) to compound (4-7). In these compounds, R ¹¹ and R ^{12 are} independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in the alkyl or alkenyl group, at least one -CH ₂ - may be through -O- Substituted, in these groups, at least one hydrogen may be substituted with fluorine.

[Chemical 26]

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

As the content of component B is increased, 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 satisfied, the content of the component B is preferably as large as possible. The content of Component B is preferably 30 wt % or more, particularly preferably 40 wt % or more, based on 100 wt % of the liquid crystal composition, and the upper limit is not particularly limited, for example, 99.95 wt %.

Component C is a compound having fluorine, chlorine or a fluorine-containing group at at least one terminal. Composition C has a large positive dielectric anisotropy. Preferable examples of component C include compound (5-1) to compound (5-16), compound (6-1) to compound (6-116), and compound (7-1) to compound (7-59). Component C in the compound, R ¹³ is a C 1 alkyl group or a C 10 alkenyl group having 2 to 10, the alkyl and alkenyl, at least one -CH ₂ - may be substituted with -O-, the plurality of In the base, at least one hydrogen can 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 .

[Chemical 27]

[Chemical 28]

[Chemical 29]

[Chemical 30]

[Chemical 31]

[Chemical 32]

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Component C has positive dielectric anisotropy and very good stability to heat, light, and the like, so it can be preferably used in the preparation of compositions for modes such as IPS, FFS, and OCB. In the case of adjusting the composition having positive dielectric anisotropy using Component C, the content of Component C relative to 100 wt % of the liquid crystal composition is suitably in the range of 1 wt % to 99 wt %, preferably 10 wt % % to 97% by weight, particularly preferably 40% to 95% by weight. When adding Component C to a composition having a negative dielectric anisotropy, the content of Component C is preferably 30 wt % or less with respect to 100 wt % 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 device can be adjusted.

Component D is a compound (8) whose single terminal group is -C≡N or -C≡CC≡N. Component D has a larger positive dielectric anisotropy because it has a cyano group. Preferred examples of component D include compound (8-1) to compound (8-64). D in the compound component, R ¹⁴ is a C 1 alkyl group or a C 10 alkenyl group having 2 to 10, the alkyl and alkenyl, at least one -CH ₂ - may be substituted with -O-, the plurality of In the group, at least one hydrogen can be substituted by fluorine; -X ¹² is -C≡N or -C≡CC≡N.

[Chemical 34]

[Chemical 35]

The dielectric anisotropy of Component D is positive and its value is large, so it is mainly used when preparing a composition for modes such as TN. By adding this component D, the dielectric anisotropy of the composition can be increased. Component D has 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 using component D to adjust the composition with positive dielectric anisotropy, the content of component D relative to 100% by weight of the liquid crystal composition is suitably in the range of 1% by weight to 99% by weight, preferably 10% by weight % to 97% by weight, particularly preferably 40% to 95% by weight. When the component D is added to a composition having a negative dielectric anisotropy, the content of the component D is preferably 30% by weight or less with respect to 100% by 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 device can be adjusted.

Component E is selected from compounds (11) to (19). Composition E has a large negative dielectric anisotropy. These compounds have a 2,3-difluoro-1,4-phenylene-like phenylene substituted with two halogens (fluorine or chlorine) in the pendant position. Preferred examples of component E include compound (11-1) to compound (11-9), compound (12-1) to compound (12-19), compound (13-1) to compound (13-2), Compound (14-1) to Compound (14-3), Compound (15-1) to Compound (15-3), Compound (16-1) to Compound (16-11), Compound (17-1) to Compound (17-3), compound (18-1) to compound (18-3) and compound (19-1). In these compounds, R ¹⁵ , R ¹⁶ and R ^{17 are} independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in the alkyl and alkenyl groups, at least one -CH ₂ - may be -O-substituted, in these groups, at least one hydrogen may be substituted with fluorine, and R ¹⁷ may also be hydrogen or fluorine.

[Chemical 36]

[Chemical 37]

The dielectric anisotropy of the component E is negative and large. Ingredient E can be preferably used in the preparation of compositions for modalities such as IPS, VA, and PSA. As the content of the component E is increased, the dielectric anisotropy of the composition becomes negative and increases, but the viscosity increases. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the content is preferably as small as possible. Considering that the dielectric anisotropy is about -5, the content of component E is preferably 40 wt % or more with respect to 100 wt % of the liquid crystal composition in order to perform sufficient voltage driving.

In the component E, since the compound (11) is a bicyclic compound, it has the effect of reducing the viscosity, adjusting the optical anisotropy, or improving the dielectric anisotropy. The compound (12) and the compound (13) are tricyclic compounds, and the compound (14) is a tetracyclic compound, and therefore have the effect of increasing the upper limit temperature, increasing the optical anisotropy, or increasing the dielectric anisotropy. Compounds (15) to (19) have an effect of increasing the dielectric anisotropy.

In the case of using the component E to adjust the composition with negative dielectric anisotropy, the content of the component E is preferably 40% by weight or more, particularly preferably 50% by weight to 95% by weight relative to 100% by weight of the liquid crystal composition. % range. When adding Component E to a composition having positive dielectric anisotropy, the content of Component E is preferably 30 wt % or less with respect to 100 wt % 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 device can be adjusted.

By appropriately combining the above-mentioned component B, component C, component D and component E, a liquid crystal composition can be prepared that fully satisfies at least one of the following characteristics: high upper limit temperature, low minimum temperature, low viscosity, optical anisotropy Appropriate, positive or negative dielectric anisotropy, high specific resistance, high stability to ultraviolet light, high stability to heat, high elastic constant, etc.

3-2. Additives The liquid crystal composition is prepared by a known method. For example, the method of mixing the said components, and making it mutually melt|dissolve by heating is mentioned. Additives may be added to the composition according to the application. Examples of additives are polymerizable compounds other than compound (1), polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, pigments, antifoaming agents, and the like. Such additives are well known to those of ordinary skill in the art and are described in the literature.

The polymerizable compound is added for the purpose of producing a polymer in the liquid crystal composition. A polymer can be produced by irradiating ultraviolet rays with a voltage applied between the electrodes to polymerize the compound (1). At this time, the compound (1) is immobilized in a state in which its polar group interacts with the substrate surface of the glass (or metal oxide) in a non-covalent bond manner. Thereby, the ability to control the alignment of the liquid crystal molecules is further improved, and an appropriate pretilt angle can be obtained, so that the response time can be shortened.

Preferable examples of the polymerizable compound are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes), and vinyl ketones. Particularly preferred examples are compounds having at least one acryloxy group and compounds having at least one methacryloyloxy group. Especially preferable examples also include compounds having both acryloxy and methacryloyloxy groups. Compound (20) is mentioned as a particularly preferable example of the polymerizable compound. Compound (20) is a different compound from compound (1). Compound (1) has a polar group. On the other hand, the compound (20) preferably does not have a polar group.

[Chemical 38]

In formula (20), ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxyl Alkyl-2-yl, pyrimidin-2-yl or pyridin-2-yl, in these rings, at least one hydrogen can be replaced by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or at least one hydrogen One hydrogen is substituted with a halogen-substituted alkyl group having 1 to 12 carbons.

Preferred ring F and ring I are cyclohexyl, cyclohexenyl, phenyl, fluorophenyl, difluorophenyl, 1-naphthyl or 2-naphthyl. Particularly preferred Ring F and Ring I are cyclohexyl, cyclohexenyl or phenyl. Particularly preferred ring F and ring I are phenyl.

In formula (20), 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, phenanthrene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-diyl Dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in these rings, at least one hydrogen can be replaced by halogen, alkyl having 1 to 12 carbons, The alkoxy group having 1 to 12 carbons or at least one hydrogen is substituted with an alkyl group having 1 to 12 carbons substituted by halogen.

Preferred ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-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. Particularly preferred ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene or 2-fluoro-1,4-phenylene. Particularly preferred ring G is 1,4-phenylene or 2-fluoro-1,4-phenylene. The most preferred ring G is 1,4-phenylene.

In formula (20), Z ²² and Z ^{23 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be through -O-, -CO-, - COO- or -OCO- substituted, at least one -CH ₂ CH ₂ - may be via -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ ) = C (CH ₃₎ - substituted, the plurality of groups, at least one hydrogen may be substituted by fluorine or chlorine. Preferred Z ²² and Z ²³ are single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-. The preferred Z ²² and Z ²³ are single bonds.

In compound (20), P ¹¹ , P ¹² and P ^{13 are} independently polymerizable groups. Desirable P ¹¹ to P ¹³ are groups selected from the group of polymerizable groups represented by formula (P-1) to formula (P-5). Particularly preferred P ¹¹ to P ¹³ are groups represented by formula (P-1), formula (P-2) or formula (P-3). Particularly preferred P ¹¹ to P ¹³ are groups represented by the formula (P-1). A preferable group represented by formula (P-1) is acryloxy (-OCO-CH=CH ₂ ) or methacryloyloxy (-OCO-C(CH ₃ )=CH ₂ ). The wavy lines in the formula (P-1) to the formula (P-5) indicate the bonding site.

[Chemical 39]

In formulas (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 at least one hydrogen substituted by halogen with a carbon number of 1 to 5 5 alkyl. In order to improve reactivity, preferable M ¹¹ , M ¹² and M ¹³ are hydrogen or methyl. Particularly preferred M ¹¹ is hydrogen or methyl, and particularly preferred M ¹² and M ¹³ are hydrogen.

In formula (20), Sp ¹¹ , Sp ¹² and Sp ^{13 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be through -O-, -COO -, -OCO- or -OCOO-, at least one -CH ₂ CH ₂ - may be substituted with -CH=CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine. Preferred Sp ¹¹ , Sp ¹² and Sp ¹³ are single bonds.

In formula (20), u is 0, 1 or 2. Desirable u is 0 or 1.

