TWI823904B - Polymeric polar compounds, liquid crystal compositions and liquid crystal display elements - Google Patents

Abstract

The present invention provides a polar compound with high chemical stability, high ability to align liquid crystal molecules, high solubility in a liquid crystal composition, and a large voltage retention rate of a liquid crystal display element. A compound represented by formula (1). R ¹ is hydrogen or a substituted alkyl group; Ring A ¹ to Ring A ² are optionally substituted cyclohexylene, phenyl, etc.; a is 0 to 4; Z ¹ is a single bond or an optionally substituted cyclohexylene group. Alkyl group; Sp ¹ to Sp ⁴ are single bonds or substituted alkylene groups; M ¹ to M ⁴ are H, F, Cl, or substituted alkyl groups; R ² and R ³ are hydrogen, or may be substituted Substituted alkyl group; R ⁴ is a group selected from the group represented by formula (1-a), formula (1-b), and formula (1-c); Sp ⁵ and Sp ⁶ are single bonds or can be Substituted alkylene group; R ⁵ is hydrogen or a substituted alkyl group; X ¹ is -OH, -NH ₂ , -COOH, -SH, etc.

Description

Polymeric polar compounds, liquid crystal compositions and liquid crystal display elements

The present invention relates to a polymerizable polar compound, a liquid crystal composition and a liquid crystal display element. More specifically, the present invention relates to a compound having two polymerizable groups such as methacryloxy groups and a polymerizable group such as propyloxy groups substituted with a polar group such as -OH group, including the compound and A liquid crystal composition having positive or negative dielectric anisotropy and a liquid crystal display element containing the composition or a partially cured product thereof.

If liquid crystal display elements are classified based on the operating 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 switching (fringe field) switching (FFS), field-induced photo-reactive alignment (FPA) and other modes. In addition, based on the driving method of the component, it can be classified into passive matrix (PM) and active matrix (AM). PM is classified into static type (static), multiplex type (multiplex), etc., and AM is classified into thin film transistor (TFT), metal-insulator-metal (metal insulator metal, MIM), etc. Furthermore, TFTs can be classified into amorphous silicon and polycrystalline silicon. The latter are classified into high-temperature type and low-temperature type according to the manufacturing steps. If classified based on the light source, it can be classified into a reflective type that uses natural light, a transmissive type that uses backlight, and a semi-transmissive type that uses both natural light and backlight.

A liquid crystal composition having a nematic phase has appropriate characteristics. By improving the characteristics of the composition, AM elements with good characteristics can be obtained. The correlation between the characteristics of the composition and the characteristics of the AM element is summarized in Table 1 below.

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

The characteristics of the composition will be further described based on commercially available AM elements. The temperature range of the nematic phase (the temperature range in which the nematic phase occurs) is related to the temperature range in which the component 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 is related to the response time of the element. In order to display dynamic images using components, it is preferable to have a short response time. A response time of less than 1 millisecond is ideal. 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 temperatures.

The optical anisotropy of the composition is related to the contrast of the element. Depending on the mode of the element, it is necessary to have large optical anisotropy or small optical anisotropy, that is, appropriate optical anisotropy. The product (Δn×d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the element is designed to maximize the contrast. The appropriate value of the product depends on the type of operating mode. In TN and other mode components, this value is approximately 0.45 μm. In VA mode devices, the value is in the range of about 0.30 μm to about 0.40 μm, and in IPS mode or FFS mode devices, the value is in the range of about 0.20 μm to about 0.30 μm. In these cases, a composition with large optical anisotropy is preferable for components with a small cell gap. The large dielectric anisotropy of the composition contributes to low threshold voltage, low power consumption and high contrast ratio of the device. Therefore, it is preferable that the positive or negative dielectric anisotropy is large. The high specific resistance of the composition contributes to the high voltage holding rate and high contrast ratio of the device. Therefore, a composition whose specific resistance is large not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase in the initial stage is preferable. Preferably, a composition has a high specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase after long-term use. The stability of the composition against UV rays and heat is related to the life of the component. When the stability is high, the life of the component is long. This characteristic is better for AM elements used in LCD projectors, LCD TVs, etc.

In a polymer sustained alignment (PSA) type liquid crystal display element, a liquid crystal composition containing a polymer is used. First, a composition to which a small amount of polymerizable compound is added is injected into the element. Here, a polymerizable compound having a plurality of polymerizable groups is generally used. Next, while applying a voltage between the substrates sandwiching the element, the composition is irradiated with ultraviolet rays. The polymerizable compound polymerizes to form a polymer network structure in the composition. When this composition is used, the alignment of liquid crystal molecules can be controlled by polymers, so the response time of the device is shortened and image afterimages are improved. This effect of the polymer can be expected for components 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 is 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 has been proposed. First, a composition containing a small amount of a polar compound and a small amount of a polymerizable compound is injected into the element. As the polymerizable compound, a polymerizable compound having a plurality of polymerizable groups is generally used. Here, liquid crystal molecules are aligned by the action of polar compounds. Next, while applying a voltage between the substrates sandwiching the element, the composition is irradiated with ultraviolet rays. Here, the polymerizable compound polymerizes and stabilizes the alignment of the liquid crystal molecules. If this composition is used, polar compounds and polymers can be used to control the alignment of liquid crystal molecules, so the response time of the device is shortened and image afterimages are improved. Furthermore, in a device without an alignment film, the step of forming an alignment film is not required. Since there is no alignment film, the resistance of the element does not decrease due to the interaction between the alignment film and the composition. This effect can be expected from the combination of polar compounds and polymers for devices with modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

Hitherto, in a liquid crystal display element without an alignment film, a polymerizable polar compound has been synthesized as a compound that has both the functions of a polar compound and a polymerizable compound (for example, Patent Document 1, Patent Document 2, and Patent document 3). Patent Document 1 describes a polymerizable compound (S-1) and a polymerizable compound (S-2) having both a methacryloxy group and a -OH-substituted polymerizable group.

[Prior Art Documents] [Patent Documents]

[Patent Document 1] International Publication No. 2017/209161 [Patent Document 2] International Publication No. 2017/047177 [Patent Document 3] International Publication No. 2016/129490

[Problem to be solved by the invention] The first object of the present invention is to provide a compound that satisfies at least one of the following requirements: high chemical stability, high ability to align liquid crystal molecules, high polymerization reactivity by ultraviolet irradiation, and high solubility in a liquid crystal composition, and When used for liquid crystal display elements, the voltage retention rate is high. The second subject is to provide a liquid crystal composition that contains the compound and satisfies the requirements of a high upper limit temperature of the nematic phase, a low lower limit temperature of the nematic phase, low viscosity, appropriate optical anisotropy, and positive or negative dielectric anisotropy. At least one of the characteristics of large anisotropy, large specific resistance, high stability to ultraviolet rays, high stability to heat, and large elastic constant. The third subject is to provide a liquid crystal display element that has the characteristics of a wide usable temperature range, short response time, high transmittance, large voltage holding rate, low threshold voltage, large contrast, long life, and good vertical alignment. of at least one. [Means to solve the problem]

The present invention relates to a compound represented by formula (1), a liquid crystal composition containing the compound, and a liquid crystal display element containing the composition and/or a polymer obtained by polymerizing at least part of the composition.

In formula (1), R ¹ is hydrogen or an alkyl group having 1 to 15 carbon atoms. Among the alkyl groups, 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-, among these groups, at least one hydrogen can be substituted by fluorine or chlorine; Ring A ¹ and Ring A ² are independently 1,2-cyclopropyl , 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-cyclohexenyl, 1,4- Phenylene, naphthalene-2,6-diyl, decalin-2,6-diyl, 1,2,3,4-tetralin-2,6-diyl, tetrahydropyran-2, 5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, at least one hydrogen in these rings can be fluorinated , chlorine, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkoxy group with 1 to 9 carbon atoms, or an alkenyloxy group with 2 to 9 carbon atoms, at least one of these groups Hydrogen may be substituted by fluorine or chlorine; a is 0, 1, 2, 3, or 4; Z ¹ is independently a single bond or an alkylene group with 1 to 10 carbon atoms, in which at least one -CH ₂ - may be substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, Among these groups, at least one hydrogen may 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 - may be substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡ C-substituted, among these groups, at least one hydrogen can be substituted by fluorine or chlorine; M ¹ , M ² , M ³ , M ⁴ , M ⁵ , and M ⁶ are independently hydrogen, fluorine, chlorine, carbon number 1 to 5 alkyl, or an alkyl group with 1 to 5 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; R ² and R ³ are independently hydrogen or an alkyl group with 1 to 10 carbon atoms, and in the alkyl group, at least One -CH ₂ - can be substituted by -O-, 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 ; R ⁴ is a group selected from the group represented by formula (1-a), formula (1-b), and formula (1-c); In formula (1-a), formula (1-b), and formula (1-c), Sp ⁵ and Sp ⁶ 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 substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C ≡C-substituted, in these groups, at least one hydrogen can be substituted by fluorine or chlorine; R ⁵ is hydrogen, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 9 carbon atoms, or an alkyl group with 1 to 9 carbon atoms. alkoxyalkyl; X ¹ is independently -OH, -NH ₂ , -N(R ⁶ ) ₂ , -COOH, -SH, or -Si(R ⁶ ) ₃ ; -N(R ⁶ ) ₂ and -Si(R ⁶ ) ₃ , R ⁶ is hydrogen or an alkyl group with 1 to 10 carbon atoms. Among the alkyl groups, at least one -CH ₂ - may be substituted by -O-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH-, and in these groups, at least one hydrogen may be substituted by fluorine or chlorine. [Effects of the invention]

The first advantage of the present invention is to provide a compound that satisfies at least one of high chemical stability, high polymerization reactivity caused by ultraviolet irradiation, high ability to align liquid crystal molecules, and high solubility in a liquid crystal composition, and When used for liquid crystal display elements, the voltage retention rate is high. The second advantage is to provide a liquid crystal composition that contains the compound and satisfies the requirements of high upper limit temperature of the nematic phase, low lower limit temperature of the nematic phase, low viscosity, appropriate optical anisotropy, and positive or negative dielectric anisotropy. At least one of the characteristics of large anisotropy, large specific resistance, high stability to ultraviolet rays, high stability to heat, and large elastic constant. The third advantage is to provide a liquid crystal display element that has the characteristics of a wide temperature range in which the element can be used, short response time, high transmittance, large voltage holding rate, low threshold voltage, large contrast, long life, and good vertical alignment. of at least one.

The terms used in this manual are as follows. The terms "liquid crystal compound", "liquid crystal composition" and "liquid crystal display element" are sometimes abbreviated to "compound", "composition" and "element" respectively. "Liquid crystal compound" is a compound that has a liquid crystal phase such as a nematic phase or a smectic phase, and that does not have a liquid crystal phase but is used for the purpose of adjusting the physical properties of the composition such as upper limit temperature, lower limit temperature, viscosity, and dielectric anisotropy. The general name of the added compounds. This compound usually has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod-like. A "polymerizable compound" is a compound added for the purpose of producing a polymer in a composition. The liquid crystal compound having an alkenyl group is not a polymerizable compound in its meaning. "Polar compounds" help liquid crystal molecules align through the interaction between polar groups and the surface of the substrate. "Liquid crystal display element" is a general term for liquid crystal display panels, liquid crystal display modules, etc.

Liquid crystal compositions are usually prepared by mixing a plurality of liquid crystal compounds. To this composition, for the purpose of further adjusting physical properties, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, Additives such as pigments and defoaming agents. The proportion (content) of the liquid crystal compound in the liquid crystal composition, even when additives are added, is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition not containing additives. The proportion (added amount) of the additive in the liquid crystal composition is represented by a weight percentage (% by weight) based on the weight of the liquid crystal composition excluding 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 ratio of the polymerization initiator and the polymerization inhibitor in the liquid crystal composition is expressed based on the weight of the polymerizable compound.

The "transparent 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, etc.) 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 a mixture of a liquid crystal compound and a mother liquid crystal or a liquid crystal composition, and may be simply referred to as the "upper limit temperature". The "lower temperature limit of the nematic phase" is sometimes referred to as the "lower limit temperature". The expression "increased dielectric anisotropy" or "large dielectric anisotropy" means that the absolute value of the value is increased or large. "High voltage holding ratio" means that the voltage holding ratio of the element is large not only at room temperature but also at temperatures close to the upper limit temperature in the initial stage. Moreover, after using the element for a long time, the voltage holding ratio is not only at room temperature but also at temperatures close to the upper limit temperature. The voltage retention rate is also large at different temperatures. In some cases, characteristics of a composition or component are studied 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 normal temperature. However, as this composition, it can be used in the following examples. The composition for evaluating solubility was set as the standard.

The compound represented by formula (1) may be simply called "compound (1)". Compound (1) refers to one compound, a mixture of two compounds, or a mixture of three or more compounds represented by formula (1). This rule also applies to at least one compound selected from the group of compounds represented by formula (2), and the like. Symbols such as A ¹ , B ¹ , and C ¹ surrounded by hexagons correspond to rings A ¹ , B ¹ , and C ¹ 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 transversing 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, etc. 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 of a compound, the symbol 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, when R ¹¹ of the compound (2) is an ethyl group, R ¹¹ of the compound (3) may be an ethyl group or other groups such as a propyl group. This rule also applies to other marks. In compound (8), when i is 2, there are two rings D ¹ . In this compound, the two groups represented by the two rings ^D1 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 marks.