In formula (20), f, g, and h are independently 0, 1, 2, 3, or 4, and the sum of f, g, and h is 1 or more. Preferred f, g or h are 0, 1 or 2. Preferred sums are 2, 3 or 4. The preferred sum is 2 or 3.

Preferred examples of the compound (20) are the compounds (20-1) to (20-7) described in Item 15 and the following compounds (20-8) to (20-11). Particularly preferred examples are compound (20-1-1) to compound (20-1-5), compound (20-2-1) to compound (20-2-5), compound (20-4-1), Compound (20-5-1), Compound (20-6-1) and Compound (20-7-1). In these compounds, R ²⁵ to R ^{31 are} independently hydrogen or methyl; R ³² , R ³³ and R ^{34 are} independently hydrogen or an alkyl group having 1 to 5 carbon atoms, and R ³² , R ³³ and R ³⁴ are At least one is an alkyl group having 1 to 5 carbon atoms; v and x are independently 0 or 1; t and u are independently an integer from 1 to 10; t+v and x+u are respectively at most 10; L ³¹ to L ^{36 is} independently hydrogen or fluorine, and L ³⁷ and L ^{38 are} independently hydrogen, fluorine or methyl.

[Chemical 40]

[Chemical 41]

The polymerizable compound in the composition can be rapidly polymerized by using a polymerization initiator such as a photoradical polymerization initiator. In addition, by optimizing the reaction conditions at the time of polymerization, the amount of the remaining polymerizable compound can be reduced. Examples of photo-radical polymerization initiators include TPO, 1173 and 4265 in the Darocure series of BASF, and 184, 369, 500, and 184 in the Irgacure series. 651, 784, 819, 907, 1300, 1700, 1800, 1850 and 2959.

Additional examples of photo-radical polymerization initiators are 4-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(4-butoxystyryl)-5-trichloro Methyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzophenazine, benzophenone/Michel's ketone mixture, hexaarylbiimidazole/mercaptobenzimidazole Mixture, 1-(4-Isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, Benzyldimethylketal, 2-methyl-1-[4-(methylthio ) Phenyl]-2-morpholinopropan-1-one, 2,4-diethylxanthone/p-dimethylaminobenzoic acid methyl ester mixture, benzophenone/methyltriethanolamine mixture .

After adding the photoradical polymerization initiator to the liquid crystal composition, the polymerization can be performed by irradiating ultraviolet rays in a state where an electric field is applied. However, the unreacted polymerization initiator or the decomposition product of the polymerization initiator may cause poor display such as image afterimage on the element. In order to prevent this, photopolymerization may be performed without adding a polymerization initiator. The preferred wavelength of the irradiated light is in the range of 150 nm to 500 nm. A particularly preferred wavelength is in the range of 250 nm to 450 nm, and an optimum wavelength is in the range of 300 nm to 400 nm.

When storing the polymerizable compound, a polymerization inhibitor may be added to prevent polymerization. When the polymerization inhibitor is contained in the polymerizable compound, it 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, and phenothiazine.

The optically active compound has an effect of preventing reverse twist by inducing a helical structure in liquid crystal molecules to impart a desired twist angle. By adding optically active compounds, the pitch of the helix can be adjusted. Two or more optically active compounds may 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. The * symbol indicates an asymmetric carbon.

[Chemical 42]

In order to maintain a large voltage holding ratio of the element, it is effective to use an antioxidant. Preferred examples of antioxidants include: the following compounds (AO-1) and compounds (AO-2); Irganox 415, Irganox 565, Irganox 1010, Irganox 1010, Irganox 1035, Irganox 3114 and Irganox 1098 (trade names; BASF).

In order to prevent the lowering of the upper limit temperature of the element, it is effective to use an ultraviolet absorber. Preferred examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives, etc. Specific examples include the following compounds (AO-3) and compounds (AO-4); Tinuvin 329, Tinuvin P, Tinuvin 326, Tinuvin 234, Tinuvin 213, Tinuvin 400, Tinuvin (Tinuvin) 328 and Dinuvin (Tinuvin) 99-2 (trade names; BASF Corporation); and 1,4-diazabicyclo[2.2.2]octane (DABCO).

In order to maintain a large voltage holding ratio of the element, it is preferable to use a light stabilizer such as an amine having steric hindrance. Preferred examples of light stabilizers include: the following compounds (AO-5), compounds (AO-6) and compounds (AO-7); Tinuvin 144, Tinuvin 765 and Tinuvin Nubin (Tinuvin) 770DF (trade name; BASF (BASF) company); LA-77Y and LA-77G (trade name; ADEKA (ADEKA) company).

In order to maintain a high voltage holding ratio of the device, it is also effective to use a thermal stabilizer, and a preferable example may be Irgafos 168 (trade name; BASF).

Dichroic dyes such as azo-based dyes and anthraquinone-based dyes may be added to the composition as necessary in order to be suitable for a guest host (GH) mode device.

To prevent foaming, antifoaming agents are effective. Preferred examples of the defoaming agent are dimethyl silicone oil, methyl phenyl silicone oil, and the like.

[Chemical 43]

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 , where R ⁴¹ is a carbon number 1 to 20 alkyl groups. In compound (AO-2) and compound (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 ^· (oxygen radical); ring G ¹ is 1,4-cyclohexylene or 1,4-phenylene; compound (AO-7) wherein, ring G ² is a group in which at least one hydrogen of 1,4-cyclohexylene, 1,4-phenylene or 1,4-phenylene is substituted with fluorine; compound (AO-5) and compound (AO- 7), z is 1, 2 or 3.

4. Liquid crystal display element The liquid crystal composition can be preferably used for liquid crystal display elements with operating modes such as PC, TN, STN, OCB, PSA, etc. and driven in an active matrix manner. The composition can also be preferably used for liquid crystal display elements with operating modes such as PC, TN, STN, OCB, VA, and IPS, which are driven in passive matrix mode. These elements can also be applied to any type of reflection type, transmission type, and semi-transmission type.

The composition is also suitable for nematic curvilinear aligned phase (NCAP) elements, where the composition is microencapsulated. The composition can also be used in polymer dispersed liquid crystal display (PDLCD) or polymer network liquid crystal display (PNLCD). To these compositions, a large amount of a polymerizable compound is added. On the other hand, with respect to the composition for a liquid crystal display element in the PSA mode, the ratio of the polymerizable compound is preferably 10% by weight or less, and more preferably 0.1% by weight to 2% by weight relative to 100% by weight of the liquid crystal composition. % range, a particularly preferred ratio is in the range of 0.2 to 1.0 wt %. The elements in the PSA mode can be driven by a driving method such as an active matrix method or a passive matrix method. This type of element can also be applied to any type of reflection type, transmission type, and semi-transmission type.

In a polymer-stabilized alignment type device, the polymer contained in the composition aligns the liquid crystal molecules. Polar compounds help the liquid crystal molecules align. That is, a polar compound can be used instead of the alignment film. An example of the method of manufacturing such an element is as follows. An element 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. The liquid crystal compound is mixed to prepare a liquid crystal composition. Compound (1) and other polymerizable compounds and polar compounds as needed are added to this composition. Further additives may be added as necessary. The composition is injected into the element. Light irradiation was performed in a state where a voltage was applied to the element. Ultraviolet rays are preferred. The polymerizable compound is polymerized by light irradiation. By this polymerization, a polymer-containing composition is produced, whereby a device having a PSA mode is produced.

In this procedure, polar compounds are arranged on the substrate due to the interaction of polar groups with the substrate surface. The polar compound aligns liquid crystal molecules. When a plurality of polar groups are present, the interaction with the substrate surface becomes stronger, and alignment can be performed at a low concentration. When a voltage is applied, the alignment of the liquid crystal molecules is further promoted by the action of the electric field. According to this alignment, the polymerizable compound is also aligned. In this state, the polymerizable compound is polymerized by ultraviolet rays, and thus a polymer maintaining the above-mentioned alignment is produced. By the effect of the polymer, the alignment of the liquid crystal molecules is additionally stabilized, so that the response time of the device is shortened. Since the afterimage of the image is caused by the malfunction of the liquid crystal molecules, the afterimage is also improved by the effect of the polymer. Compound (1) is polymerizable and therefore consumed by polymerization. Compound (1) is also consumed by copolymerizing with other polymerizable compounds. Therefore, although the compound (1) has a polar group, it is consumed, so that a liquid crystal display element having a large voltage holding ratio can be obtained. In addition, when a polymerizable polar compound is used, the effects of both the polar compound and the polymerizable compound can be achieved with one compound, so the polymerizable compound without a polar group may not be necessary. [Example]

The present invention will be further described in detail with reference to examples (including synthesis examples and usage examples). The present invention is not limited by these Examples. The present invention also includes mixtures prepared by mixing at least two of the compositions of the use examples.

1. Examples of compound (1) Unless otherwise specified, the reaction was carried out in a nitrogen atmosphere. Compound (1) was synthesized by the procedures shown in Example 1 and the like. The synthesized compounds were identified by nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) analysis and other methods. The properties of the compound (1), the liquid crystal compound, the composition, and the device were measured by the following methods.

NMR analysis: For the measurement, DRX-500 manufactured by Bruker BioSpin was used. In ^{the measurement of 1} H-NMR, the sample is dissolved in a _{deuterated solvent such as CDCl 3 ,} and the measurement is performed at room temperature under the conditions of 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 carried out under the conditions of 24 cumulative times. In the description of NMR spectra, s means singlet, d means doublet, t means triplet, q means quartet, and quin means quintet (quintet), sext refers to sextet (sextet), m refers to multiplet (multiplet), br refers to broad peak (broad).

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

High Performance Liquid Chromatography (HPLC) analysis: Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used for the measurement. The column was a YMC-Pack (YMC-Pack) ODS-A (150 mm length, 4.6 mm inner diameter, 5 μm particle size) manufactured by Vemex (YMC). The eluate is used by appropriately mixing acetonitrile and water. As a detector, an ultraviolet (Ultraviolet, UV) detector, a refractive index (Reflective Index, RI) detector, a Corona (CORONA) detector, etc. are suitably used. In the case of using a UV detector, the detection wavelength was set to 254 nm. The sample was dissolved in acetonitrile to prepare a 0.1 wt % solution, and 1 μL of this solution was introduced into the sample chamber. The recorder is a C-R7A plus manufactured by Shimadzu Corporation.

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

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

Measurement method: The measurement of the characteristic was performed by the following method. Most of these methods are methods described or modified in the JEITA standard (JEITA·ED-2521B) reviewed and formulated by the Japan Electronics and Information Technology Industries Association (JEITA). Thin film transistors (TFTs) were not mounted on the TN elements used for the measurement.

(1) Phase structure The sample was placed on a hot plate (manufactured by Mettler, FP-52 hot stage) equipped with a melting point measuring apparatus equipped with a polarizing microscope. While heating this sample at a rate of 3° C./min, the phase state and its change were observed with a polarizing microscope, and the type of the phase was determined.

(2) Transition temperature (°C) In the measurement, a scanning calorimeter Diamond DSC system manufactured by Perkin Elmer Co., Ltd. or a high-sensitivity scanning calorimeter manufactured by Hitachi High-Tech Science Co., Ltd. was used. Differential Scanning Calorimeter X-DSC7000. The temperature of the sample was raised and lowered at a rate of 3°C/min, and the starting point of the endothermic peak or the exothermic peak accompanying the phase change of the sample was obtained by extrapolation, and the transition temperature was determined. The melting point of the compound and the polymerization initiation temperature were also measured using this apparatus. The temperature at which the compound changes from a solid to a smectic phase or a nematic phase liquid crystal phase is sometimes simply referred to as "the lower limit temperature of the liquid crystal phase". The temperature at which a compound changes from a liquid crystal phase to a liquid is sometimes abbreviated as "clear point".

The crystal is represented as C. When distinguishing the types of crystals, they are represented as C ₁ and C ₂ , respectively. Denote the smectic phase as S and the nematic phase as N. Smectic phase, smectic A phase in the layered region, smectic B phase, a smectic C phase or a smectic F phase of the case, are expressed as S _A, S _B, S _C or S _F. Denote the liquid (isotropic) as I. The transition temperature is expressed as, for example, "C 50.0 N 100.0 I". It means that the temperature at which the self-crystallizing phase is transformed into a nematic phase is 50.0°C, and the temperature at which the self-nematic phase is transformed into a liquid is 100.0°C.

(3) Upper limit temperature of nematic phase (T _NI or NI; °C) The sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope, and heated at a rate of 1 °C/min. The temperature at which a part of the sample changes from the nematic phase to the isotropic liquid is measured. The upper limit temperature of the nematic phase is sometimes abbreviated as "upper limit temperature". When the sample is a mixture of compound (1) and mother liquid crystal, it is represented by the symbol of _TNI. When the sample is a mixture of compound (1) and compounds such as Component B, Component C, and Component D, it is represented by the symbol of NI.

(4) lower limit temperature (T _C; ℃) nematic phase A sample having a nematic phase at 0 ℃, -10 ℃, -20 ℃ , a freezer of -30 ℃ and -40 ℃ for 10 days , observe the liquid crystal phase. For example, when a sample maintains a nematic phase at -20°C and changes to a crystalline or smectic phase at -30°C, the T _{C is} described as ≦-20°C. The lower limit temperature of the nematic phase is sometimes abbreviated as "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) Measurement was performed by an Abbe refractometer with a polarizing plate attached to the eyepiece using light having a wavelength of 589 nm. After rubbing the surface of the main pole in one direction, drop the sample onto the main pole. The refractive index (n∥) was measured when the direction of polarized light was parallel to the direction of rubbing. The refractive index (n⊥) was measured when the direction of polarized light was perpendicular to the direction of rubbing. The value of optical anisotropy (Δn) is calculated according to the formula of Δn=n∥-n⊥.

(7) Specific resistance (ρ; measured at 25° C.; Ωcm) A 1.0 mL sample was injected into a container equipped with an electrode. A DC voltage (10 V) was applied to this container, and the DC current after 10 seconds was measured. The specific resistance is calculated according to the following formula. (specific resistance)={(voltage)×(capacitance of container)}/{(direct current)×(dielectric constant of vacuum)}.

The method for measuring properties may be different between a sample with positive dielectric anisotropy and a sample with negative dielectric anisotropy. The measurement method when the dielectric anisotropy is positive is described in the items (8a) to (12a). In the case where the dielectric anisotropy is negative, the measurement method 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 "Molecular Crystals and Liquid Crystals" by M. Imai et al. and Liquid Crystals)" (Vol. 259, 37 (1995)). A sample was placed in a TN device with a twist angle of 0 degrees and a gap (cell gap) between two glass substrates of 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 the voltage was not applied for 0.2 seconds, the voltage was repeatedly applied under 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 were measured. The value of the rotational viscosity was obtained from these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al. The value of the dielectric anisotropy necessary for this calculation was obtained by the method described below using the element that measured the rotational viscosity.

(8b) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s) Negative dielectric anisotropy: The measurement is based on "Molecular Crystals and Liquid Crystals" by M. Imai et al. and Liquid Crystals)" (Vol. 259, 37 (1995)). A sample was placed in a VA element with a gap (cell gap) between two glass substrates of 20 μm. A voltage was applied to the element in steps of 1 volt in the range of 39 volts to 50 volts. After the voltage was not applied for 0.2 seconds, the voltage was repeatedly applied under 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 were measured. The value of the rotational viscosity was obtained from these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al. The dielectric anisotropy necessary for this calculation is the value measured using the term of the dielectric anisotropy described below.

(9a) Dielectric anisotropy (Δε; measured at 25° C.) Positive dielectric anisotropy: In a TN device in which the distance between two glass substrates (cell gap) is 9 μm and the twist angle is 80 degrees Put in the sample. A sine wave (10 V, 1 kHz) was applied to this element, and after 2 seconds, the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecules was measured. A sine wave (0.5 V, 1 kHz) was applied to this element, and after 2 seconds, the dielectric constant (ε⊥) in the short axis direction of the liquid crystal molecules was measured. The value of dielectric anisotropy is calculated according to the formula of Δε=ε∥-ε⊥.

(9b) Dielectric anisotropy (Δε; measured at 25° C.) Negative dielectric anisotropy: The value of the dielectric anisotropy is calculated according to the formula of Δε=ε∥−ε⊥. The dielectric constants (ε∥ and ε⊥) were measured as follows. 1) Determination of dielectric constant (ε∥): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was coated on a fully cleaned glass substrate. After rotating the glass substrate with a spinner, it heated at 150° C. for 1 hour. A sample was placed in a VA element having a distance (cell gap) between two glass substrates of 4 μm, and the element was sealed with an adhesive cured by ultraviolet rays. A sine wave (0.5 V, 1 kHz) was applied to this element, and after 2 seconds, the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecules was measured. 2) Determination of dielectric constant (ε⊥): apply a polyimide solution on the fully cleaned glass substrate. After the glass substrate was fired, a rubbing treatment was performed on the obtained alignment film. A sample was placed in a TN device with a gap (cell gap) between two glass substrates of 9 μm and a twist angle of 80 degrees. A sine wave (0.5 V, 1 kHz) was applied to this element, and after 2 seconds, the dielectric constant (ε⊥) in the short axis direction of the liquid crystal molecules was measured.

(10a) Elastic constant (K; measured at 25° C.; pN) Positive dielectric anisotropy: In the measurement, an LCR meter HP4284A manufactured by Agilent Technologies was used. A sample was placed in a horizontal alignment element with a gap (cell gap) between two glass substrates of 20 μm. An electric charge of 0 volt to 20 volts was applied to this element, and the electrostatic capacitance and the applied voltage were measured. Using equations (2.98) and (2.101) in "Liquid Crystal Element Handbook" (Nikkan Kogyo Shimbun) on page 75, the measured values of electrostatic capacitance (C) and applied voltage (V) were fitted, according to equation (2.99) And the values of _{K 11} and K _{33 are obtained.} Next, in Formula (3.18) on page 171, _{K 22} is calculated using the values _{of K 11} and K ₃₃ obtained previously. The elastic constant K is represented by the average value _{of K 11} , K ₂₂ and K _{33 thus obtained.}

(10b) Elastic constants (K ₁₁ and K ₃₃ ; measured at 25° C.; pN) Negative dielectric anisotropy: In the measurement, EC-1 type elastic constant manufactured by TOYO Technica Co., Ltd. was used measurer. A sample was placed in a vertical alignment element with a gap (cell gap) between two glass substrates of 20 μm. A charge of 20 volts to 0 volts was applied to this element, and the electrostatic capacitance and the applied voltage were measured. Using equations (2.98) and (2.101) in "Liquid Crystal Element Handbook" (Nikkan Kogyo Shimbun) on page 75, the values of electrostatic capacitance (C) and applied voltage (V) are fitted, and elasticity is obtained from equation (2.100) The value of the constant.

(11a) Threshold voltage (Vth; measured at 25° C.; V) Positive dielectric anisotropy: In the measurement, an LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was set to a halogen lamp. A sample was placed in a normally white mode TN element with an interval (cell gap) of two glass substrates of 0.45/Δn (μm) and a twist angle of 80 degrees. The voltage (32 Hz, rectangular wave) applied to the element was increased from 0 V to 10 V in steps of 0.02 V. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was 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 smallest. The threshold voltage is represented by the voltage at which the transmittance becomes 90%.