The expression "at least one 'A'" means that the number of 'A's is arbitrary. The expression "at least one 'A' can be replaced by 'B'" includes the case of 'A' itself without being replaced by 'B', the case of one 'A' replaced by 'B', the case of two or more 'A' In the case of 'B' substitution, in these cases, the position of 'A' substituted by 'B' is arbitrary. The rule that the substitution position is arbitrary also applies to the expression "at least one 'A' is replaced by 'B'". The expression "at least one A may be substituted by B, C, or D" means that A is not substituted, at least one A is substituted by B, at least one A is substituted by C, and at least one A is substituted by D. Substitution, and substitution of multiple A's with at least two of B, C, and D. For example, alkyl groups in which at least one -CH ₂ - (or -CH ₂ CH ₂ -) can be substituted by -O- (or -CH=CH-) include alkyl, alkenyl, alkoxy, and alkoxy Alkyl, alkoxyalkenyl, alkenyloxyalkyl. Furthermore, it is unfavorable that two consecutive -CH ₂ - are replaced by -O- to become -OO-. In alkyl groups, etc., it is also undesirable that -CH ₂ - of the methyl moiety (-CH ₂ -H) is substituted by -O- to become -OH.

Sometimes "R ¹¹ and R ¹² are independently an alkyl group with 1 to 10 carbon atoms or an alkenyl group with 2 to 10 carbon atoms. In the alkyl group and alkenyl group, 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 according to sentences. In this expression, "these groups" refer to alkyl groups, alkenyl groups, alkoxy groups, alkenyloxy groups, etc. That is, "these groups" means the groups described before the term "these groups". This common sense explanation also applies to other terms.

Halogen refers to 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 include a cyclic alkyl group. Generally speaking, linear alkyl groups are preferred over branched alkyl groups. The same applies to terminal groups such as alkoxy groups and alkenyl groups. Regarding the stereoconfiguration related to 1,4-cyclohexylene group, in order to increase the upper limit temperature of the nematic phase, the trans configuration is preferred over the cis configuration. 2-Fluoro-1,4-phenylene group refers to the following two divalent groups. In the chemical formula, fluorine can move to the left (L) or to the right (R). This rule also applies to tetrahydropyran-2,5-diyl and other left-right asymmetric divalent radicals generated by removing two hydrogens from the ring.

The present invention includes the following items and the like.

Item 1. A compound represented by formula (1). In formula (1), R ¹ is hydrogen or an alkyl group having 1 to 15 carbon atoms. Among the alkyl groups, 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-, among these groups, at least one hydrogen can be substituted by fluorine or chlorine; Ring A ¹ and Ring A ² are independently 1,2-cyclopropyl , 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-cyclohexenyl, 1,4- Phenylene, naphthalene-2,6-diyl, decalin-2,6-diyl, 1,2,3,4-tetralin-2,6-diyl, tetrahydropyran-2, 5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, at least one hydrogen in these rings can be fluorinated , chlorine, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkoxy group with 1 to 9 carbon atoms, or an alkenyloxy group with 2 to 9 carbon atoms, at least one of these groups Hydrogen may be substituted by fluorine or chlorine; a is 0, 1, 2, 3, or 4; Z ¹ is independently a single bond or an alkylene group with 1 to 10 carbon atoms, in which at least one -CH ₂ - may be substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, Among these groups, at least one hydrogen may 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 - may be substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡ C-substituted, among these groups, at least one hydrogen can be substituted by fluorine or chlorine; M ¹ , M ² , M ³ , M ⁴ , M ⁵ , and M ⁶ are independently hydrogen, fluorine, chlorine, carbon number 1 to 5 alkyl, or an alkyl group with 1 to 5 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; R ² and R ³ are independently hydrogen or an alkyl group with 1 to 10 carbon atoms, and in the alkyl group, at least One -CH ₂ - can be substituted by -O-, 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 ; R ⁴ is a group selected from the group represented by formula (1-a), formula (1-b), and formula (1-c); In formula (1-a), formula (1-b), and formula (1-c), Sp ⁵ and Sp ⁶ 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 substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C ≡C-substituted, in these groups, at least one hydrogen can be substituted by fluorine or chlorine; R ⁵ is hydrogen, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 9 carbon atoms, or an alkyl group with 1 to 9 carbon atoms. alkoxyalkyl; X ¹ is independently -OH, -NH ₂ , -N(R ⁶ ) ₂ , -COOH, -SH, or -Si(R ⁶ ) ₃ ; -N(R ⁶ ) ₂ and -Si(R ⁶ ) ₃ , R ⁶ is hydrogen or an alkyl group with 1 to 10 carbon atoms. Among the alkyl groups, at least one -CH ₂ - may be substituted by -O-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH-, and in these groups, at least one hydrogen may be substituted by fluorine or chlorine.

Item 2. The compound according to Item 1, wherein in formula (1), Z ¹ is independently 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 2, wherein in formula (1), ring A ¹ and ring A ² are independently 1,4-cyclohexylene, 1,4-cyclohexenyl, 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 pass through fluorine, chlorine, alkyl group with 1 to 10 carbon atoms, alkenyl group with 2 to 10 carbon atoms, or alkenyl group with 1 to 9 carbon atoms. substituted by an alkoxy group or an alkenoxy group having 2 to 9 carbon atoms. 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). 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 2 carbon atoms. ~14 alkenyloxy groups, 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 -Cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl group, in these rings, at least one hydrogen can pass through fluorine, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkoxy group with 1 to 9 carbon atoms, or an alkenyl group with 2 to 9 carbon atoms. Oxygen substituted, among these groups, at least one hydrogen can be substituted by fluorine; Z ¹ , Z ² , and Z ³ are independently single bonds, -(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 is independently a single bond or an alkylene group with 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-, and in these groups, at least one hydrogen can be substituted by fluorine; M ¹ , M ² , M ³ , M ⁴ , M ⁵ , and M ⁶ 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 by fluorine; R ² and R ³ are independently hydrogen, an alkyl group having 1 to 7 carbon atoms, or an alkyl group having 1 carbon atoms. to 6 alkoxy groups, or alkoxyalkyl groups with 1 to 6 carbon atoms. Among these groups, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, at least One hydrogen may be substituted by fluorine; R ⁴ is a group selected from the group represented by formula (1-a), formula (1-b), and formula (1-c); In formula (1-a), formula (1-b), and formula (1-c), Sp ⁵ and Sp ⁶ 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 substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C ≡C-substituted, in these groups, at least one hydrogen can be substituted by fluorine or chlorine; R ⁵ is hydrogen, an alkyl group with 1 to 7 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, or an alkyl group with 1 to 6 carbon atoms. alkoxyalkyl; X ¹ is independently -OH, -NH ₂ , -COOH, or -SH.

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).

In Formula (1-5) to Formula (1-7), R ¹ is an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, or an alkoxy group with 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-cyclohexenyl, 1,4-phenylene, and naphthalene-2,6-diyl , tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl, in these rings, at least one hydrogen can pass through fluorine, an alkyl group with 1 to 5 carbon atoms, Substituted with an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; Z ¹ , Z ² , and Z ³ are independently single bonds, -(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 the alkylene group is In the group, at least one -CH ₂ - can be substituted by -O-, and at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH-; R ² and R ³ are independently an alkyl group with 1 to 5 carbon atoms. , an alkoxy group with 1 to 4 carbon atoms, or an alkoxyalkyl group with 1 to 4 carbon atoms, in which at least one hydrogen may be substituted by fluorine; R ⁴ is selected from formula (1-a-1) and the radical in the radical represented by formula (1-b-1); In formula (1-a-1) and formula (1-b-1), Sp ⁵ and Sp ⁶ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and among the alkylene groups, at least one - CH ₂ - may be substituted by -O-; R ⁵ is hydrogen or an alkyl group having 1 to 7 carbon atoms.

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 (1-37).

In Formula (1-8) to Formula (1-37), Ring A ¹ , Ring A ² , and Ring A ³ are independently 1,4-cyclohexylene or 1,4-phenylene. Among these rings, , at least one hydrogen may be substituted by fluorine or an alkyl group with 1 to 5 carbon atoms; R ¹ is an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, or an alkoxy group with 1 to 9 carbon atoms; Z ¹ and Z ² are independently a single bond or -(CH ₂ ) 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 the alkylene group has 1 to 5 carbon atoms. In the alkyl group, at least one -CH ₂ - may be substituted by -O-; R ⁵ is hydrogen or an alkyl group having 1 to 5 carbon atoms.

Item 7. The compound according to any one of Items 1 to 6, which is represented by any one of Formula (1-38) to Formula (1-49).

In Formula (1-38) to Formula (1-49), R ¹ is an alkyl group with 1 to 10 carbon atoms; Z ¹ and Z ² are independently a single bond or -(CH ₂ ) ₂ -; Y ¹ , Y ^2. Y ³ , Y ⁴ , Y ⁵ , and Y ⁶ are independently hydrogen, fluorine, methyl, or ethyl; Sp ¹ and Sp ⁴ are independently a single bond or an alkylene group with 1 to 5 carbon atoms, so In the alkylene group, at least one -CH ₂ - may be substituted by -O-; R ⁵ is hydrogen, methyl, or ethyl.

Item 8. The compound according to any one of Items 1 to 6, which is represented by any one of Formula (1-50) to Formula (1-55).

In Formula (1-50) to Formula (1-55), R ¹ is an alkyl group with 1 to 10 carbon atoms; Z ¹ and Z ² are independently a single bond or -(CH ₂ ) ₂ -; Y ¹ , Y ^2. Y ³ , Y ⁴ , Y ⁵ , and Y ⁶ are independently hydrogen, fluorine, methyl, or ethyl; Sp ¹ and Sp ⁴ are independently a single bond or an alkylene group with 1 to 5 carbon atoms, so In the alkylene group, at least one -CH ₂ - may be substituted by -O-.

Item 9. A liquid crystal composition containing at least one of the compounds described in any one of items 1 to 8.

Item 10. The liquid crystal composition according to Item 9, which contains at least one compound selected from the group of compounds represented by Formula (2) to Formula (4).

In formulas (2) to (4), R ¹¹ and R ¹² are independently an alkyl group with 1 to 10 carbon atoms or an alkenyl group with 2 to 10 carbon atoms. Among the alkyl groups and alkenyl groups, at least one -CH ₂ -can be substituted by -O-, and among these groups, at least one hydrogen can be substituted by fluorine; Ring B ¹ , Ring B ² , Ring B ³ , and Ring B ⁴ are independently 1,4-cyclohexyl, 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 is independently a single bond, -COO-, -CH ₂ CH ₂ -, -CH=CH-, or -C≡C-.

Item 11. The liquid crystal composition according to Item 9 or 10, which contains at least one compound selected from the group of compounds represented by Formula (5) to Formula (7).

In Formula (5) to Formula (7), R ¹³ is an alkyl group with 1 to 10 carbon atoms or an alkenyl group with 2 to 10 carbon atoms. Among the alkyl groups and alkenyl groups, at least one -CH ₂ - can be passed through - _O - _{substituted ,} in the above group _{, at} ^least _one hydrogen can be substituted by _fluorine ; , or -OCF ₂ CHFCF ₃ ; Ring C ¹ , Ring C ² , and Ring C ³ are independently 1,4-cyclohexylene, 1,4-phenylene, or tetrahydropyran-2,5-diyl , 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or 1,4-phenylene with at least one hydrogen substituted by fluorine; Z ¹⁴ , Z ¹⁵ , and Z ¹⁶ Independently single 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.

Item 12. The liquid crystal composition according to any one of Items 9 to 11, which contains at least one compound selected from the group of compounds represented by Formula (8).

In formula (8), R ¹⁴ is an alkyl group with 1 to 10 carbon atoms or an alkenyl group with 2 to 10 carbon atoms. Among the alkyl groups and alkenyl groups, at least one -CH ₂ - may be substituted by -O-, and the Among these groups, at ^{least one} hydrogen can be substituted by fluorine; Phenyl-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or 1,4-phenylene group with at least one hydrogen substituted by 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 are independently hydrogen or fluorine; i is 1, 2, 3, or 4.

Item 13. The liquid crystal composition according to any one of Items 9 to 12, which contains at least one compound selected from the group of compounds represented by Formula (11) to Formula (19).