(11b) Threshold voltage (Vth; measured at 25° C.; V) Negative dielectric anisotropy: In the measurement, an LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was set to 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 anti-parallel, and the element was sealed with an adhesive cured by ultraviolet rays. . The voltage (60 Hz, rectangular wave) applied to the element was increased from 0 V to 20 V in steps of 0.02 V. At this time, the element was irradiated with light from a vertical direction, and the amount of light transmitted 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 smallest. The threshold voltage is represented by the voltage at which the transmittance becomes 10%.

(12a) Response time (τ; measured at 25° C.; ms) Positive dielectric anisotropy: In the measurement, an LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was set to a halogen lamp. The low-pass filter is set to 5 kHz. A sample was placed in a normally white mode TN element with a gap (cell gap) between two glass substrates of 5.0 μm and a twist angle of 80 degrees. A rectangular wave (60 Hz, 5 V, 0.5 sec) was applied to the element. At this time, the element was irradiated with light from a vertical direction, and the amount of light transmitted through the element was measured. When the light amount reached the maximum, the transmittance was regarded as 100%, and when the light amount was the smallest, the transmittance was regarded as 0%. The rise time (τr: rise time; milliseconds) is the time required for the transmittance to change from 90% to 10%. The fall time (τf: fall time; milliseconds) is the time required for the transmittance to change from 10% to 90%. The response time is represented by the sum of the rise time and fall time thus obtained.

(12b) Response time (τ; measured at 25° C.; ms) Negative dielectric anisotropy: In the measurement, an LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was set to a halogen lamp. The low-pass filter is set to 5 kHz. A sample was placed in a normally black mode (normally black mode) PVA element in which the distance between two glass substrates (cell gap) was 3.2 μm and the rubbing direction was antiparallel. The element is hermetically sealed with an adhesive that cures with ultraviolet rays. A voltage slightly exceeding the threshold voltage was applied to the element for 1 minute, and then 23.5 mW/cm ² of ultraviolet rays were irradiated for 8 minutes while applying a voltage of 5.6 V. A rectangular wave (60 Hz, 10 V, 0.5 sec) was applied to the element. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. When the light amount reached the maximum, the transmittance was regarded as 100%, and when the light amount was the smallest, the transmittance was regarded as 0%. The response time is expressed as the time (fall time; fall time; milliseconds) required for the transmittance to change from 90% to 10%.

(13) Voltage holding ratio The polymerizable compound was polymerized by irradiating ultraviolet rays using black light, F40T10/BL (peak wavelength 369 nm) manufactured by Eye Graphics Co., Ltd. The element was charged by applying a pulse voltage (1 V for 60 microseconds) at 60°C. The decaying voltage was measured with a high-speed voltmeter for a period of 1.67 seconds, and the area A between the voltage curve per unit cycle and the horizontal axis was obtained. Area B is the area without attenuation. Voltage retention is expressed as a percentage of area A relative to area B.

The raw material solmix (registered trademark) A-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (IPA) (1.1%), and is sold from Nippon Alcohol ( shares) to obtain.

[Synthesis example 1] Synthesis of compound (1-2-2) [Chem. 44]

Step 1 Trifluoromethanesulfonic anhydride (25.0 g) and dichloromethane (80.0 ml) were placed in a reactor and cooled to 0°C. A solution of compound (T-1) (10.3 g) and triethylamine (8.97 g) in dichloromethane (160 ml) was slowly added dropwise thereto. The obtained solution was poured into ethylene glycol (165 g) and stirred at room temperature for 12 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The obtained 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, heptane:ethyl acetate=1:1) to obtain Compound (T-2) (6.18 g; 44%).

In the second step, compound (T-2) (6.18 g), 3,4-dihydro-2H-pyran (3.57 g), pyridinium p-toluenesulfonate (PPTS) (0.970 g) and dichloromethane (60.0 ml) into the reactor and stirred at room temperature for 12 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The obtained 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, heptane:ethyl acetate=4:1) to obtain Compound (T-3) (9.15 g; 97%). In addition, THP represents a tetrahydropyranyl group.

Step 3 Compound (T-3) (9.15 g), Tetrahydrofuran (THF) (45.0 ml) and water (45.0 ml) were put into a reactor and cooled to 0°C. Lithium hydroxide monohydrate (3.14 g) was added thereto, and the mixture was stirred for 7 hours while returning to room temperature. The reaction mixture was poured into water, 6 N hydrochloric acid (15 ml) was gradually added to make it acidic, and then the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to obtain Compound (T-4) (5.07 g; 59%).

The fourth step The compound (T-5) (124 g), triethylamine (52.4 g) and THF (3100 ml) synthesized according to the method described in International Publication No. WO 2014/097952 were put into a reactor , and cooled to 0°C. Compound (T-6) (50.0 g) was gradually added dropwise thereto, and the mixture was stirred at 50° C. for 3 hours. The reaction mixture was poured into brine, and the aqueous layer was extracted with t-butyl methyl ether. The obtained organic layer was washed with water and brine in this order, and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=4:1) to obtain Compound (T-7) (55.6 g; 37%).

Step 5 Compound (T-4) (3.64 g), compound (T-7) (5.00 g), DMAP (0.807 g) and dichloromethane (75.0 ml) were put into the reactor and cooled to 0 °C. A solution of DCC (4.09 g) in dichloromethane (25.0 ml) was slowly added dropwise thereto, and the mixture was stirred for 12 hours while returning to room temperature. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The obtained 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, heptane:ethyl acetate=5:1) to obtain Compound (T-8) (7.35 g; 94%).

Step 6 Compound (T-8) (7.35 g), PPTS (1.56 g), THF (37.0 ml) and methanol (37.0 ml) were put into a reactor and stirred at 50°C for 4 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=2:1). Further, it was purified by recrystallization from heptane to obtain compound (1-2-2) (3.54 g; 56%).

The NMR analysis values of the obtained compound (1-2-2) are as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.30 (s, 1H), 6.09 (s, 1H), 5.88 (d, J=1.2 Hz, 1H), 5.57 (s, 1H), 4.35- 4.26 (m, 2H), 4.24 (s, 2H), 4.21-4.14 (m, 2H), 3.78-3.73 (m, 2H), 3.62 (t, J=4.7 Hz, 2H), 2.27 (t, J= 6.3 Hz, 1H), 1.97-1.90 (m, 4H), 1.85-1.64 (m, 8H), 1.48-1.38 (m, 1H), 1.34-1.18 (m, 6H), 1.18-0.78 (m, 16H) .

[Synthesis example 2] Synthesis of compound (1-2-6) [Chem. 45]

Step 1 Compound (T-9) (30.0 g), compound (T-10) (28.2 g) and toluene (90.0 ml) were put into a reactor, and cooled to 0°C. Sodium ethoxide (20% by weight; ethanol solution; 42.8 g) was gradually added thereto, followed by stirring at 0°C for 1 hour. The reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with brine, and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=9:1) to obtain Compound (T-11) (36.5 g; 95%).

In the second step, compound (T-11) (36.5 g), toluene (190 ml), IPA (190 ml) and palladium-carbon catalyst (PH type of 5% Pd/C; Fine chemical) ( stock) manufacture; 0.242 g) was placed in the reactor and stirred under hydrogen atmosphere for 12 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=9:1) to obtain Compound (T-12) (34.8 g; 95%).

Step 3 Lithium aluminum hydride (2.46 g) and THF (200 ml) were placed in the reactor and cooled to 0°C. To this, a solution of Compound (T-12) (34.8 g) in THF (150 ml) was gradually added, and the mixture was stirred for 3 hours while returning to room temperature. The reaction mixture was poured into water, the insoluble matter was separated by filtration, and the aqueous layer was extracted with ethyl acetate. The obtained 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 recrystallization from heptane to obtain Compound (T-13) (18.3 g; 61%).

In the fourth step, compound (T-13) (18.3 g), p-toluenesulfonyl chloride (TsCl) (13.7 g), N,N-dimethylaminopyridine (DMAP) (9.58 g) and dichloromethane ( 275 ml) into the reactor and stirred at room temperature for 12 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with water and brine in this order, and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=9:1). Further, purification was performed by recrystallization from heptane to obtain Compound (T-14) (23.0 g; 81%). In addition, Ts represents a tosylate group.

Step 5 Compound (T-14) (19.0 g), THF (190 ml) and DMF (190 ml) were put into a reactor and cooled to 0°C. Sodium hydride (3.81 g) was gradually added thereto, and the mixture was stirred for 1 hour while returning to room temperature. Compound (T-10) (14.7 g) and sodium iodide (1.32 g) were added thereto, and the mixture was stirred at 80° C. for 2 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with brine, and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=9:1) to obtain Compound (T-15) (13.1 g; 71%).

Step 6 Sodium borohydride (4.69 g), lithium chloride (0.263 g) and ethanol (65.0 ml) were placed in the reactor and cooled to 0°C. To this, a solution of Compound (T-15) (13.1 g) in THF (130 ml) was gradually added, and the mixture was stirred at 60° C. for 3 hours. The reaction mixture was poured into 1 N hydrochloric acid (400 ml), and the precipitated solid was separated by filtration. The obtained solid was washed with water and ethyl acetate in this order to obtain Compound (T-16) (9.37 g; 89%).

Step 7 Compound (T-16) (45.0 g), potassium carbonate (25.3 g) and THF (1120 ml) were put into a reactor and heated to 30°C. Compound (T-17) (24.3 ml) was gradually added thereto, followed by stirring at 50°C for 10 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with brine, and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=4:1) to obtain Compound (T-18) (22.9 g; 42%).

Step 8 Compound (T-18) (5.00 g) was used as a starting material, and by the same method as Step 5 of Synthesis Example 1, Compound (T-19) (6.67 g; 88%) was obtained.

9th step Compound (1-2-6) (4.32 g; 75%) was obtained by the same method as in the 6th step of Synthesis Example 1 using compound (T-19) (6.67 g) as a starting material.

The NMR analysis values of the obtained compound (1-2-6) are as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.31 (d, J=0.8 Hz, 1H), 6.10 (s, 1H), 5.89 (d, J=1.5 Hz, 1H), 5.57 (t, J=1.7 Hz, 1H), 4.27-4.09 (m, 6H), 3.79-3.73 (m, 2H), 3.62 (t, J=4.8 Hz, 2H), 2.27 (t, J=6.2 Hz, 1H), 2.12-2.03 (m, 1H), 1.94 (s, 3H), 1.78-1.65 (m, 8H), 1.46-1.38 (m, 2H), 1.34-1.18 (m, 8H), 1.18-1.05 (m, 4H) ), 1.04-0.90 (m, 6H), 0.90-0.78 (m, 7H).

[Synthesis example 3] Synthesis of compound (1-3-4) [Chem. 46]

Step 1 Compound (T-20) (200 g) and THF (2000 ml) were put into a reactor and cooled to 0°C. Isopropylmagnesium chloride x lithium chloride complex (1.30 M; n-THF solution; 421 ml) was slowly added dropwise thereto, and the mixture was stirred at 0° C. for 60 minutes. DMF (42.4 ml) was gradually added dropwise thereto, and the mixture was stirred for 3 hours while returning to room temperature. The reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The obtained 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, heptane:toluene=1:1) to obtain Compound (T-21) (149 g; 96%).

Step 2 Sodium borohydride (16.6 g) and methanol (745 ml) were placed in the reactor and cooled to 0°C. To this, a solution of Compound (T-21) (149 g) in THF (745 ml) was gradually added, and the mixture was stirred for 3 hours while returning to room temperature. The reaction mixture was poured into a saturated aqueous ammonium chloride solution, and the aqueous layer was extracted with ethyl acetate. The obtained 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 recrystallization from heptane to obtain Compound (T-22) (137 g; 91%).

Step 3 Compound (T-22) (137 g), triphenylphosphine (115 g) and dichloromethane (850 ml) were put into a reactor and cooled to 0°C. A solution of carbon tetrabromide (145 g) in THF (500 ml) was gradually added thereto, and the mixture was stirred for 12 hours while returning to room temperature. The reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The obtained 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 (heptane) to obtain Compound (T-23) (132 g; 82%).

Fourth step Compound (T-23) (132 g), triphenylphosphine (94.1 g) and toluene (2500 ml) were put into a reactor, and the mixture was heated under reflux at 110°C for 15 hours. The reaction mixture was cooled to 0°C, and the precipitated crystals were separated by filtration, whereby Compound (T-24) (178 g; 82%) was obtained.

Step 5 Compound (T-24) (178 g) and THF (900 ml) were put into a reactor and cooled to -30°C. To this, potassium tert-butoxide (29.9 g) was added, and the mixture was stirred at -30°C for 1 hour. Then, a solution of Compound (T-25) (38.4 g) in THF (900 ml) was gradually added dropwise, and the mixture was stirred for 12 hours while returning to room temperature. The reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The obtained 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 column chromatography (toluene) to obtain Compound (T-26) (78.1 g, yield 65%) as a mixture of Z body and E body. (Z body:E body = 95:5)).

Step 6 Compound (T-26) (78.1 g) was used as a starting material, and by the same method as the second step of Synthesis Example 2, compound (T-27) (78.0 g; 99%) was obtained.

Step 7 Compound (T-27) (74.6 g), p-toluenesulfonic acid monohydrate (PTSA), toluene (800 ml) and methanol (800 ml) were put into the reactor and stirred at room temperature for 12 Hour. The reaction mixture was poured into saturated aqueous sodium bicarbonate solution, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to obtain Compound (T-28) (59.0 g, yield 87%).

8th step Compound (T-28) (12.9 g) was used as a starting material, and by the same method as in the 7th step of Synthesis Example 2, compound (T-29) (6.44 g; 43%) was obtained.

9th step Compound (T-29) (22.0 g) was used as a raw material, and by the same method as in the 5th step of Synthesis Example 1, compound (T-30) (24.6 g; 78%) was obtained.

10th step Compound (1-3-4) (19.5 g; 90%) was obtained by the same method as in the 6th step of Synthesis Example 1 using compound (T-30) (24.6 g) as a starting material.

The NMR analysis values of the obtained compound (1-3-4) are as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.17-7.09 (m, 4H), 6.33 (d, J=0.9 Hz, 1H), 6.13 (s, 1H), 5.91 (d, J=1.3 Hz, 1H), 5.60 (t, J=1.3 Hz, 1H), 4.31-4.19 (m, 6H), 3.81-3.75 (m, 2H), 3.64 (t, J=4.7 Hz, 2H), 2.70 (t , J=7.9 Hz, 2H), 2.44 (tt, J=12.1 Hz, J=3.3 Hz, 1H), 2.25 (t, J=6.3 Hz, 1H), 2.23-2.15 (m, 1H), 1.99-1.72 (m, 13H), 1.49-1.38 (m, 2H), 1.38-0.97 (m, 15H), 0.95-0.83 (m, 5H).

[Synthesis example 4] Synthesis of compound (1-2-16) [Chem. 47]

In the first step, the compound (T-1) (14.6 g) was used as a raw material, and diethylene glycol (400 g) was used instead of ethylene glycol, and the compound was obtained by the same method as in the first step of Synthesis Example 1. (T-31) (13.9 g; 54%).

Second step Compound (T-31) (13.9 g) was used as a starting material, and by the same method as in the second step of Synthesis Example 1, compound (T-32) (19.2 g; 98%) was obtained.

3rd step Compound (T-32) (19.2 g) was used as a raw material, and by the same method as in the 3rd step of Synthesis Example 1, compound (T-33) (9.75 g; 54%) was obtained.

Step 4 Using compound (T-18) (5.00 g) and compound (T-33) (4.72 g) as starting materials, compound (T-34) was obtained by the same method as step 5 of Synthesis Example 1 ) (7.32 g; 90%).

5th step Compound (1-2-16) (4.56 g; 71%) was obtained by the same method as in the 6th step of Synthesis Example 1 using compound (T-34) (7.32 g) as a starting material.

The NMR analysis values of the obtained compound (1-2-16) are as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.31 (d, J=0.8 Hz, 1H), 6.10 (s, 1H), 5.91 (d, J=1.4 Hz, 1H), 5.57 (t, J=1.7 Hz, 1H), 4.27-4.09 (m, 6H), 3.77-3.65 (m, 6H), 3.62 (t, J=4.3 Hz, 2H), 2.36 (t, J=6.3 Hz, 1H), 2.12-2.03 (m, 1H), 1.94 (s, 3H), 1.78-1.65 (m, 8H), 1.46-1.38 (m, 2H), 1.34-1.18 (m, 8H), 1.18-1.05 (m, 4H) ), 1.04-0.78 (m, 13H).

[Synthesis example 5] Synthesis of compound (1-2-17) [Chem. 48]

In the first step, the compound (T-1) (10.3 g) was used as a raw material, and 1,6-hexanediol (314 g) was used instead of ethylene glycol, and the same method as in the first step of Synthesis Example 1 was carried out. And compound (T-35) (11.3 g; 59%) was obtained.

Second step Compound (T-35) (11.3 g) was used as a starting material, and by the same method as in the second step of Synthesis Example 1, compound (T-36) (15.0 g; 96%) was obtained.

3rd step Compound (T-36) (15.0 g) was used as a raw material, and by the same method as in the 3rd step of Synthesis Example 1, compound (T-37) (13.0 g; 91%) was obtained.

Step 4 Compound (T-38) was obtained by the same method as Step 5 of Synthesis Example 1 using Compound (T-18) (5.00 g) and Compound (T-37) (4.23 g) as starting materials ) (6.84 g; 82%).

5th step Compound (1-2-17) (2.33 g; 39%) was obtained by the same method as in the 6th step of Synthesis Example 1 using compound (T-38) (6.84 g) as a starting material.

The NMR analysis values of the obtained compound (1-2-17) are as follows. ¹ H-NMR: chemical shift δ (ppm; CDCl ₃ ): 6.28 (s, 1H), 6.10 (s, 1H), 5.88 (d, J=1.3 Hz, 1H), 5.57 (s, 1H), 4.24- 4.08 (m, 6H), 3.69-3.61 (m, 2H), 3.52-3.45 (m, 2H), 2.06 (t, J=6.4 Hz, 1H), 1.94 (s, 3H), 1.78-1.53 (m, 12H), 1.46-1.35 (m, 6H), 1.34-1.18 (m, 9H), 1.18-1.05 (m, 4H), 1.04-0.78 (m, 13H).

The following compound (1-1-1) to compound (1-4-40) can be synthesized by referring to the method described in the synthesis example or the section "2. Synthesis of compound (1)".

[Chemical 49]

[Chemical 50]

[Chemical 51]

[Chemical 52]

[Chemical 53]

[Chemical 54]

[Chemical 55]

[Chemical 56]

[Chemical 57]

[Chemical 58]

[Chemical 59]

[Chemical 60]

[Chemical 61]

[Comparative Example 1] As a comparative compound, the following compound (S-1) described in the publication was synthesized based on the description of International Publication No. WO 2017/047177, and the properties thereof were measured.

[Chemical 62]

The NMR analysis values of the comparative compound (S-1) are as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.48-7.46 (m, 2H), 7.27-7.26 (m, 2H), 6.75 (d, J=2.3 Hz, 2H), 6.47-6.46 (m , 1H), 6.30 (s, 2H), 5.86 (d, J=1.1 Hz, 2H), 4.54 (t, 4.4 Hz, 4H), 4.33 (s, 4H), 4.27-4.25 (m, 4H), 2.52 -2.47 (m, 1H), 2.34 (s, 2H), 1.98-1.83 (m, 4H), 1.51-1.44 (m, 2H), 1.35-1.20 (m, 9H), 1.09-1.02 (m, 2H) , 0.90 (t, J=6.9 Hz, 3H).