In Formula (11) to Formula (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. Among the alkyl groups and alkenyl groups, At least one -CH ₂ - can be substituted by -O-, in the group, 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 is independently 1,4-cyclohexylene, 1,4-cyclohexenyl, 1,4-phenylene, tetrahydropyran-2,5-diyl, decalin-2,6 -Diyl, or 1,4-phenylene with at least one hydrogen substituted by fluorine; Ring E ⁵ and Ring E ⁶ are independently 1,4-cyclohexylene, 1,4-cyclohexenyl, 1, 4-phenylene, tetrahydropyran-2,5-diyl, or decalin-2,6-diyl; Z ¹⁸ , Z ¹⁹ , Z ²⁰ , and Z ²¹ are independently single bonds, -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 are independently fluorine or chlorine; S ¹¹ is hydrogen or methyl; X is -CHF- or -CF ₂ -; j, k, m, n, p, q, r, and s is 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 14. The liquid crystal composition according to any one of Items 9 to 13, 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, and 1,3-dioxanyl. Alk-2-yl, pyrimidin-2-yl, or pyridin-2-yl, in these rings, at least one hydrogen can be passed through halogen, alkyl group with 1 to 12 carbon atoms, alkoxy group with 1 to 12 carbon atoms, Or at least 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, at least one hydrogen in these rings Can be substituted by halogen, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, or 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 single bond or an alkylene group with 1 to 10 carbon atoms. In the alkylene group, 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 )-, these groups in , 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 extension having 1 to 10 carbon atoms. Alkyl group, in the alkylene group, at least one -CH ₂ - can be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ - can be substituted by -CH=CH - or -C≡C-substituted, in these groups, at least one hydrogen can 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 15. The compound according to Item 14, wherein in formula (20), P ¹¹ , P ¹² , and P ¹³ are independently selected from the group consisting of polymers represented by formula (P-1) to formula (P-5). A base in a group of bases.

In formulas (P-1) to formula (P-5), M ¹¹ , M ¹² , and M ¹³ are independently hydrogen, fluorine, an alkyl group with 1 to 5 carbon atoms, or at least one hydrogen substituted with a halogen. Alkyl groups from 1 to 5.

Item 16. The liquid crystal composition according to Item 14 or 15, 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 in the group.

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 with 1 to 10 carbon atoms. Among the alkylene groups, at least one -CH ₂ - can be passed through -O-, -COO-, -OCO -, or -OCOO-substituted, at least one -CH ₂ CH 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; P ¹¹ , P ¹² , and P ¹³ are independently selected from the group of polymerizable groups represented by formula (P-1) to formula (P-3),

In formulas (P-1) to formula (P-3), M ¹¹ , M ¹² , and M ¹³ are independently hydrogen, fluorine, an alkyl group with 1 to 5 carbon atoms, or at least one hydrogen substituted with a halogen. Alkyl groups from 1 to 5.

Item 17. The liquid crystal composition according to any one of Items 9 to 16, which contains a polymerizable compound selected from the group consisting of a polymerizable compound different from the compound represented by Formula (1) or Formula (20), a polymerization initiator, a polymerization inhibitor, At least one from the group consisting of optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, pigments, and defoaming agents.

Item 18. A liquid crystal display element formed by polymerizing at least a portion selected from the liquid crystal composition described in any one of Items 9 to 17 and the liquid crystal composition described in any one of Items 9 to 17 at least one of the groups formed by them.

The present invention also includes the following items. (a) The liquid crystal composition 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, a defoaming agent, etc. At least two kinds of 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 containing the liquid crystal composite. (f) A polymer-stable alignment type element produced 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 aspects of the compound (1), the synthesis of the compound (1), the liquid crystal composition, and the liquid crystal display element will be described in order below.

1. Appearance of compound (1) The compound (1) of the present invention is characterized by having a mesogen moiety composed of at least one ring, and having a polymerizable group such as two methacryloxy groups connected to the same carbon atom via a spacer group, and- Acryloxy group substituted by polar groups such as OH. Compound (1) is useful because the polar group interacts with the surface of a substrate such as glass (or metal oxide) in a non-covalent bonding manner. One of the uses is an additive for a liquid crystal composition used in a liquid crystal display element. In this use, the compound (1) is added for the purpose of controlling the alignment of liquid crystal molecules. This kind of additive is preferably chemically stable when sealed in a component, has high ability to align liquid crystal molecules, has a high voltage retention rate when used in a liquid crystal display component, and has high solubility in the liquid crystal composition. . Compound (1) has polymerizable groups such as two methacryloxy groups connected to the same carbon atom through a spacer group. Therefore, when polymerized, it can form a high-quality polymer network with high symmetry, so it is used in liquid crystal display elements. The voltage retention rate in the case of the compound is extremely high, and an element with excellent alignment and long-term stability can be easily obtained compared to the case of using a conventional compound.

Preferred examples of compound (1) will be described. Preferred examples of symbols such as R ¹ , A ¹ , and Sp ¹ in compound (1) also apply to the lower formula of compound (1), such as formula (1-1). In compound (1), by appropriately combining the types of these groups, the characteristics can be arbitrarily adjusted. Since there is no large difference in the properties of the compounds, compound (1) may contain isotopes such as ² H (deuterium) and ¹³ C in greater amounts than in natural abundance.

R ¹ is hydrogen or an alkyl group with 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 - may be substituted by -CH= CH- or -C≡C-substituted, at least one hydrogen in these groups may be substituted by fluorine or chlorine.

Preferred 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 alkenyl group having 2 to 14 carbon atoms. Among these groups, At least one hydrogen may be substituted by fluorine. Particularly preferred 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. Particularly preferred R ¹ is an alkyl group having 1 to 10 carbon atoms.

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 has high chemical stability. Compounds 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 alkenyl group having 2 to 14 carbon atoms have high solubility in the liquid crystal composition. A compound in which R ¹ is an alkyl group having 1 to 15 carbon atoms has a high ability to align liquid crystal molecules.

Ring A ¹ and ring A ² are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cyclohexylene, Cycloheptyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, decalin-2,6-diyl, 1,2,3,4- Tetralin-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 pass through fluorine, chlorine, alkyl group with 1 to 10 carbon atoms, alkenyl group with 2 to 10 carbon atoms, alkoxy group with 1 to 9 carbon atoms, or Alkenyloxy groups having 2 to 9 carbon atoms are substituted, 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-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, and tetrahydropyran -2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, at least one hydrogen in these rings Can be substituted by fluorine, chlorine, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkoxy group with 1 to 9 carbon atoms, or an alkenyloxy group with 2 to 9 carbon atoms. Among these groups , at least one hydrogen may be substituted by fluorine or chlorine.

More preferred ring A ¹ and ring A ² are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, and tetrahydropyran -2,5-diyl, or 1,3-dioxane-2,5-diyl. In these rings, at least one hydrogen can be passed through fluorine, an alkyl group with 1 to 10 carbon atoms, or an alkyl group with 2 to 10 carbon atoms. substituted with an alkenyl group, an alkoxy group having 1 to 9 carbon atoms, or an alkenyloxy group having 2 to 9 carbon atoms, 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, and tetrahydropyran -2,5-diyl, or 1,3-dioxane-2,5-diyl. In these rings, at least one hydrogen can pass through fluorine, an alkyl group with 1 to 5 carbon atoms, or an alkyl group with 2 to 5 carbon atoms. substituted by an alkenyl group or an alkoxy group having 1 to 4 carbon atoms.

Particularly preferred ring A ¹ and ring A ² are 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene substituted at the 2-position, 1,4-phenylene substituted at the 3-position, or 1,4-phenylene group is substituted at the 2-position and 3-position, and the substituent is preferably hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyl group having 1 to 4 carbon atoms. alkoxy group, 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, and at least one hydrogen is substituted by fluorine 1,4-phenylene, at least one hydrogen substituted by an alkyl group having 1 to 5 carbon atoms, 1,4-phenylene, decalin-2,6-diyl, or tetrahydropyran-2, 5-diyl compounds have high chemical stability. Ring A ¹ and Ring A ² are independently 1,4-cyclohexylene, 1,4-cyclohexenyl, 1,4-phenylene, and 1,4-phenylene in which at least one hydrogen is substituted by fluorine , a 1,4-phenylene group in which at least one hydrogen is substituted by an alkyl group having 1 to 5 carbon atoms, or a 1,4-phenylene group in which at least one hydrogen is substituted by an alkenyl group having 2 to 5 carbon atoms, composed of a liquid crystal High solubility in substances. A compound in which Ring A ¹ and Ring A ² are independently 1,4-cyclohexylene, 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is substituted by an alkyl group having 1 to 2 carbon atoms is Liquid crystal molecules have high alignment ability. Ring A ¹ and Ring A ² are independently 1,4-phenylene, 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. Polymerization of alkoxy-substituted 1,4-phenylene, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl compounds caused by ultraviolet irradiation High reactivity.

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

Z ¹ is independently a single bond or an alkylene group with 1 to 10 carbon atoms. In the alkylene group, at least one -CH ₂ - can be passed through -O-, -CO-, -COO-, -OCO-, or -OCOO- is substituted, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, and among these groups, at least one hydrogen can be substituted by fluorine or chlorine.

Preferable 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 preferred 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-. Particularly preferred Z ¹ is a single bond, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C-, -CH ₂ O-, or -OCH ₂ -, and more preferably Z ¹ is a single bond or -(CH ₂ ) ₂ -, especially Z ¹ is a single bond.

Compounds in which Z ¹ is a single bond have high chemical stability. Compounds in which Z ¹ is a single bond, -(CH ₂ ) ₂ -, -CF ₂ O-, or -OCF ₂ - have high solubility in the liquid crystal composition. Compounds in which Z ¹ is a single bond or -(CH ₂ ) ₂ - have 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-, -OCH ₂ - have high polymerization reactivity by ultraviolet irradiation.

Sp ¹ , Sp ² , Sp ³ , and Sp ⁴ are independently a single bond or an alkylene group with 1 to 10 carbon atoms. In the alkylene group, at least one -CH ₂ - can be passed through -O-, -CO-, -COO-, -OCO-, or -OCOO- is substituted, 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 substitution.

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. In the alkylene group, at least one -CH ₂ - can pass through -O-, - COO- or -OCO- is substituted, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH-, and among these groups, at least one hydrogen can be substituted by 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 have high chemical stability. Sp ¹ , Sp ² , Sp ³ , and Sp ⁴ are independently an alkylene group having 1 to 7 carbon atoms, or at least one -CH ₂ -substituted -O- group of an alkylene group having 1 to 7 carbon atoms. The compound has high solubility in the liquid crystal composition.

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 one -(CH ₂ ) ₂ - may be substituted with -CH=CH-.

In terms of becoming a compound with more excellent solubility in a liquid crystal composition, it is particularly preferred that Sp ¹ and Sp ⁴ independently be 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-; Sp ² and Sp ³ are a single bond or an alkylene group with 1 to 5 carbon atoms. In the alkylene group, at least one -CH ₂ - may be substituted by -O- Replacement, preferably -CH ₂ -.

M ¹ , M ² , M ³ , M ⁴ , M ⁵ , and M ⁶ are independently hydrogen, fluorine, chlorine, an alkyl group with 1 to 5 carbon atoms, or at least one hydrogen with 1 to 1 carbon atoms substituted by fluorine or chlorine. 5 alkyl group, preferably 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, becomes a special polymerization reactivity caused by ultraviolet irradiation. In terms of high-density compounds, hydrogen is more preferred.

R ² and R ³ are independently 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- or -C≡C-substituted, at least one hydrogen in these groups may be substituted by fluorine or chlorine.

Preferred R ² and R ³ are independently hydrogen, an alkyl group with 1 to 7 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, or an alkoxyalkyl group with 1 to 6 carbon atoms. Among these groups, At least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, and at least one hydrogen may be substituted by fluorine. It is particularly preferred that R ² and R ³ independently be an alkane having 1 to 5 carbon atoms, in terms of a compound having better solubility in a liquid crystal composition, high chemical stability, and high ability to align liquid crystal molecules. group, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 1 to 4 carbon atoms. In these groups, at least one hydrogen may be substituted by fluorine. Particularly preferred R ² and R ³ are methyl.

R ⁴ is a group selected from the group represented by formula (1-a), formula (1-b), and formula (1-c). Preferable R ⁴ is a group represented by formula (1-a) or formula (1-b).

When R ⁴ is a group represented by formula (1-a), the solubility in the liquid crystal composition is high, and the voltage retention rate when used in a liquid crystal display element is high. When R ⁴ is a group represented by formula (1-b) or formula (1-c), the ability to align liquid crystal molecules is high. When R ⁴ is a group represented by formula (1-b), the solubility in the liquid crystal composition is high, and the ability to align liquid crystal molecules is high.

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

Preferred Sp ⁵ and Sp ⁶ are independently a single bond or an alkylene group with 1 to 10 carbon atoms. In the alkylene group, at least one -CH ₂ - can be substituted by -O-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH-, and in these groups, at least one hydrogen may be substituted by fluorine. More preferably, Sp ⁵ and Sp ⁶ are alkylene groups having 1 to 10 carbon atoms, and in the alkylene groups, at least one -CH ₂ - may be substituted by -O-.

A compound in which Sp ⁵ and Sp ⁶ are independently a single bond or an alkylene group having 1 to 10 carbon atoms has high chemical stability. A compound in a liquid crystal composition in which Sp ⁵ and Sp ⁶ are independently an alkylene group having 1 to 10 carbon atoms, or at least one -CH ₂ -substituted -O- group of an alkylene group having 1 to 10 carbon atoms. High solubility, high ability to align liquid crystal molecules.

In formula (1-b), R ⁵ is hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or an alkoxyalkyl group having 1 to 9 carbon atoms. Preferred R ⁵ is hydrogen, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 1 to 6 carbon atoms. Particularly preferred R ⁵ is hydrogen or an alkyl group having 1 to 7 carbon atoms. Particularly preferred R ⁵ is hydrogen or an alkyl group having 1 to 5 carbon atoms.

In formula (1-a), formula (1-b), and formula (1-c), X ¹ is independently -OH, -NH ₂ , -N(R ⁶ ) ₂ , -COOH, -SH, or In -Si(R ⁶ ) ₃ , -N(R ⁶ ) ₂ , and -Si(R ⁶ ) ₃ , R ⁶ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and in the alkyl group, at least one -CH ₂ - may be substituted by -O-, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH-, and in these groups, at least one hydrogen may be substituted by fluorine or chlorine.

Preferred X ¹ is independently -OH, -NH ₂ , -COOH, or -SH. A particularly preferred X ¹ is -OH. When X ¹ is independently -OH, -NH ₂ , -COOH, or -SH, the ability to align liquid crystal molecules is high. When X ¹ is -OH, the solubility in the liquid crystal composition is high, the ability to align liquid crystal molecules is high, and the voltage retention rate when used in a liquid crystal display element is high.

Preferred examples of the compound (1) are the compounds (1-1) to (1-4) described in item 4. More preferred examples of the compound (1) are the compounds (1-5) to (1-7) described in Item 5. Particularly preferred examples of the compound (1) are the compounds (1-8) to (1-37) described in Item 6. The best examples of the compound (1) are the compounds (1-38) to (1-49) 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 methods are not documented can be synthesized by "Organic Syntheses" (John Wiley & Sons, Inc), "Organic Reactions" (John Wiley & Sons, Inc) Methods described in books such as John Wiley & Sons, Inc), "Comprehensive Organic Synthesis" (Pergamon Press), "New Experimental Chemistry Lectures" (Maruzen), etc. synthesis.

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

(I) Generation of single bonds Compound (1A) is synthesized by reacting boric acid compound (21) and compound (22) in the presence of carbonate and tetrakis(triphenylphosphine)palladium catalyst. The compound (1A) can also be synthesized in the following manner: compound (23) is reacted with n-butyllithium, and then reacted with zinc chloride in the presence of dichlorobis(triphenylphosphine) palladium catalyst. Compound (22) is reacted.

(II) Generation of -COO- and -OCO- Compound (23) is reacted with n-butyllithium and then reacted with carbon dioxide to obtain carboxylic acid (24). The carboxylic acid (24) and the alcohol (25) derived from the compound (21) are mixed with 1,3-dicyclohexyl carbodiimide (DCC) and 4-dimethylamine Compound (1B) having -COO- was synthesized by dehydration in the presence of 4-dimethylaminopyridine (DMAP). Compounds with -OCO- are also synthesized by this method.

(III) Generation of -CF ₂ O- and -OCF ₂ - Compound (1B) is sulfurized using Lawesson's reagent to obtain compound (26). Compound (26) was fluorinated using a hydrogen fluoride pyridine complex and N-bromosuccinimide (NBS) to synthesize compound (1C) having -CF ₂ O-. Refer to "Chem. Lett." 1992 Issue 827 by M. Kuroboshi et al. Compound (1C) can also be synthesized by fluorinating compound (26) using (diethylamino)sulfur trifluoride (DAST). Refer to "Journal of Organic Chemistry (J.Org.Chem.)" by WH Bunnelle et al., Issue 55, 1990, page 768. Compounds having -OCF ₂ - can also be synthesized by this method.

(IV) Generation of -CH=CH- Compound (22) is reacted with n-butyllithium, and then reacted with N,N-dimethyl formamide (DMF) to obtain aldehyde (27). The phosphonium salt (28) is reacted with potassium tert-butoxide to generate a phosphorus ylide, and the phosphorus dipole is reacted with the aldehyde (27) to synthesize the compound (1D). Since the cis isomer is generated depending on the reaction conditions, the cis isomer is isomerized into the trans isomer by a known method if necessary.

(V) -CH ₂ CH ₂ - is generated by hydrogenating compound (1D) in the presence of a palladium-carbon catalyst to synthesize compound (1E).

(VI) Generation of -C≡C- Compound (23) is reacted with 2-methyl-3-butyn-2-ol in the presence of a catalyst of palladium dichloride and copper iodide, and then deprotected under alkaline conditions to obtain compound (29) ). Compound (29) and compound (22) are reacted in the presence of a catalyst of dichlorobis(triphenylphosphine)palladium and copper halide to synthesize compound (1F).

(VII) Generation of -CH ₂ O- and -OCH ₂ - Compound (27) is reduced with sodium borohydride to obtain compound (30). It is brominated with hydrobromic acid to obtain compound (31). Compound (25) and compound (31) are reacted in the presence of potassium carbonate to synthesize compound (1G). Compounds with -OCH ₂ - can also be synthesized by this method.

(VIII) Generation of -CF=CF- Compound (23) is treated with n-butyllithium, and then tetrafluoroethylene is reacted to obtain compound (32). Compound (22) is treated with n-butyllithium and then reacted with compound (32) to synthesize compound (1H).

2-2. Generation of Ring A ¹ and Ring A ² Regarding 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1 ,4-cycloheptyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, decalin-2,6-diyl, 1,2, 3,4-tetralin-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl , pyridine-2,5-diyl and other rings, the starting materials are commercially available, or the synthesis method is well known.

2-3. Synthesis Examples Examples of methods for synthesizing compound (1) are as follows. In these compounds, the definitions of R ¹ , A ¹ , A ² , Z ¹ , Sp ¹ , Sp ⁴ and a are the same as those described in Item 1.

In formula (1), Sp ² and Sp ³ are -CH ₂ -, M ¹ , M ² , M ³ and M ⁴ are hydrogen, R ⁴ is a group represented by formula (1-a), and Sp ⁵ is - The compound (1-51) in which CH ₂ - and X ¹ is -OH can be synthesized by the following method. Compound (53) is obtained by reacting sodium hydride and compound (52) on compound (51). Compound (54) is obtained by reacting palladium hydroxide on compound (53) in a hydrogen environment. Compound (54) is obtained by reacting 3,4-dihydro-2H-pyran and pyridinium p-Toluenesulfonate (PPTS) on compound (54). Compound (55) is reduced using lithium aluminum hydride to obtain compound (56). Methacrylic acid chloride and triethylamine act on compound (56) to obtain compound (57), and then deprotection is performed using PPTS to obtain compound (58). Compound (58) and compound (59) are reacted in the presence of DCC and DMAP to obtain compound (60), and then PPTS is used for deprotection, whereby compound (1-51) can be derived.

In formula (1), Sp ² and Sp ³ are -CH ₂ -, M ¹ , M ² , M ³ and M ⁴ are hydrogen, R ⁴ is a group represented by formula (1-a), and Sp ⁵ is - (CH ₂ ) ₂ -, the compound (1-52) in which X ¹ is -OH can be synthesized by the following method. Compound (1-52) can be derived by causing phosphorus tribromide to act on compound (1-51) to perform bromination, and then allowing formaldehyde to act in the presence of an indium catalyst.

In formula (1), Sp ² and Sp ³ are -CH ₂ -, M ¹ , M ² , M ³ and M ⁴ are hydrogen, R ⁴ is a group represented by formula (1-a), and Sp ⁵ is - CH ₂ O(CH ₂ ) _a -, the compound (1-53) in which X ¹ is -OH can be synthesized by the following method. By allowing trifluoromethanesulfonic anhydride (Tf ₂ O) and triethylamine to act on compound (1-51), it reacts with a diol corresponding to carbon number a (HO-(CH ₂ ) _a -OH) And the compound (1-53) can be derived.

In formula (1), Sp ² and Sp ³ are -CH ₂ -, M ¹ , M ² , M ³ and M ⁴ are hydrogen, R ⁴ is a group represented by formula (1-b), Sp ⁵ and Sp The compound (1-54) in which ⁶ is -CH ₂ -, R ⁵ is hydrogen, and X ¹ is -OH can be synthesized by the following method. Compound (61) is iodized with iodine, triphenylphosphine, and imidazole to obtain compound (62), and then reacted with compound (63), sodium hydride, formaldehyde, and potassium carbonate in sequence to obtain compound (64). Compound (64) is hydrolyzed using lithium hydroxide to obtain compound (65). Compound (58) and compound (65) are reacted in the presence of DCC and DMAP to obtain compound (66), and then PPTS is used for deprotection, whereby compound (1-54) can be derived.

3. Liquid crystal composition 3-1. Component compounds The liquid crystal composition of the present invention contains compound (1) as component A. Compound (1) can control the alignment of liquid crystal molecules by interacting with the substrate of the device in a non-covalent bonding manner. This composition preferably contains compound (1) as component A, and further contains at least one liquid crystal compound selected from the following component B, component C, component D, and component E. Component B is compound (2) to compound (4). Component C is compound (5) to compound (7). Component D is compound (8). Component E is compound (11) to compound (19). The composition may also contain other liquid crystal compounds different from the compounds (2) to (8) and the compounds (11) to (19). When preparing this 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, etc. A composition with appropriately selected ingredients has a high upper limit temperature, a low lower limit temperature, low viscosity, appropriate optical anisotropy (i.e., large optical anisotropy or small optical anisotropy), large positive or negative dielectric anisotropy, and It has a large specific resistance, is stable to heat or ultraviolet rays, and has an appropriate elastic constant (i.e., a large elastic constant or a small elastic constant).

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

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

Component B has a small absolute value of dielectric anisotropy, so it is a nearly neutral compound. 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 raising the upper limit temperature, or are effective in adjusting optical anisotropy.

As the content of component B increases, the dielectric anisotropy of the composition becomes smaller, but the viscosity becomes smaller. Therefore, as long as the required threshold voltage of the component is met, the content of component B should be as high as possible. The content of component B is preferably 30 wt% or more, particularly 40 wt% or more, based on 100 wt% of the liquid crystal composition. 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. Component C has large positive dielectric anisotropy. Preferable examples of component C include compounds (5-1) to compounds (5-16), compounds (6-1) to compounds (6-116), and compounds (7-1) to compounds (7-59). In the compound of component C, R ¹³ is an alkyl group with 1 to 10 carbon atoms or an alkenyl group with 2 to 10 carbon atoms. In the alkyl group and the alkenyl group, at least one -CH ₂ - may be substituted by -O-, and at least one ^Hydrogen _{may be substituted with fluorine ; _ _ _}

Component C has positive dielectric anisotropy and very good stability against heat, light, etc., so it can be preferably used to prepare compositions for patterns such as IPS, FFS, and OCB. The content of component C relative to 100% by weight of the liquid crystal composition is suitably in the range of 1 to 99% by weight, preferably in the range of 10 to 97% by weight, and particularly preferably in the range of 40 to 95% by weight. . When component C is added to a composition with negative dielectric anisotropy, the content of component C is preferably 30% by weight or less based on 100% by weight of the liquid crystal composition. By adding component C, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the device can be adjusted.

Component D is a compound (8) whose single terminal group is -C≡N or -C≡CC≡N. Since component D has a cyano group, it has greater positive dielectric anisotropy. Preferable examples of component D include compounds (8-1) to compounds (8-64). In the compound of component D, R ¹⁴ is an alkyl group with 1 to 10 carbon atoms or an alkenyl group with 2 to 10 carbon atoms. In the alkyl group and the alkenyl group, at least one -CH ₂ - may be substituted by -O-, and at least one Hydrogen may be substituted by fluorine; -X ¹² is -C≡N or -C≡CC≡N.

The dielectric anisotropy of component D is positive and has a large value, so it is mainly used when preparing compositions 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 component.

The content of component D relative to 100% by weight of the liquid crystal composition is suitably in the range of 1 to 99% by weight, preferably in the range of 10 to 97% by weight, and particularly preferably in the range of 40 to 95% by weight. . When component D is added to a composition with negative dielectric anisotropy, the content of component D is preferably 30% by weight or less based on 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 element can be adjusted.

Component E is compound (11) to compound (19). Component E has large negative dielectric anisotropy. These compounds have a phenylene group substituted with two halogens (fluorine or chlorine) at the side positions like 2,3-difluoro-1,4-phenylene. Preferred examples of component E include compounds (11-1) to compounds (11-9), compounds (12-1) to compounds (12-19), compounds (13-1) and compounds (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. Among the alkyl groups and alkenyl groups, at least one -CH ₂ - can be By -O- substitution, at least one hydrogen in these groups may be substituted by fluorine, and R ¹⁷ may also be hydrogen or fluorine.

The dielectric anisotropy of component E is negative and large. Component E can be preferably used when preparing compositions for models such as IPS, VA, and PSA. As the content of component E increases, the dielectric anisotropy of the composition becomes negative and becomes larger, but the viscosity becomes larger. Therefore, as long as the required threshold voltage of the component is met, the content should be as low as possible. Considering that the dielectric anisotropy is about -5, in order to perform sufficient voltage driving, the content of component E is preferably 40% by weight or more based on 100% by weight of the liquid crystal composition.

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

The content of component E is preferably 40% by weight or more based on 100% by weight of the liquid crystal composition, particularly preferably in the range of 50% by weight to 95% by weight. When component E is added to a composition with positive dielectric anisotropy, the content of component E is preferably 30% by weight or less based on 100% by weight of the liquid crystal composition. By adding component E, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the element can be adjusted.