The physical properties of the comparative compound (S-1) are as follows. Transition temperature: C 58.8 I.

Compound (1-2-2), compound (1-2-6), compound (1-3-4), compound (1-2-16) and compound (1-2-17) were compared with the comparative compound (S -1) Compatibility in liquid crystal compositions was compared. The composition (i) containing the following compounds (i-1) to (i-9) was used for the evaluation.

The ratio of the components of the composition (i) is expressed in % by weight.

[Chemical 63]

Compound (1-2-2), compound (1-2-6), and compound (1) were added at any ratio of 0.1% by weight to 1.0% by weight shown in Table A with respect to 100% by weight of composition (i) -3-4), the compound (1-2-16) and the compound (1-2-17) or the comparative compound (S-1) were prepared as samples. After the sample was left to stand at 25° C. for 7 days, it was visually observed, and the case where the nematic phase was maintained was shown as ○, and the case where a crystal or smectic phase was precipitated was shown as ×.

[Table A]

Compatibility was compared, the results: compound (1-2-2), compound (1-2-6), compound (1-3-4), compound (1-2-16) and compound (1-2) -17) Even if 1.0 wt % is added to the mother liquid crystal (composition (i)), the nematic phase is maintained, while the comparative compound (S-1) is crystallized even if 0.2 wt % is added. These compounds are similar compounds in that they have a plurality of polymerizable groups, but the sameness with respect to the mother liquid crystal differs greatly. The reason for this is considered to be that the comparative compound (S-1) has a plurality of hydroxyl groups as polar groups, whereas the compound (1-2-2), the compound (1-2-6), the compound (1-3-4) ), compound (1-2-16) and compound (1-2-17) have only one hydroxyl group as a polar group, so the affinity for mother liquid crystal is improved. The compound (1) can be called a compound having a plurality of polymerizable groups and having practical compatibility.

2. Examples of compositions The compounds in the examples are represented by symbols based on the definitions in Table 2 below. In Table 2, the steric configuration related to the 1,4-cyclohexylene group is the trans configuration. The number in parentheses after the symbol corresponds to the number of the compound. The symbol (-) refers to other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is the weight percentage (% by weight) based on the weight of the liquid crystal composition. Finally, the characteristic values of the liquid crystal composition are summarized. The properties are measured according to the methods described above, and the measured values are directly described (without extrapolation).

[Table 2]

[Example 1] 1-BB-3 (2-8) 5% 1-BB-5 (2-8) 8% 2-BTB-1 (2-10) 2% 3-HHB-1 (3-1 ) 6% 3-HHB-3 (3-1) 14% 3-HHB-O1 (3-1) 5% 3-HHB-F (6-1) 4% 2-HHB(F)-F (6- 2) 7% 3-HHB(F)-F (6-2) 8% 5-HHB(F)-F (6-2) 8% 3-HHB(F,F)-F (6-3) 5 % 3-HHEB-F (6-10) 4% 5-HHEB-F (6-10) 5% 2-HB-C (8-1) 5% 3-HB-C (8-1) 14%

The following compound (1-2-2) was added to 100% by weight of the composition containing these components in a ratio of 1% by weight.

[Chemical 64]

NI=98.1℃; η=18.8 mPa·s; Δn=0.107; Δε=5.1.

[Use example 2] 3-HH-4 (2-1) 11% 7-HB-1 (2-5) 1% 5-HB-O2 (2-5) 7% 5-HBB(F)B-2 (4-5) 6% 5-HBB(F)B-3 (4-5) 6% 3-HB-CL (5-2) 15% 3-HHB(F,F)-F (6-3) 4% 3-HBB(F,F)-F (6-24) 28% 5-HBB(F,F)-F (6-24) 22%

The following compound (1-2-6) was added to 100 wt % of the composition containing these components at a ratio of 0.5 wt %.

[Chemical 65]

NI=73.1℃; η=19.3 mPa·s; Δn=0.116; Δε=5.7.

[Use example 3] 1V2-HH-1 (2-1) 3% 1V2-HH-3 (2-1) 5% 7-HB(F,F)-F (5-4) 3% 2-HHB( F)-F (6-2) 11% 3-HHB(F)-F (6-2) 11% 5-HHB(F)-F (6-2) 10% 2-HBB-F (6-22 ) 5% 3-HBB-F (6-22) 4% 5-HBB-F (6-22) 3% 2-HBB(F)-F (6-23) 9% 3-HBB(F)-F (6-23) 8% 5-HBB(F)-F (6-23) 15% 3-HBB(F,F)-F (6-24) 4% 5-HBB(F,F)-F ( 6-24) 9%

The following compound (1-3-4) was added to 100% by weight of the composition containing these components in a ratio of 2% by weight.

[Chemical 66]

NI=85.7℃; η=24.4 mPa·s; Δn=0.110; Δε=5.5.

[Use example 4] 2-HH-3 (2-1) 4% 3-HH-4 (2-1) 12% 1O1-HBBH-5 (4-1) 4% 5-HB-CL (5-2 ) 16% 3-HHB-F (6-1) 4% 3-HHB-CL (6-1) 3% 4-HHB-CL (6-1) 4% 3-HHB(F)-F (6- 2) 12% 4-HHB(F)-F (6-2) 9% 5-HHB(F)-F (6-2) 9% 7-HHB(F)-F (6-2) 7% 5 -HBB(F)-F (6-23) 5% 3-HHBB(F,F)-F (7-6) 2% 4-HHBB(F,F)-F (7-6) 3% 5- HHBB(F,F)-F (7-6) 2% 3-HH2BB(F ,F)-F (7-15) 2% 4-HH2BB(F,F)-F (7-15) 2%

The following compound (1-3-21) was added to 100% by weight of the composition containing these components in a ratio of 5% by weight.

[Chemical 67]

NI=113.1℃; η=18.0 mPa·s; Δn=0.090; Δε=3.7.

[Example 5] V-HBB-2 (3-4) 12% 1O1-HBBH-4 (4-1) 5% 1O1-HBBH-5 (4-1) 4% 3-HHB(F,F)- F (6-3) 9% 3-H2HB(F,F)-F (6-15) 9% 4-H2HB(F,F)-F (6-15) 9% 5-H2HB(F,F) -F (6-15) 8% 3-HBB(F,F)-F (6-24) 11% 5-HBB(F,F)-F (6-24) 18% 3-H2BB(F,F )-F (6-27) 9% 5-HHBB(F,F)-F (7-6) 2% 3-HH2BB(F,F)-F (7-15) 2% 5-HHEBB-F ( 7-17) 2%

The following compound (1-3-66) was added to 100 wt % of the composition containing these components at a ratio of 1.5 wt %.

[Chemical 68]

NI=107.4℃; η=31.4 mPa·s; Δn=0.123; Δε=8.0.

[Use example 6] 5-HBBH-3 (4-1) 3% 3-HB(F)BH-3 (4-2) 3% 5-HB-F (5-2) 12% 6-HB-F (5-2) 9% 7-HB-F (5-2) 7% 2-HHB-OCF3 (6-1) 7% 3-HHB-OCF3 (6-1) 9% 4-HHB-OCF3 (6 -1) 7% 5-HHB-OCF3 (6-1) 5% 3-HHB(F,F)-OCF2H (6-3) 6% 3-HHB(F,F)-OCF3 (6-3) 4 % 3-HH2B-OCF3 (6-4) 3% 5-HH2B-OCF3 (6-4) 4% 3-HH2B(F)-F (6-5) 3% 3-HBB(F)-F (6 -23) 9% 5-HBB(F)-F (6-23) 9%

The following compound (1-3-62) was added to 100 wt % of the composition containing these components in a ratio of 2 wt %.

[Chemical 69]

NI=85.8℃; η=15.0 mPa·s; Δn=0.091; Δε=4.5.

[Example 7] 2-HH-5 (2-1) 6% 3-HH-4 (2-1) 5% 5-B(F)BB-2 (3-8) 5% 5-HB-CL (5-2) 11% 3-HHB(F,F)-F (6-3) 8% 3-HHEB(F,F)-F (6-12) 10% 4-HHEB(F,F)- F (6-12) 3% 5-HHEB(F,F)-F (6-12) 4% 3-HBB(F,F)-F (6-24) 20% 5-HBB(F,F) -F (6-24) 15% 2-HBEB(F,F)-F (6-39) 2% 3-HBEB(F,F)-F (6-39) 4% 5-HBEB(F,F )-F (6-39) 2% 3-HHBB(F,F)-F (7-6) 5%

The following compound (1-3-88) was added to 100% by weight of the composition containing these components in a ratio of 0.8% by weight.

[Chemical 70]

NI=75.9℃; η=20.8 mPa·s; Δn=0.107; Δε=7.8.

[Use example 8] V2-HHB-1 (3-1) 7% 3-HB-CL (5-2) 7% 5-HB-CL (5-2) 5% 3-HHB-OCF3 (6-1 ) 5% 5-HHB(F)-F (6-2) 4% V-HHB(F)-F (6-2) 5% 3-H2HB-OCF3 (6-13) 5% 5-H2HB(F ,F)-F (6-15) 4% 5-H4HB-OCF3 (6-19) 15% 5-H4HB(F,F)-F (6-21) 7% 3-H4HB(F,F)- CF3 (6-21) 8% 5-H4HB(F,F)-CF3 (6-21) 10% 2-H2BB(F)-F (6-26) 5% 3-H2BB(F)-F (6 -26) 9% 3-HBEB(F,F)-F (6-39) 4%

The following compound (1-2-2) was added to 100% by weight of the composition containing these components in a ratio of 3% by weight.

[Chemical 71]

NI=72.1℃; η=23.5 mPa·s; Δn=0.099; Δε=7.8.

[Use example 9] 3-HH-4 (2-1) 10% 3-HH-5 (2-1) 5% 3-HB-O2 (2-5) 15% 3-HHB-1 (3-1 ) 10% 3-HHB-O1 (3-1) 6% 5-HB-CL (5-2) 17% 7-HB(F,F)-F (5-4) 4% 2-HHB(F) -F (6-2) 7% 3-HHB(F)-F (6-2) 7% 5-HHB(F)-F (6-2) 6% 3-HHB(F,F)-F ( 6-3) 5% 3-H2HB(F,F)-F (6-15) 4% 4-H2HB(F,F)-F (6-15) 4%

The following compound (1-2-6) was added to 100 wt % of the composition containing these components in a ratio of 4 wt %.

[Chemical 72]

NI=72.2℃; η=13.1 mPa·s; Δn=0.074; Δε=2.6.

[Use example 10] 3-HH-4 (2-1) 10% 3-HH-5 (2-1) 11% 3-HHB-1 (3-1) 12% 5-HB-CL (5-2 ) 3% 7-HB(F)-F (5-3) 7% 2-HHB(F,F)-F (6-3) 5% 3-HHB(F,F)-F (6-3) 6% 3-HHEB-F (6-10) 8% 5-HHEB-F (6-10) 9% 3-HHEB(F,F)-F (6-12) 10% 4-HHEB(F,F )-F (6-12) 4% 3-GHB(F,F)-F (6-109) 4% 4-GHB(F,F)-F (6-109) 5% 5-GHB(F, F)-F (6-109) 6%

The following compound (1-3-4) was added to 100 wt % of the composition containing these components in a ratio of 5 wt %.

[Chemical 73]

NI=87.7℃; η=20.3 mPa·s; Δn=0.070; Δε=5.5.

[Example 11] 3-HH-VFF (2-1) 6% 5-HH-VFF (2-1) 25% 2-BTB-1 (2-10) 10% 3-HHB-1 (3-1 ) 5% VFF-HHB-1 (3-1) 9% VFF2-HHB-1 (3-1) 12% 3-H2BTB-2 (3-17) 5% 3-H2BTB-3 (3-17) 3 % 3-H2BTB-4 (3-17) 3% 3-HB-C (8-1) 17% 1V2-BEB(F,F)-C (8-15) 5%

The following compound (1-3-21) was added to 100% by weight of the composition containing these components at a ratio of 1.5% by weight.

[Chemical 74]

NI=82.0℃; η=10.2 mPa·s; Δn=0.126; Δε=5.8. [Industrial Availability]

The liquid crystal composition containing the compound (1) can be used for display elements such as liquid crystal projectors and liquid crystal televisions.

none

none

Claims (17)

A compound represented by formula (1),

In formula (1), R ¹ is hydrogen or an alkyl group having 1 to 15 carbon atoms, in the alkyl group, at least one -CH ₂ - may be substituted by -O- or -S-, and at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by fluorine or chlorine; ring A ¹ and ring A ^{2 are} independently 1,2-cycloextended propyl group , 1,3-cyclohexylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-cyclohexenyl, 1,4-cyclohexylene 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 or pyridine-2,5-diyl, in these rings, at least one hydrogen can be through fluorine, Chlorine, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons or alkenyloxy having 2 to 9 carbons, among these groups, at least one hydrogen may be substituted Substituted by fluorine or chlorine; a is 0, 1, 2, 3 or 4; Z ¹ is a single bond or an alkylene group having 1 to 6 carbon atoms, in the alkylene group, at least one -CH ₂ - can be - O-, -CO-, -COO-, -OCO- or -OCOO- substituted, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, among these groups, at least one One hydrogen can be substituted by fluorine or chlorine; Sp ¹ , Sp ² , Sp ³ and Sp ^{4 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - can be Substituted by -O-, -CO-, -COO-, -OCO- or -OCOO-, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, among these groups , at least one hydrogen can be substituted by fluorine or chlorine; Sp ⁵ is an alkylene with 2 to 10 carbon atoms, in the alkylene, at least one -CH ₂ - can be substituted by -O-; M ¹ , M ² , M ³ and M ^{4 are} independently hydrogen, fluorine, chlorine, 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 is substituted by fluorine or chlorine; R ² is hydrogen or an alkyl group having 1 carbon carbon number. Alkyl to 5, in which at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by fluorine or chlorine ; X ¹ is -OH, -NH ₂ , -OR ³ , -N(R ³ ) ₂ , -COOH, -SH or -Si(R ³ ) ₃ , -OR ³ , -N(R ³ ) ₂ and - In Si(R ³ ) ₃ , R ³ is hydrogen or an alkyl group having 1 to 10 carbon atoms, in the alkyl group, at least one -CH ₂ - may be substituted by -O-, and at least one -(CH ₂ ) ₂ - Can be substituted by -CH=CH-, in these groups, at least one hydrogen can be substituted by fluorine or chlorine; where a is 1, ring A ¹ is 1,4-cyclohexylene, and ring A ² is 1,4-extended Phenyl, Z ¹ is a single bond , Sp ² , Sp ³ and Sp ⁴ are -CH ₂ -, Sp ⁵ is -(CH ₂ ) ₂ -, R ² is methyl, and when X ¹ is -OH, Sp ¹ is not -CH ₂ -; is 1, Ring A ¹ is 1,4-phenylene, Ring A ² is naphthalene-2,6-diyl, Z ¹ is a single bond, Sp ² , Sp ³ and Sp ⁴ are -CH ₂ -, Sp ⁵ is -(CH ₂ ) ₂ -, R ² is methyl, and when X ¹ is -OH, Sp ¹ is not -CH ₂ -; when a is 3, the four rings are 1,4-extended respectively ^{from the side of R 1} Phenyl, 2-ethyl-1,4-phenylene, 1,4-cyclohexylene and 1,4-cyclohexylene, Z ¹ is a single bond, Sp ² , Sp ³ and Sp ⁴ are -CH ₂ -, Sp ⁵ is -(CH ₂ ) ₂ -, R ² is methyl, and when X ¹ is -OH, Sp ¹ is not -CH ₂ -. The compound described in item 1 of the claimed scope, wherein in formula (1), Z ¹ is a single bond, -(CH ₂ ) ₂ -, -(CH ₂ ) ₄ -, -CH=CH-, -C≡ C -, - COO -, - OCO -, - CF 2 O -, - OCF 2 -, - CH 2 O -, - OCH 2 - or -CF = CF-. The compound according to claim 1 or claim 2, wherein in formula (1), ring A ¹ and ring A ^{2 are} independently 1,4-cyclohexylene, 1,4-cyclohexenylene , 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5 -diyl or pyridine-2,5-diyl, in these rings, at least one hydrogen can be changed through fluorine, chlorine, alkyl with 1 to 10 carbons, alkenyl with 2 to 10 carbons, 1 to 9 carbons alkoxy group or alkenyloxy group having 2 to 9 carbon atoms is substituted, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine. The compound described in item 1 or item 2 of the claimed scope, which is represented by any one of formula (1-1) to formula (1-4),

In formula (1-1) to formula (1-4), R ¹ is an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, or an alkyl group having 2 to 15 carbon atoms. The alkenyloxy group of 14, in these groups, at least one hydrogen can be substituted by fluorine; Ring A ¹ , Ring A ² , Ring A ³ and Ring A ^{4 are} independently 1,4-cyclohexylene, 1,4-cyclohexylene cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl, the In these rings, at least one hydrogen may be substituted by fluorine, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons or alkenyloxy having 2 to 9 carbons, In these groups, at least one hydrogen may be substituted by fluorine; Z ¹ , Z ² and Z ^{3 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-; Sp ¹ , Sp ² , Sp ³ and Sp ^{4 are} independently a single bond or An alkylene group having 1 to 7 carbon atoms, in the alkylene group, at least one -CH ₂ - can be substituted by -O-, -COO- or -OCO-, and at least one -(CH ₂ ) ₂ - can be substituted by - CH=CH-substituted, in these groups, at least one hydrogen can be substituted by fluorine; Sp ⁵ is an alkylene group having 2 to 7 carbon atoms, and in the alkylene group, at least one -CH ₂ - can be replaced by -O- Substituted; M ¹ , M ² , M ³ and M ^{4 are} independently hydrogen, fluorine, alkyl with 1 to 5 carbons or alkyl with 1 to 5 carbons in which at least one hydrogen is substituted with fluorine; R ² is hydrogen or Alkyl having 1 to 5 carbon atoms; X ¹ is -OH, -NH ₂ or -SH; in formula (1-2), ring A ¹ is 1,4-cyclohexylene, and ring A ² is 1,4 -phenylene, Z ¹ is a single bond, Sp ² , Sp ³ and Sp ⁴ are -CH ₂ -, Sp ⁵ is -(CH ₂ ) ₂ -, R ² is methyl, and when X ¹ is -OH, Sp ¹ is not -CH ₂ -; in formula (1-2), ring A ¹ is 1,4-phenylene, ring A ² is naphthalene-2,6-diyl, Z ¹ is a single bond, Sp ² , Sp ³ and Sp ⁴ are -CH ₂ -, Sp ⁵ is -(CH ₂ ) ₂ -, R ² is methyl, and when X ¹ is -OH, Sp ¹ is not -CH ₂ -; formula (1-4 ), in Ring A ¹ is 1,4-phenylene, Ring A ² is 2-ethyl-1,4-phenylene, Ring A ³ and Ring A ⁴ are both 1,4-cyclohexylene, When Z ¹ , Z ² and Z ³ are single bonds, Sp ² , Sp ³ and Sp ⁴ are -CH ₂ -, Sp ⁵ is -(CH ₂ ) ₂ -, R ² is methyl, and X ¹ is -OH, Sp ¹ is not -CH ₂ -. The compound described in item 1 or item 2 of the claimed scope, which is represented by any one of formula (1-5) to formula (1-7),