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

3-2. Additives The liquid crystal composition is prepared by a known method. For example, the above-mentioned components are mixed and then heated to dissolve each other. Additives may also be added to the composition according to the intended use. Examples of additives include polymerizable compounds other than compound (1), polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, pigments, defoaming 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 generating a polymer in the liquid crystal composition. A polymer can be produced by irradiating ultraviolet rays with voltage applied between the electrodes to polymerize the compound (1). At this time, the compound (1) is immobilized in a state where its polar group interacts with the surface of the glass (or metal oxide) substrate in a non-covalent bonding manner. Thereby, the ability to control the alignment of liquid crystal molecules is further improved, and an appropriate pretilt angle can be obtained, thereby shortening the response time.

Preferable examples of the polymerizable compound are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, allyl ethers, epoxy compounds (oxirane, oxetane), and vinyl ketones. Particularly preferred examples are compounds having at least one acryloxy group and compounds having at least one methacryloxy group. Particularly preferred examples include compounds having both an acryloxy group and a methacryloyloxy group. A particularly preferred example of the polymerizable compound is compound (20). Compound (20) is a compound different from compound (1). Compound (1) has a polar group. On the other hand, compound (20) preferably does not have a polar group.

In formula (20), ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, and 1,3-dioxanyl. Alk-2-yl, pyrimidin-2-yl, or pyridin-2-yl, in these rings, at least one hydrogen can be passed through halogen, alkyl group with 1 to 12 carbon atoms, alkoxy group with 1 to 12 carbon atoms, Or at least one hydrogen is substituted by a halogen-substituted alkyl group having 1 to 12 carbon atoms.

Preferred ring F or ring I are cyclohexyl, cyclohexenyl, phenyl, fluorophenyl, difluorophenyl, 1-naphthyl, or 2-naphthyl. Particularly preferred ring F or ring I is cyclohexyl, cyclohexenyl or phenyl. A particularly preferred ring F or ring I is 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 passed through halogen or alkyl group with 1 to 12 carbon atoms. , an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms substituted with at least one hydrogen 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. In the alkylene group, at least one -CH ₂ - can be passed through -O-, -CO-, - COO-, or -OCO- is substituted, and at least one -CH ₂ CH ₂ - can be replaced by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )-, or -C(CH ₃ )=C(CH ₃ )-substituted, at least one hydrogen in these groups may be substituted by fluorine or chlorine. Preferred Z ²² or Z ²³ is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, or -OCO-. Preferably Z ²² or Z ²³ are single keys.

In compound (20), P ¹¹ , P ¹² , and P ¹³ are independently polymerizable groups. Preferred 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 formula (P-1). A preferred group represented by the formula (P-1) is an acryloxy group (-OCO-CH=CH ₂ ) or a methacryloxy group (-OCO-C(CH ₃ )=CH ₂ ). The wavy lines in Formula (P-1) to Formula (P-5) represent the bonding sites.

In formulas (P-1) to formula (P-5), M ¹¹ , M ¹² , and M ¹³ are independently hydrogen, fluorine, an alkyl group with 1 to 5 carbon atoms, or at least one hydrogen substituted with a halogen. Alkyl groups from 1 to 5. In order to improve the reactivity, preferably M ¹¹ , M ¹² or M ¹³ is hydrogen or methyl. Particularly preferred M ¹¹ is hydrogen or methyl, and particularly preferred M ¹² or M ¹³ is 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. In the alkylene group, at least one -CH ₂ - can be passed through -O-, - COO-, -OCO-, or -OCOO- substituted, at least one -CH ₂ CH 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 . Preferably, Sp ¹¹ , Sp ¹² or Sp ¹³ is a single bond.

In formula (20), u is 0, 1, or 2. Preferably 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. Preferable f, g, or h are 1 or 2. The preferred sum is 2, 3 or 4. A particularly preferred sum is 2 or 3.

Preferable examples of compound (20) are compounds (20-1) to compounds (20-7) and compounds (20-8) to compounds (20-11) described in item 15. 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 At least one of ³⁴ is an alkyl group with 1 to 5 carbon atoms; v, and x are independently 0 or 1; t and u are independently integers from 1 to 10; t+v and x+u are each up to 10; L ³¹ to L ³⁶ are independently hydrogen or fluorine, and L ³⁷ and L ³⁸ are independently hydrogen, fluorine, or methyl.

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 during polymerization, the amount of remaining polymerizable compounds can be reduced. Examples of photoradical polymerization initiators include TPO, 1173, and 4265 in BASF's Darocure series, and 184, 369, and 500 in the Irgacure series. , 651, 784, 819, 907, 1300, 1700, 1800, 1850, and 2959.

Additional examples of photoradical polymerization initiators include 4-methoxyphenyl-2,4-bis(trichloromethyl)triazine and 2-(4-butoxystyryl)-5-trichloro Methyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzophenidazine, benzophenone/Michelone mixture, hexaarylbimidazole/mercaptobenzimidazole Mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, benzyldimethyl ketal, 2-methyl-1-[4-(methylthio) )Phenyl]-2-morpholinylpropan-1-one, 2,4-diethylxanthone/methyl p-dimethylaminobenzoate mixture, benzophenone/methyltriethanolamine mixture .

After adding a photoradical polymerization initiator to the liquid crystal composition, polymerization can be performed by irradiating ultraviolet rays while applying an electric field. However, unreacted polymerization initiator or decomposition products of the polymerization initiator may cause display defects such as image afterimage to the device. 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. Particularly preferred wavelengths are in the range of 250 nm to 450 nm, and optimal wavelengths are in the range of 300 nm to 400 nm.

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

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

Antioxidants are effective in maintaining a large voltage holding ratio. Preferable examples of antioxidants include: the following compounds (AO-1) and compounds (AO-2); Irganox 415, Irganox 565, Irganox 1010, Irganox Irganox 1035, Irganox 3114, and Irganox 1098 (trade names; BASF). Ultraviolet absorbers are effective in preventing the upper limit temperature from lowering. Preferred examples of ultraviolet absorbers 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, Tinubin (Tinuvin) 328, and Tinuvin 99-2 (trade name; BASF); and 1,4-diazabicyclo[2.2.2]octane (DABCO).

Light stabilizers such as amines with steric hindrance are preferred because they maintain a large voltage retention rate. Preferable examples of light stabilizers include the following compounds (AO-5), compounds (AO-6), and compounds (AO-7); Tinuvin 144, Tinuvin 765, and Tinuvin 770DF (trade name; BASF Company); LA-77Y and LA-77G (trade name; ADEKA Company). Thermal stabilizers are also effective in maintaining a large voltage retention rate, and a preferred example is Irgafos 168 (trade name; BASF Corporation). In order to be suitable for a guest host (GH) mode device, dichroic dyes (dichroic dyes) such as azo dyes and anthraquinone dyes are added to the composition if necessary. To prevent foaming, defoamers are effective. Preferred examples of defoaming agents are dimethyl silicone oil, methylphenyl silicone oil, etc.

In compound (AO-1), R ⁴⁰ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, -COOR ⁴¹ , or -CH ₂ CH ₂ COOR ⁴¹ , where R ⁴¹ is carbon Alkyl group with number 1 to 20. 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) Among them, ring G ² is a 1,4-cyclohexylene group, a 1,4-phenylene group, or a group in which at least one hydrogen of the 1,4-phenylene group is substituted by fluorine; compound (AO-5) and compound (AO -7), z is 1, 2, or 3.

4. Liquid crystal display components The liquid crystal composition can be preferably used in liquid crystal display elements that have PC, TN, STN, OCB, PSA and other operating modes and are driven in an active matrix manner. The composition can also be preferably used in liquid crystal display elements that have PC, TN, STN, OCB, VA, IPS and other operating modes and are driven in a passive matrix manner. These elements can also be applied to any type of reflective type, transmissive type, or semi-transmissive type.

The composition is also suitable for nematic curvilinear aligned phase (NCAP) devices, where the composition is microencapsulated. The composition can also be used in polymer dispersed liquid crystal display elements (polymer dispersed liquid crystal display, PLCD) or polymer network liquid crystal display elements (polymer network liquid crystal display, PNLCD). To these compositions, a polymerizable compound is added in large amounts. On the other hand, regarding the composition used for a liquid crystal display element in the PSA mode, the proportion of the polymerizable compound is preferably 10% by weight or less, and a more preferable proportion is 0.1% by weight to 2% by weight relative to 100% by weight of the liquid crystal composition. % range, and a particularly preferable ratio is in the range of 0.2% by weight to 1.0% by weight. Components in PSA mode can be driven in active matrix mode, passive matrix mode and other driving modes. This type of element can also be applied to any type of reflective, transmissive, or semi-transmissive type.

In a polymer-stabilized alignment type device, the polymer contained in the composition aligns the liquid crystal molecules. Polar compounds help liquid crystal molecules align. That is, a polar compound can be used instead of the alignment film. An example of a method of manufacturing such a component is described below. An element having two substrates called an array substrate and a color filter substrate is prepared. This substrate does not have an alignment film. At least one piece of the substrate has an electrode layer. Liquid crystal compounds are mixed to prepare a liquid crystal composition. To this composition, compound (1) and other polymerizable compounds and polar compounds are added as necessary. Further additives can be added as needed. The composition is injected into the component. Light irradiation was performed with voltage applied to the element. Ultraviolet rays are preferred. The polymerizable compound is polymerized by light irradiation. By this polymerization, a composition containing a polymer is produced, thereby producing a device having a PSA pattern.

In this procedure, polar compounds are arranged on the substrate due to the interaction of polar groups with the surface of the substrate. This polar compound aligns the liquid crystal molecules. In the presence of multiple polar groups, 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. Based on this alignment, the polymerizable compound is also aligned. In this state, the polymerizable compound is polymerized by ultraviolet rays, thereby producing a polymer that maintains the alignment. Due to the effect of this polymer, the alignment of liquid crystal molecules is additionally stabilized, so the response time of the element is shortened. Since the residual image of the image is due to the poor operation of the liquid crystal molecules, the effect of the polymer also improves the residual image at the same time. Compound (1) is polymerizable and is consumed by polymerization. Compound (1) is also consumed by copolymerization with other polymerizable compounds. Therefore, although the compound (1) has a polar group, it is consumed, so that a liquid crystal display element with a large voltage holding ratio can be obtained. Furthermore, when a polymerizable polar compound is used, the effects of both the polar compound and the polymerizable compound can be achieved with one compound. Therefore, a polymerizable compound that does not have a polar group may not be necessary. [Example]

The present invention will be further described in detail through examples (including synthesis examples and usage examples). The present invention is not limited by these examples. The present invention also includes a mixture prepared by mixing at least two of the compositions of the usage examples.

1. Examples of compound (1) Unless otherwise stated, the reaction is carried out under a nitrogen atmosphere. Compound (1) was synthesized by the procedure shown in Example 1 and so on. The synthesized compounds are identified by methods such as Nuclear Magnetic Resonance (NMR) analysis. The properties of compound (1), liquid crystal compounds, compositions, and devices are measured by the following methods.

NMR analysis: For 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 measured 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 performed with a cumulative count of 24 times. In the description of nuclear magnetic resonance spectrum, s refers to singlet, d refers to doublet, t refers to triplet, q refers to quartet, and quin refers to quintet. (quintet), sext refers to sextet, m refers to multiplet (multiplet), and br refers to broad peak (broad).

Gas chromatography analysis: During measurement, a GC-2010 gas chromatograph manufactured by Shimadzu Corporation was used. The column was a capillary column DB-1 manufactured by Agilent Technologies Inc. (length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm). 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)) part was set to 300°C. The sample was dissolved in acetone to prepare a 1% by weight solution, and 1 μl of the obtained solution was injected into the sample vaporization chamber. The recorder uses a 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 measurement. The column is made of YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle size 5 μm) manufactured by Vimex (YMC). The eluate is suitably mixed with acetonitrile and water. The detector is suitable for using an ultraviolet (UV) detector, a refractive index (Reflective Index, RI) detector, a CORONA (CORONA) detector, etc. When using a UV detector, set the detection wavelength to 254 nm. The sample was dissolved in acetonitrile to prepare a 0.1% by weight solution, and 1 μL of this solution was introduced into the sample chamber. The recorder is C-R7A plus manufactured by Shimadzu Corporation.

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

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

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

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

(2)Transition temperature (℃) For measurement, a scanning calorimeter Diamond DSC system manufactured by Perkin Elmer or a high-sensitivity differential scanning calorimeter X-DSC7000 manufactured by Hitachi High-Tech Science Co., Ltd. was used. The temperature of the sample is 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 is determined by extrapolation, and the transition temperature is determined. The melting point and polymerization starting temperature of the compound are also measured using this device. The temperature at which a compound changes from a solid to a liquid crystal phase such as a smectic phase or a nematic phase is 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 referred to as the "clear point."

Denote the crystal 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. Among the smectic phases, when distinguishing between the smectic A phase, the smectic B phase, the smectic C phase, or the smectic F phase, they are represented by _SA , _SB , _SC , or _SF respectively. Denote the liquid (isotropic) as I. The transition temperature is expressed as "C 50.0 N 100.0 I", for example. It means that the temperature at which the crystalline phase changes to the nematic phase is 50.0°C, and the temperature at which the nematic phase changes to the liquid phase is 100.0°C.