In formula (1-5) to formula (1-7), R ¹ is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkoxy group having 1 to 9 carbon atoms; ring A ¹ , Ring A ² , Ring A ³ and Ring A ^{4 are} independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrakis Hydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl, in these rings, at least one hydrogen can be through fluorine, alkyl with 1 to 5 carbons, 2 with carbons Alkenyl to 5 or alkoxy of carbon number 1 to 4 is substituted; Z ¹ , Z ² and Z ^{3 are} independently a single bond, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C- , -CH ₂ O- or -OCH ₂ -; Sp ¹ , Sp ² , Sp ³ and Sp ^{4 are} independently a single bond or an alkylene group having 1 to 5 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be substituted by -O-, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH-; R ² is an alkyl group with 1 to 3 carbon atoms; in formula (1-5), in ring A ¹ is 1,4-cyclohexylene, Ring A ² is 1,4-phenylene, Z ¹ is a single bond, Sp ² , Sp ³ and Sp ⁴ are -CH ₂ -, and when R ² is methyl, Sp ¹ is not -CH ₂ -; in formula (1-5), in ring A ¹ is 1,4-phenylene, ring A ² is naphthalene-2,6-diyl, Z ¹ is a single bond, Sp ² , Sp ³ and Sp ⁴ are -CH ₂ -, and when R ² is methyl, Sp ¹ is not -CH ₂ -; in formula (1-7), ring A ¹ is 1,4-phenylene, and the ring A ² is 2-ethyl-1,4-phenylene, both ring A ³ and ring A ⁴ are 1,4-cyclohexylene, Z ¹ , Z ² and Z ³ are single bonds, Sp ² and Sp ³ When Sp ⁴ is -CH ₂ - and R ² is methyl, Sp ¹ is not -CH ₂ -. The compound described in item 1 or item 2 of the claimed scope, which is represented by any one of formula (1-8) to formula (1-16),

In formula (1-8) to formula (1-16), R ¹ is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkoxy group having 1 to 9 carbon atoms; Z ¹ and Z ^{2 is} independently a single bond or -(CH ₂ ) ₂ -; Sp ¹ , Sp ² and Sp ^{3 are} independently a single bond or an alkylene group having 1 to 5 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be substituted by -O-; Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ^{6 are} independently hydrogen, fluorine, alkyl having 1 to 5 carbons, alkenyl having 2 to 5 carbons or an alkoxy group with 1 to 4 carbon atoms; in formula (1-9), when Z ¹ is a single bond, Sp ² and Sp ³ are -CH ₂ -, and Y ¹ and Y ² are hydrogen, Sp ¹ is not -CH ₂ -. The compound described in item 1 or item 2 of the claimed scope, which is represented by any one of formula (1-17) to formula (1-23),

In formula (1-17) to formula (1-23), R ¹ is an alkyl group having 1 to 10 carbon atoms; Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ^{6 are} independently hydrogen, fluorine , methyl or ethyl, Sp ¹ is a single bond or an alkylene group having 1 to 5 carbon atoms, in the alkylene group, at least one -CH ₂ - may be substituted by -O-; in formula (1-18) , when Y ¹ and Y ² are hydrogen, Sp ¹ is not -CH ₂ -. A liquid crystal composition comprising at least one of the compounds described in any one of items 1 to 7 of the scope of the patent application, wherein the ratio of the compound to 100% by weight of the liquid crystal composition is 0.05% by weight more than 10% by weight or less. The liquid crystal composition according to item 8 of the claimed scope, 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 an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in the alkyl and alkenyl groups, at least one -CH _2- may be substituted by -O-, in these groups, at least one hydrogen 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 independently a single _{bond, -COO -, - CH 2 CH} 2 -, - CH = CH- or -C≡C-. The liquid crystal composition according to item 8 or item 9 of the claimed scope, comprising at least one compound selected from the group of compounds represented by formula (5) to formula (7),

In 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, and in the alkyl and alkenyl groups, at least one -CH ₂ - may be through - O-substituted, in these groups, at least one hydrogen can 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, tetrahydropyran-2,5-diyl, 1 ,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or 1,4-phenylene substituted with at least one hydrogen by fluorine; Z ¹⁴ , Z ¹⁵ and Z ^{16 are} independently mono Bond, -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CH=CH-, -C≡C- or -(CH ₂ ) ₄ -; L ¹¹ and L ^{12 are} independently hydrogen or fluorine. The liquid crystal composition according to claim 8 or claim 9, comprising at least one compound selected from the group of compounds 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. Among the alkyl and alkenyl groups, at least one -CH ₂ - may be substituted by -O-, which In these groups, at least one hydrogen can be substituted by fluorine; X ¹² is -C≡N or -C≡CC≡N; Ring D ¹ is 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyridine Pyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or 1,4-phenylene in which at least one hydrogen is substituted with fluorine; Z ¹⁷ is a single bond, -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ - or -C≡C-; L ¹³ and L ^{14 is} independently hydrogen or fluorine; i is 1, 2, 3 or 4. The liquid crystal composition according to claim 8 or claim 9, comprising at least one compound selected from the group consisting of compounds represented by formula (11) to formula (19),

In formulas (11) to (19), R ¹⁵ , R ¹⁶ and R ^{17 are} independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and among the alkyl and alkenyl groups, at least One -CH ₂ - can be substituted by -O-, in these groups, at least one hydrogen can be substituted by fluorine, and R ¹⁷ can also be hydrogen or fluorine; Ring E ¹ , Ring E ² , Ring E ³ and Ring E ⁴ independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, decalin-2,6-di or 1,4-phenylene in which at least one hydrogen is substituted with fluorine; ring E ⁵ and ring E ^{6 are} independently 1,4-cyclohexylene, 1,4-cyclohexenyl, 1,4-cyclohexylene Phenyl, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6-diyl; Z ¹⁸ , Z ¹⁹ , Z ²⁰ and Z ^{21 are} independently a single bond, -COO-, -OCO- , -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ OCH ₂ CH ₂ - or -OCF ₂ CH ₂ CH ₂ -; L ¹⁵ and L ^{16 is} 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. The liquid crystal composition according to claim 8 or claim 9, which contains at least one polymerizable compound represented by formula (20) other than the compound represented by formula (1),

In formula (20), ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxyl Alkyl-2-yl, pyrimidin-2-yl or pyridin-2-yl, in these rings, at least one hydrogen can be replaced by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or at least one hydrogen One hydrogen is substituted by halogen-substituted alkyl group with carbon number from 1 to 12; Ring G is 1,4-cyclohexylene, 1,4-cyclohexenyl, 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, phenanthrene-2,7-diyl, tetrahydropyran-2 ,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in these rings, at least one hydrogen can be passed through halogen , an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group 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 a carbon number The alkylene of 1 to 10, in the alkylene, at least one -CH ₂ - can be substituted by -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ CH ₂ - can be substituted by -O-, -CO-, -COO- or -OCO- -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ )- substituted, 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; Sp ¹¹ , Sp ¹² and Sp ^{13 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, the alkylene group at least one -CH ₂ - may be -O -, - - OCO-, or -OCOO- substituted with at least one -CH ₂ CH ₂ -, - COO may be substituted with -CH = CH- or -C≡C-, In these groups, at least one hydrogen may be substituted with 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 1 or more. The liquid crystal composition according to claim 13, wherein in formula (20), P ¹¹ , P ¹² and P ^{13 are} independently selected from formula (P-1) to formula (P-5) represented by a group in the group of polymerizable groups,

In 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 at least one hydrogen substituted by halogen with a carbon number of 1 to 5 5 alkyl. The liquid crystal composition according to claim 13, wherein the polymerizable compound represented by formula (20) is selected from the group of polymerizable compounds represented by formula (20-1) to formula (20-7) at least one compound of

In formula (20-1) to formula (20-7), L ³¹ , L ³² , L ³³ , L ³⁴ , L ³⁵ , L ³⁶ , L ³⁷ and L ^{38 are} independently hydrogen, fluorine or methyl; Sp ¹¹ , Sp ¹² and Sp ^{13 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be via -O-, -COO-, -OCO- or - OCOO-substituted, at least one -CH ₂ CH ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by fluorine or chlorine; P ¹¹ , P ¹² and P ¹³ is independently a group selected from the group of polymerizable groups represented by formula (P-1) to formula (P-3),

In formula (P-1) to formula (P-3), M ¹¹ , M ¹² and M ^{13 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen substituted by halogen and having a carbon number of 1 to 5 5 alkyl. The liquid crystal composition according to claim 8 or claim 9, comprising a polymerizable compound, a polymerization initiator, and a polymerization inhibitor selected from the group consisting of compounds represented by formula (1) and formula (20) , at least one of the group of optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, pigments, and defoaming agents,

In formula (20), ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxyl Alkyl-2-yl, pyrimidin-2-yl or pyridin-2-yl, in these rings, at least one hydrogen can be replaced by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or at least one hydrogen One hydrogen is substituted by halogen-substituted alkyl group with carbon number from 1 to 12; Ring G is 1,4-cyclohexylene, 1,4-cyclohexenyl, 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, phenanthrene-2,7-diyl, tetrahydropyran-2 ,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in these rings, at least one hydrogen can be passed through halogen , an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group 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 a carbon number The alkylene of 1 to 10, in the alkylene, at least one -CH ₂ - can be substituted by -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ CH ₂ - can be substituted by -O-, -CO-, -COO- or -OCO- -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ )- substituted, 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; Sp ¹¹ , Sp ¹² and Sp ^{13 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, the alkylene group at least one -CH ₂ - may be -O -, - - OCO-, or -OCOO- substituted with at least one -CH ₂ CH ₂ -, - COO may be substituted with -CH = CH- or -C≡C-, In these groups, at least one hydrogen may be substituted with 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 1 or more. A liquid crystal display element comprising a liquid crystal composition selected from the group consisting of the liquid crystal composition described in any one of the 8th to 16th claims in the application scope and the liquid crystal according to any one of the 8th to 16th claims in the application scope At least one of the group consisting of those obtained by polymerizing at least a part of the composition.