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

(4) Lower limit temperature of nematic phase ( _TC ;°C). Store the sample with nematic phase in a freezer at 0°C, -10°C, -20°C, -30°C, and -40°C for 10 days. Finally, observe the liquid crystal phase. For example, when the sample maintains the nematic phase at -20°C and changes to the crystalline or smectic phase at -30°C, _TC is recorded as ≦-20°C. The lower limit temperature of the nematic phase is sometimes simply called the "lower limit temperature".

(5) Viscosity (bulk viscosity; eta; measured at 20°C; mPa·s) During 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 is performed using light with a wavelength of 589 nm and an Abbe refractometer with a polarizing plate attached to the eyepiece. After rubbing the surface of the main drum in one direction, drop the sample onto the main drum. The refractive index (n∥) is measured when the direction of polarized light is parallel to the direction of rubbing. The refractive index (n⊥) is measured when the direction of polarized light is perpendicular to the direction of rubbing. The value of optical anisotropy (Δn) is calculated according to the formula Δn=n∥-n⊥.

(7) Specific resistance (ρ; measured at 25°C; Ωcm) Inject 1.0 mL of sample into the container equipped with the electrode. A DC voltage (10 V) was applied to the 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 the container)}/{(DC current) × (dielectric constant of vacuum)}.

A sample with positive dielectric anisotropy and a sample with negative dielectric anisotropy may have different characteristics measurement methods. The measurement method when the dielectric anisotropy is positive is described in items (8a) to (12a). When 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: Measurement is based on the method described in "Molecular Crystals and Liquid Crystals" (Vol. 259, 37 (1995)) by M. Imai et al. . A sample was placed in a TN device with a twist angle of 0 degrees and a distance (cell gap) between two glass substrates of 5 μm. A voltage was applied to the component in steps of 0.5 V in the range of 16 V to 19.5 V. After no voltage was applied for 0.2 seconds, voltage was repeatedly applied with only one rectangular wave (rectangular pulse; 0.2 seconds) and no voltage applied (2 seconds). The peak current and peak time of the transient current generated by this application are measured. The rotational viscosity value is obtained based on these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al. The value of the dielectric anisotropy necessary for this calculation is determined by the method described below using an element that measured the rotational viscosity.

(8b) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s) Negative dielectric anisotropy: Measurement is based on the method described in "Molecular Crystals and Liquid Crystals" (Vol. 259, 37 (1995)) by M. Imai et al. . A sample was placed in a VA element with a distance (cell gap) of 20 μm between two glass substrates. A voltage was applied to the component in steps of 1 volt in the range of 39 volts to 50 volts. After no voltage was applied for 0.2 seconds, voltage was repeatedly applied with only one rectangular wave (rectangular pulse; 0.2 seconds) and no voltage applied (2 seconds). The peak current and peak time of the transient current generated by this application are measured. The rotational viscosity value is obtained based on these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al. The dielectric anisotropy necessary for this calculation is a value measured using the item of dielectric anisotropy described below.

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

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

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

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

(11a) Threshold voltage (Vth; measured at 25°C; V) Positive dielectric anisotropy: During measurement, an LCD5100 model luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source is set to halogen lamp. A sample was placed in a normally white mode TN element with a distance (cell gap) of 0.45/Δn (μm) between two glass substrates and a twist angle of 80 degrees. The voltage (32 Hz, rectangular wave) applied to this element is increased from 0 V to 10 V in steps of 0.02 V. At this time, the element is irradiated with light from the vertical direction, and the amount of light transmitted through the element is measured. A voltage-transmittance curve is created in which the transmittance is 100% when the light amount reaches the maximum and the transmittance is 0% when the light amount is the minimum. The threshold voltage is expressed as the voltage when the transmittance reaches 90%.

(11b) Threshold voltage (Vth; measured at 25°C; V) Negative dielectric anisotropy: During measurement, an LCD5100 model luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source is set to halogen lamp. A sample is placed in a normally black mode VA device with an anti-parallel rubbing direction and a gap (cell gap) of 4 μm between two glass substrates. The device is sealed with an adhesive that is cured by ultraviolet rays. . The voltage (60 Hz, rectangular wave) applied to this element is increased from 0 V to 20 V in steps of 0.02 V. At this time, the element is irradiated with light from the vertical direction, and the amount of light transmitted through the element is measured. A voltage-transmittance curve is created in which the transmittance is 100% when the light amount reaches the maximum and the transmittance is 0% when the light amount is the minimum. The threshold voltage is expressed as the voltage when the transmittance reaches 10%.

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

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

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

raw material Solmix (registered trademark) A-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (IPA) (1.1%). It is purchased from Japan Alcohol Sales Co., Ltd. ) get.

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

first step Put sodium hydride (6.52 g) and tetrahydrofuran (THF) (380 ml) into the reactor and cool to 0°C. A THF (210 ml) solution of compound (T-1) (39.3 g) was slowly added dropwise thereto, and the mixture was stirred for 20 minutes while returning to room temperature. Benzyl chloromethyl ether (27.5 ml) was added dropwise thereto, and the mixture was heated to reflux at 55°C for 6 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, heptane:ethyl acetate=10:1) to obtain compound (T-2) (38.6 g; 75%).

Second step Put compound (T-2) (38.6 g), palladium hydroxide (1.93 g), toluene (115 ml), and IPA (115 ml) into the reactor, and stir at room temperature for 12 hours under a hydrogen atmosphere. . After filtering and separating the catalyst, it was concentrated under reduced pressure, and the residue was purified using silica gel chromatography (volume ratio, heptane:ethyl acetate = 2:1) to obtain compound (T-3) (25.0 g; 79%).

The third step Compound (T-3) (25.0 g), 3,4-dihydro-2H-pyran (5.45 g), and dichloromethane (250 ml) were put into the reactor and cooled to 0°C. Pyridinium p-toluenesulfonate (PPTS) (1.48 g) was slowly added thereto, and the mixture was stirred for 8 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 (volume ratio, heptane:ethyl acetate=10:1) to obtain compound (T-4) (29.7 g; 99%). In addition, THP represents tetrahydropyranyl group.

Step 4 Put lithium aluminum hydride (3.68 g) and THF (300 ml) into the reactor and cool to 0°C. A THF (200 ml) solution of compound (T-4) (29.7 g) was slowly added dropwise thereto, and the mixture was stirred for 2 minutes while returning to room temperature. The reaction mixture was poured into a saturated aqueous ammonium chloride solution, and the insoluble matter was separated by filtration, and then 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 to obtain compound (T-5) (19.7 g; 77%).

Step 5 Compound (T-5) (8.00 g), triethylamine (7.88 ml), and THF (160 ml) were put into the reactor and cooled to 0°C. Methacryloyl chloride (4.56 ml) was slowly added dropwise thereto, and the mixture was stirred for 8 hours while returning to room temperature. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried 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=10:1) to obtain compound (T-6) (6.84 g; 65%).

Step 6 Compound (T-6) (6.84 g), PPTS (1.53 g), THF (34.0 ml), and methanol (34.0 ml) were put into the 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, heptane:ethyl acetate=4:1). Further, the compound (T-7) (3.77 g; 65%) was obtained by recrystallization and purification using a mixed solvent of heptane and ethyl acetate (volume ratio, 20:1).

Step 7 Compound (T-8) (1.77 g), compound (T-7) (3.77 g), DMAP (0.483 g), and dichloromethane (45.0 ml) synthesized according to the method described in WO2017209161A1 were put into the reaction In a container, cool to 0°C. A solution of DCC (2.45 g) in methylene chloride (10.0 ml) was slowly added dropwise thereto, and the mixture was stirred for 12 hours while returning to room temperature. After filtering and separating the insoluble matter, the reaction mixture was poured into water, and the aqueous layer was extracted with methylene chloride. 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 = 6:1) to obtain compound (T-9) (5.05 g; 99%).

Step 8 Compound (T-9) (5.05 g), PPTS (0.984 g), THF (25.0 ml), and methanol (25.0 ml) were put into the 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, heptane:ethyl acetate=3:1). Further, the compound (1-2-1) (3.30 g; 75%) was obtained by recrystallization and purification using a mixed solvent of heptane and ethyl acetate (volume ratio, 5:1).

The NMR analysis value of the obtained compound (1-2-1) is as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.22 (s, 1H), 6.08 (s, 2H), 5.86 (s, 1H), 5.58 (t, J = 1.2 Hz, 2H), 4.45- 4.38(m,2H), 4.38-4.29(m,6H), 2.22(t,J=6.4 Hz,1H), 1.93(s,6H), 1.86-1.78(m,4H), 1.78-1.65(m, 4H), 1.55-1.48(m,2H), 1.34-1.07(m,10H), 1.07-0.78(m,11H).

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

first step Put trifluoromethanesulfonic anhydride (43.6 g) and dichloromethane (230 ml) into the reactor and cool to 0°C. A solution of compound (T-10) (30.9 g) and triethylamine (37.1 ml) in methylene chloride (460 ml) was slowly added dropwise thereto. The obtained solution was poured into ethylene glycol (500 ml) 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-11) (21.9 g; 51%).

Second step Using compound (T-11) (19.6 g) as a raw material, compound (T-12) (29.0 g; 97%) was obtained by the same method as the third step of Synthesis Example 1.

The third step Compound (T-12) (29.0 g), THF (145 ml), and water (145 ml) were put into the reactor and cooled to 0°C. Lithium hydroxide monohydrate (9.96 g) was added thereto, and the mixture was stirred for 8 hours while returning to room temperature. The reaction mixture was poured into water, and a 10% citric acid aqueous solution (150 ml) was slowly added to make it acidic, 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-13) (26.0 g; 95%).

Step 4 Using compound (T-14) (40.0 g) as a raw material, compound (T-15) (50.1 g; 97%) was obtained by the same method as the first step of Synthesis Example 1.

Step 5 Using compound (T-15) (50.1 g) as a raw material, compound (T-16) (40.4 g; 97%) was obtained by the same method as the second step of Synthesis Example 1.

Step 6 Using compound (T-16) (40.4 g) as a raw material, compound (T-17) (43.2 g; 90%) was obtained by the same method as the third step of Synthesis Example 1.

Step 7 Using compound (T-17) (43.2 g) as a raw material, compound (T-18) (30.1 g; 83%) was obtained by the same method as the fourth step of Synthesis Example 1.

Step 8 Using compound (T-18) (30.1 g) as a raw material, compound (T-19) (25.2 g; 63%) was obtained by the same method as the fifth step of Synthesis Example 1.

Step 9 Using compound (T-19) (25.2 g) as a raw material, compound (T-20) (18.1 g; 84%) was obtained by the same method as the sixth step of Synthesis Example 1.

Step 10 Using compound (T-20) (5.00 g) and compound (T-13) (3.19 g) as raw materials, compound (T-21) (6.66 g) was obtained by the same method as the seventh step of Synthesis Example 1; 94%).

Step 11 Using compound (T-21) (6.66 g) as a raw material, compound (1-2-15) (2.10 g; 36%) was obtained by the same method as the eighth step of Synthesis Example 1.

The NMR analysis value of the obtained compound (1-2-15) is as follows. ¹ H-NMR: chemical shift δ (ppm; CDCl ₃ ): 6.32 (d, J = 0.7 Hz, 1H), 6.11 (s, 2H), 5.91 (d, J = 1.2 Hz, 1H), 5.61 (t, J=1.2 Hz,2H),4.25(s,2H),4.19(s,2H),4.17(s,4H),3.81-3.75(m,2H),3.66-3.61(m,2H),2.31(t ,J=6.3 Hz,1H), 1.96(s,6H), 1.80-1.66(m,8H), 1.56-1.50(m,2H), 1.36-0.80(m,25H).

[Synthesis Example 3] Synthesis of compound (1-2-27)

first step Compound (T-22) (150 g), triphenylphosphine (350 g), imidazole (175 g), and toluene (2.25 l) were put into the reactor and cooled to 0°C. Iodine (326 g) was slowly added thereto, and the mixture was stirred for 2 hours while returning to room temperature. After filtering and separating the insoluble matter, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with a saturated sodium thiosulfate aqueous solution 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 = 10:1) to obtain compound (T-23) (197 g; 75%).

Second step Put sodium hydride (21.8 g) and THF (800 ml) into the reactor, slowly add a solution of compound (T-24) (107 g) in THF (240 ml) dropwise and stir for 1 hour, then cool to 0 ℃. A solution of compound (T-23) (61.0 g) in THF (360 ml) was slowly added dropwise thereto, and the mixture was heated to reflux at 55°C for 6 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. The obtained intermediate was put into another reactor together with formaldehyde (28.6 g), potassium carbonate (65.8 g), and water (610 ml), and stirred at 80°C for 6 hours. The aqueous layer was extracted with ethyl acetate, and 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 = 15:1) to obtain compound (T-25) (19.6 g; 36%).

The third step Using compound (T-25) (19.6 g) as a raw material, compound (T-26) (15.4 g; 95%) was obtained by the same method as the third step of Synthesis Example 2.

Step 4 Using compound (T-20) (5.00 g) and compound (T-26) (2.78 g) as raw materials, compound (T-27) (6.53 g) was obtained by the same method as the seventh step of Synthesis Example 1; 96%).

Step 5 Compound (T-27) (6.53 g), PPTS (0.478 g), THF (100 ml), and methanol (100 ml) were put into the reactor, and stirred at room temperature for 3 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried 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=1:2). It was further purified by recrystallization using a mixed solvent of heptane and toluene (volume ratio, 5:1) to obtain compound (1-2-27) (5.05 g; 82%).

The NMR analysis value of the obtained compound (1-2-27) is as follows. ¹ H-NMR: chemical shift δ (ppm; CDCl ₃ ): 6.24 (s, 1H), 6.10 (s, 2H), 5.66 (s, 1H), 5.60 (t, J = 1.2 Hz, 2H), 4.15 ( s,6H), 3.80-3.72(m,2H), 3.67-3.60(m,2H), 2.55(t,J=5.7 Hz,2H), 2.35(d,J=7.4 Hz,2H), 1.94(s ,6H), 1.87-1.79(m,1H), 1.78-1.64(m,8H), 1.55-1.48(m,2H), 1.34-1.03(m,12H), 1.03-0.78(m,13H).

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

first step Using compound (T-20) (12.0 g) as a raw material, compound (T-28) (13.1 g; 82%) was obtained by the same method as the sixth step of Synthesis Example 1.

Second step Using compound (T-28) (13.1 g) as a raw material, compound (1-2-3) (10.1 g; 88%) was obtained by the same method as the seventh step of Synthesis Example 1.

The NMR analysis value of the obtained compound (1-2-3) is as follows. ¹ H-NMR: chemical shift δ (ppm; CDCl ₃ ): 6.24 (s, 1H), 6.09 (s, 2H), 5.87 (d, J = 1.0 Hz, 1H), 5.59 (t, J = 1.3 Hz. 2H), 4.35-4.31(m,2H), 4.19-4.12(m,6H), 2.28(t,J=6.5 Hz,1H), 1.94(s,6H), 1.78-1.64(m,8H), 1.54 -1.47(m,2H), 1.33-0.78(m,25H).

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

first step Using compound (T-29) (32.0 g) as a raw material, compound (T-30) (34.7 g; 87%) was obtained by the same method as the first step of Synthesis Example 1.

Second step Using compound (T-30) (34.7 g) as a raw material, compound (T-31) (22.8 g; 77%) was obtained by the same method as the second step of Synthesis Example 1.

The third step Using compound (T-31) (22.8 g) as a raw material, compound (T-32) (24.5 g; 93%) was obtained by the same method as the third step of Synthesis Example 1.

Step 4 Using compound (T-32) (24.5 g) as a raw material, compound (T-33) (21.1 g; 100%) was obtained by the same method as the fourth step of Synthesis Example 1.

Step 5 Using compound (T-33) (21.1 g) as a raw material, compound (T-34) (15.0 g; 56%) was obtained by the same method as the fifth step of Synthesis Example 1.

Step 6 Using compound (T-34) (15.0 g) as a raw material, compound (T-35) (13.0 g; 99%) was obtained by the same method as the sixth step of Synthesis Example 1.

Step 7 Using compound (T-35) (13.0 g) as a raw material, compound (T-36) (16.0 g; 95%) was obtained by the same method as the seventh step of Synthesis Example 1.

Step 8 Using compound (T-36) (16.0 g) as a raw material, compound (1-3-4) (5.86 g; 41%) was obtained by the same method as the eighth step of Synthesis Example 1.

The NMR analysis value of the obtained compound (1-3-4) is as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.12(d,J=8.1 Hz,2H), 7.05(d,J=8.1 Hz,2H), 6.26(s,1H), 6.12(s, 2H), 5.89(d,J=1.1 Hz,1H), 5.61(t,J=1.2 Hz,2H),4.36-4.32(m,2H), 4.26-4.22(m,6H), 2.67-2.60(m ,2H), 2.41(tt,J=12.2 Hz,J=3.3 Hz,1H), 2.23(t,J=6.4 Hz,1H), 1.95(s,6H), 1.92-1.70(m,10H), 10.45 -1.34(m,2H), 1.34-0.94(m,15H), 0.91-0.81(m,5H).

[Synthesis Example 6] Synthesis of compound (1-3-40)

first step Using the compound (T-37) (2.12 g) synthesized by the same method as the first to sixth steps of Synthesis Example 5 as a raw material, a compound was obtained by the same method as the sixth step of Synthesis Example 1 (T-38) (2.57 g; 95%).

Second step Using compound (T-38) (2.57 g) as a raw material, compound (1-3-40) (1.70 g; 74%) was obtained by the same method as the seventh step of Synthesis Example 1.

The NMR analysis value of the obtained compound (1-3-40) is as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.17(d,J=8.1 Hz,2H), 7.07(d,J=8.1 Hz,2H), 6.28(s,1H), 6.14(s, 2H), 5.91(s,1H), 5.63(s,2H), 4.36-4.32(m,2H), 4.27-4.23(m,6H), 2.68-2.62(m,2H), 2.45(tt,J= 12.1 Hz,J=3.3 Hz,1H), 2.29(t,J=6.4 Hz,1H), 1.97(s,6H), 1.90-1.60(m,8H), 1.50-0.80(m,28H).

[Synthesis Example 7] Synthesis of compound (1-2-37)

first step Put sodium hydride (4.96 g) and THF (200 ml) into the reactor and cool to 0°C. A THF (120 ml) solution of compound (T-14) (32.0 g) was slowly added dropwise thereto, and the mixture was stirred for 20 minutes while returning to room temperature. Benzyl 2-chloroethyl ether (23.3 ml) was added dropwise thereto, and the mixture was heated to reflux at 55°C for 6 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, heptane:ethyl acetate = 10:1) to obtain compound (T-39) (32.5 g; 77%).

Second step Using compound (T-39) (32.5 g) as a raw material, compound (T-40) (19.9 g; 73%) was obtained by the same method as the second step of Synthesis Example 1.

The third step Using compound (T-40) (19.9 g) as a raw material, compound (T-41) (22.1 g; 94%) was obtained by the same method as the third step of Synthesis Example 1.

Step 4 Using compound (T-41) (22.1 g) as a raw material, compound (T-42) (17.8 g; 95%) was obtained by the same method as the fourth step of Synthesis Example 1.

Step 5 Using compound (T-42) (17.8 g) as a raw material, compound (T-43) (15.2 g; 66%) was obtained by the same method as the fifth step of Synthesis Example 1.

Step 6 Using compound (T-43) (15.2 g) as a raw material, compound (T-44) (12.9 g; 99%) was obtained by the same method as the sixth step of Synthesis Example 1.

Step 7 Using compound (T-44) (2.00 g) as a raw material, compound (T-45) (1.74 g; 95%) was obtained by the same method as the seventh step of Synthesis Example 1.

Step 8 Using compound (T-45) (1.74 g) as a raw material, compound (1-2-37) (1.12 g; 73%) was obtained by the same method as the eighth step of Synthesis Example 1.

The NMR analysis value of the obtained compound (1-2-37) is as follows. ¹ H-NMR: chemical shift δ (ppm; CDCl ₃ ): 6.23 (s, 1H), 6.09 (s, 2H), 5.84 (s, 1H), 5.58 (t, J = 1.0 Hz, 2H), 4.35- 4.27(m,4H), 4.13-4.05(m,4H), 2.26(t,J=6.4 Hz,1H), 1.94(s,6H), 1.83(t,J=6.7 Hz,2H), 1.78-1.63 (m,8H), 1.50-1.42(m,2H), 1.33-0.78(m,25H).

[Comparative example 1] Compound (S-1) and compound (S-2) were synthesized as comparative compounds, and their properties were measured. This compound is described in International Publication No. 2017/209161 and is similar to the compound of the present invention, so this compound was selected.

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

The NMR analysis values of comparative compound (S-2) are as follows. ¹ H-NMR: chemical shift δ (ppm; CDCl ₃ ): 6.24 (s, 1H), 6.09 (s, 2H), 5.87 (s, 1H), 5.57-5.60 (m, 2H), 4.36-4.26 (m ,6H), 4.21-4.17(m,2H), 2.34-2.31(m,1H), 1.97-1.85(m,8H), 1.78-1.64(m,6H), 1.54-1.47(m,2H), 1.33 -0.78(m,27H).

The voltage holding ratio (VHR) of compound (1-2-1) and compound (1-2-3) and comparative compound (S-1) and comparative compound (S-2) was compared. In addition, composition (i) was used for evaluation.

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

To the composition (i), each compound was added at a ratio of 3.0% by weight to prepare a sample. This sample was injected into an element without an alignment film in which the distance between two glass substrates (cell gap) was 3.5 μm. Using the backlight F40T10/BL (peak wavelength 355 nm) manufactured by Eye Graphics Co., Ltd., the element is irradiated with ultraviolet light (20 J) to polymerize the added compound. This element was charged by applying a pulse voltage (1 V for 60 microseconds) at 60°C. Use a high-speed voltmeter to measure the attenuated voltage during 1.67 milliseconds, and find the area A between the voltage curve per unit period and the horizontal axis. Area B is the area without attenuation. The voltage retention rate is expressed as the percentage of area A relative to area B.

The voltage holding ratios of compound (1-2-1) and compound (1-2-3) and comparative compound (S-1) and comparative compound (S-2) are summarized in Table 2. When the compound (1-2-1) or the compound (1-2-3) is used, a larger voltage holding ratio can be obtained than when the comparative compound (S-1) or the comparative compound (S-2) is used. The reason is that the compound of the present invention has multiple polymerizable groups such as methacrylyl groups, and the polymerizable groups are connected to the same carbon atom through a spacer group, so it can form a high-quality polymer network with high symmetry. , the decrease in voltage holding ratio is suppressed. Therefore, the compound (1-2-1) and the compound (1-2-3) can be said to be excellent compounds having a high voltage retention when used in liquid crystal display elements.

The following compounds can be synthesized by referring to the method described in the synthesis examples or "2. Synthesis of Compound (1)".

2. Examples of compositions The compounds in the examples are represented by symbols based on the definitions in Table 3 below. In Table 3, the stereoconfiguration related to 1,4-cyclohexylene 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 crystalline 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 characteristics are measured according to the method described above, and the measured values are reported directly (without extrapolation).

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

The following compound (1-2-1) was added to the composition at a ratio of 1% by weight.

NI=95.9℃; η=17.7 mPa·s; Δn=0.108; Δε=5.0.

[Use example 2] 3-HH-4 (2-1) 13% 5-HB-O2 (2-5) 4% 7-HB-1 (2-5) 3% 5-HBB(F)B-2 (4-5) 5% 5-HBB(F)B-3 (4-5) 5% 3-HB-CL (5-2) 12% 3-HHB(F,F)-F (6-3) 4% 3-HBB(F,F)-F (6-24) 29% 5-HBB(F,F)-F (6-24) 25%

The following compound (1-2-27) was added to the composition in a proportion of 3% by weight.

NI=71.3℃; η=19.8 mPa·s; Δn=0.113; Δε=5.7.

[Use example 3] 1V2-HH-1 (2-1) 4% 1V2-HH-3 (2-1) 5% 7-HB(F,F)-F (5-4) 4% 2-HHB(F)-F (6-2) 10% 3-HHB(F)-F (6-2) 10% 5-HHB(F)-F (6-2) 8% 2-HBB-F (6-22) 4% 3-HBB-F (6-22) 4% 5-HBB-F (6-22) 3% 2-HBB(F)-F (6-23) 8% 3-HBB(F)-F (6-23) 9% 5-HBB(F)-F (6-23) 16% 3-HBB(F,F)-F (6-24) 5% 5-HBB(F,F)-F (6-24) 10%

The following compound (1-2-15) was added to the composition in a proportion of 7% by weight.

NI=82.6℃; η=24.2 mPa·s; Δn=0.109; Δε=5.4.

[Use example 4] 2-HH-3 (2-1) 4% 3-HH-4 (2-1) 12% 1O1-HBBH-5 (4-1) 5% 5-HB-CL (5-2) 14% 3-HHB-F (6-1) 4% 3-HHB-CL (6-1) 4% 4-HHB-CL (6-1) 4% 3-HHB(F)-F (6-2) 10% 4-HHB(F)-F (6-2) 8% 5-HHB(F)-F (6-2) 9% 7-HHB(F)-F (6-2) 7% 5-HBB(F)-F (6-23) 3% 3-HHBB(F,F)-F (7-6) 3% 4-HHBB(F,F)-F (7-6) 3% 5-HHBB(F,F)-F (7-6) 4% 3-HH2BB(F,F)-F (7-15) 3% 4-HH2BB(F,F)-F (7-15) 3%

The following compound (1-3-15) was added to the composition in a proportion of 3.5% by weight.

NI=119.8℃; η=20.4 mPa·s; Δn=0.094; Δε=3.7.

[Use example 5] V-HBB-2 (3-4) 11% 1O1-HBBH-4 (4-1) 3% 1O1-HBBH-5 (4-1) 3% 3-HHB(F,F)-F (6-3) 9% 3-H2HB(F,F)-F (6-15) 9% 4-H2HB(F,F)-F (6-15) 8% 5-H2HB(F,F)-F (6-15) 8% 3-HBB(F,F)-F (6-24) 9% 5-HBB(F,F)-F (6-24) 21% 3-H2BB(F,F)-F (6-27) 10% 5-HHBB(F,F)-F (7-6) 3% 3-HH2BB(F,F)-F (7-15) 4% 5-HHEBB-F (7-17) 2%

The following compound (1-2-12) was added to the composition in a proportion of 5% by weight.

NI=104.9℃; η=32.1 mPa·s; Δn=0.122; Δε=8.3.

[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) 8% 3-HHB-OCF3 (6-1) 6% 4-HHB-OCF3 (6-1) 7% 5-HHB-OCF3 (6-1) 4% 3-HHB(F,F)-OCF2H (6-3) 4% 3-HHB(F,F)-OCF3 (6-3) 4% 3-HH2B-OCF3 (6-4) 5% 5-HH2B-OCF3 (6-4) 4% 3-HH2B(F)-F (6-5) 3% 3-HBB(F)-F (6-23) 11% 5-HBB(F)-F (6-23) 10%

The following compound (1-2-30) was added to the composition in a proportion of 0.1% by weight.

NI=85.1℃; η=14.7 mPa·s; Δn=0.092; Δε=4.4.

[Use example 7] 2-HH-5 (2-1) 4% 3-HH-4 (2-1) 5% 5-B(F)BB-2 (3-8) 4% 5-HB-CL (5-2) 10% 3-HHB(F,F)-F (6-3) 11% 3-HHEB(F,F)-F (6-12) 8% 4-HHEB(F,F)-F (6-12) 3% 5-HHEB(F,F)-F (6-12) 3% 3-HBB(F,F)-F (6-24) 18% 5-HBB(F,F)-F (6-24) 17% 2-HBEB(F,F)-F (6-39) 5% 3-HBEB(F,F)-F (6-39) 3% 5-HBEB(F,F)-F (6-39) 4% 3-HHBB(F,F)-F (7-6) 5%

The following compound (1-2-1) was added to the composition in a proportion of 2% by weight.

NI=75.7℃; η=22.7 mPa·s; Δn=0.108; Δε=8.8.

[Use example 8] V2-HHB-1 (3-1) 6% 3-HB-CL (5-2) 6% 5-HB-CL (5-2) 4% 3-HHB-OCF3 (6-1) 4% 5-HHB(F)-F (6-2) 6% V-HHB(F)-F (6-2) 5% 3-H2HB-OCF3 (6-13) 5% 5-H2HB(F,F)-F (6-15) 5% 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) 5%

The following compound (1-2-27) was added to the composition in a proportion of 1% by weight.

NI=73.3℃; η=24.7 mPa·s; Δn=0.098; Δε=8.1.

[Use example 9] 3-HH-4 (2-1) 8% 3-HH-5 (2-1) 9% 3-HB-O2 (2-5) 13% 3-HHB-1 (3-1) 7% 3-HHB-O1 (3-1) 5% 5-HB-CL (5-2) 13% 7-HB(F,F)-F (5-4) 4% 2-HHB(F)-F (6-2) 7% 3-HHB(F)-F (6-2) 8% 5-HHB(F)-F (6-2) 7% 3-HHB(F,F)-F (6-3) 7% 3-H2HB(F,F)-F (6-15) 6% 4-H2HB(F,F)-F (6-15) 6%

The following compound (1-2-15) was added to the composition in a proportion of 0.5% by weight.

NI=73.1℃; η=15.0 mPa·s; Δn=0.073; Δε=3.0.

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

The following compound (1-3-15) was added to the composition in a proportion of 4% by weight.

NI=87.9℃; η=21.5 mPa·s; Δn=0.071; Δε=5.8.

[Use example 11] 3-HH-VFF (2-1) 10% 5-HH-VFF (2-1) 20% 2-BTB-1 (2-10) 9% 3-HHB-1 (3-1) 5% VFF-HHB-1 (3-1) 9% VFF2-HHB-1 (3-1) 10% 3-H2BTB-2 (3-17) 3% 3-H2BTB-3 (3-17) 5% 3-H2BTB-4 (3-17) 5% 3-HB-C (8-1) 16% 1V2-BEB(F,F)-C (8-15) 8%

The following compound (1-2-12) was added to the composition in a proportion of 3% by weight.

NI=81.3℃; η=11.7 mPa·s; Δn=0.129; Δε=7.8.

[Use example 12] 1-BB-3 (2-8) 7% 1-BB-5 (2-8) 8% 2-BTB-1 (2-10) 3% 3-HHB-1 (3-1) 8% 3-HHB-3 (3-1) 10% 3-HHB-O1 (3-1) 6% 3-HHB-F (6-1) 5% 2-HHB(F)-F (6-2) 7% 3-HHB(F)-F (6-2) 8% 5-HHB(F)-F (6-2) 7% 3-HHB(F,F)-F (6-3) 5% 3-HHEB-F (6-10) 5% 5-HHEB-F (6-10) 4% 2-HB-C (8-1) 7% 3-HB-C (8-1) 10%

The following compound (1-2-3) was added to the composition at a ratio of 1% by weight.

NI=95.9℃; η=17.7 mPa·s; Δn=0.108; Δε=5.0.

[Use example 13] V-HBB-2 (3-4) 11% 1O1-HBBH-4 (4-1) 3% 1O1-HBBH-5 (4-1) 3% 3-HHB(F,F)-F (6-3) 9% 3-H2HB(F,F)-F (6-15) 9% 4-H2HB(F,F)-F (6-15) 8% 5-H2HB(F,F)-F (6-15) 8% 3-HBB(F,F)-F (6-24) 9% 5-HBB(F,F)-F (6-24) 21% 3-H2BB(F,F)-F (6-27) 10% 5-HHBB(F,F)-F (7-6) 3% 3-HH2BB(F,F)-F (7-15) 4% 5-HHEBB-F (7-17) 2%

The following compound (1-3-4) was added to the composition in a proportion of 5% by weight.

NI=104.9℃; η=32.1 mPa·s; Δn=0.122; Δε=8.3.

[Use example 14] V2-HHB-1 (3-1) 6% 3-HB-CL (5-2) 6% 5-HB-CL (5-2) 4% 3-HHB-OCF3 (6-1) 4% 5-HHB(F)-F (6-2) 6% V-HHB(F)-F (6-2) 5% 3-H2HB-OCF3 (6-13) 5% 5-H2HB(F,F)-F (6-15) 5% 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) 5%

The following compound (1-3-40) was added to the composition at a ratio of 1% by weight.

NI=73.3℃; η=24.7 mPa·s; Δn=0.098; Δε=8.1.

[Use example 15] 3-HH-VFF (2-1) 10% 5-HH-VFF (2-1) 20% 2-BTB-1 (2-10) 9% 3-HHB-1 (3-1) 5% VFF-HHB-1 (3-1) 9% VFF2-HHB-1 (3-1) 10% 3-H2BTB-2 (3-17) 3% 3-H2BTB-3 (3-17) 5% 3-H2BTB-4 (3-17) 5% 3-HB-C (8-1) 16% 1V2-BEB(F,F)-C (8-15) 8%

The following compound (1-2-37) was added to the composition in a proportion of 3% by weight.

NI=81.3℃; η=11.7 mPa·s; Δn=0.129; Δε=7.8. [Industrial availability]

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

without

without

Claims (18)

A polymerizable polar compound represented by formula (1),

In formula (1), R ¹ is hydrogen or an alkyl group having 1 to 15 carbon atoms. Among the alkyl groups, 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-, among these groups, at least one hydrogen can be substituted by fluorine or chlorine; Ring A ¹ and Ring A ² are independently 1,2-cyclopropyl , 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-cyclohexenyl, 1,4- Phenylene, naphthalene-2,6-diyl, decalin-2,6-diyl, 1,2,3,4-tetralin-2,6-diyl, tetrahydropyran-2, 5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, at least one hydrogen in these rings can be fluorinated , chlorine, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkoxy group with 1 to 9 carbon atoms, or an alkenyloxy group with 2 to 9 carbon atoms, at least one of these groups Hydrogen can be substituted by fluorine or chlorine; a is 0, 1, 2, 3, or 4; Z ¹ is independently a single bond or an alkylene group with 1 to 10 carbon atoms, in which at least one -CH ₂ - may be substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, Among these groups, at least one hydrogen may 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 - may be substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡ C-substituted, among these groups, at least one hydrogen can be substituted by fluorine or chlorine; M ¹ , M ² , M ³ , M ⁴ , M ⁵ , and M ⁶ are independently hydrogen, fluorine, chlorine, carbon number 1 to 5 alkyl, or an alkyl group with 1 to 5 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; R ² and R ³ are independently hydrogen or an alkyl group with 1 to 10 carbon atoms, and in the alkyl group, at least One -CH ₂ - can be substituted by -O-, 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 ; R ⁴ is a group selected from the group represented by formula (1-a), formula (1-b), and formula (1-c);

In formula (1-a), formula (1-b), and formula (1-c), Sp ⁵ and Sp ⁶ 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 substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C ≡C-substituted, in these groups, at least one hydrogen can be substituted by fluorine or chlorine; R ⁵ is hydrogen, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 9 carbon atoms, or an alkyl group with 1 to 9 carbon atoms. alkoxyalkyl; X ¹ is independently -OH, -NH ₂ , -N(R ⁶ ) ₂ , -COOH, -SH, or -Si(R ⁶ ) ₃ ; -N(R ⁶ ) ₂ and -Si(R ⁶ ) ₃ , R ⁶ is hydrogen or an alkyl group with 1 to 10 carbon atoms. Among the alkyl groups, at least one -CH ₂ - may be substituted by -O-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH-, and in these groups, at least one hydrogen may be substituted by fluorine or chlorine. The polymerizable polar compound as described in item 1 of the patent application, wherein in formula (1), Z ¹ is independently 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 polymerizable polar compound as described in item 1 or 2 of the patent application, wherein in formula (1), ring A ¹ and ring A ² are independently 1,4-cyclohexylene and 1,4-cyclohexylene. Cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxan-2,5-diyl, pyrimidine -2,5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen can pass through fluorine, chlorine, alkyl group with 1 to 10 carbon atoms, alkenyl group with 2 to 10 carbon atoms, It is substituted by an alkoxy group having 1 to 9 carbon atoms or an alkenoxy group having 2 to 9 carbon atoms. In these groups, at least one hydrogen may be substituted with fluorine or chlorine. For example, the polymerizable polar compound described in item 1 or 2 of the patent application 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 with 1 to 15 carbon atoms, an alkenyl group with 2 to 15 carbon atoms, an alkoxy group with 1 to 14 carbon atoms, or 2 carbon atoms. ~14 alkenyloxy groups, among 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-cyclohexyl, 1,4 -Cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl group, in these rings, at least one hydrogen can pass through fluorine, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkoxy group with 1 to 9 carbon atoms, or an alkenyl group with 2 to 9 carbon atoms. Oxygen substituted, among these groups, at least one hydrogen can be substituted by fluorine; Z ¹ , Z ² , and Z ³ are independently single bonds, -(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 is independently a single bond or an alkylene group with 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-, and in these groups, at least one hydrogen can be substituted by fluorine; M ¹ , M ² , M ³ , M ⁴ , M ⁵ , and M ⁶ 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 by fluorine; R ² and R ³ are independently hydrogen, an alkyl group having 1 to 7 carbon atoms, or an alkyl group having 1 carbon atoms. to 6 alkoxy groups, or alkoxyalkyl groups with 1 to 6 carbon atoms. Among these groups, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, at least One hydrogen may be substituted by fluorine; R ⁴ is a group selected from the groups represented by formula (1-a), formula (1-b), and formula (1-c);

In formula (1-a), formula (1-b), and formula (1-c), Sp ⁵ and Sp ⁶ 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 substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C ≡C-substituted, in these groups, at least one hydrogen can be substituted by fluorine or chlorine; R ⁵ is hydrogen, an alkyl group with 1 to 7 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, or an alkyl group with 1 to 6 carbon atoms. alkoxyalkyl; X ¹ is independently -OH, -NH ₂ , -COOH, or -SH. For example, the polymerizable polar compound described in item 1 or 2 of the patent application 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 with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, or an alkoxy group with 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-cyclohexenyl, 1,4-phenylene, and naphthalene-2,6-diyl , tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl, in these rings, at least one hydrogen can pass through fluorine, an alkyl group with 1 to 5 carbon atoms, Substituted with an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; Z ¹ , Z ² , and Z ³ are independently single bonds, -(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 the alkylene group is In the base, at least one -CH ₂ - can be substituted by -O-, and at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH-; R ² and R ³ are independently an alkyl group with 1 to 5 carbon atoms. , an alkoxy group with 1 to 4 carbon atoms, or an alkoxyalkyl group with 1 to 4 carbon atoms. In these groups, at least one hydrogen may be substituted by fluorine; R ⁴ is selected from formula (1-a-1) and the radical in the radical represented by formula (1-b-1);

In formula (1-a-1) and formula (1-b-1), Sp ⁵ and Sp ⁶ 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 substituted by -O-; R ⁵ is hydrogen or an alkyl group having 1 to 7 carbon atoms. For example, the polymerizable polar compound described in item 1 or 2 of the patent application is represented by any one of formula (1-8) to formula (1-37),

In formulas (1-8) to formula (1-37), ring A ¹ , ring A ² , and ring A ³ are independently 1,4-cyclohexylene or 1,4-phenylene, and among these rings , at least one hydrogen can be substituted by fluorine or an alkyl group with 1 to 5 carbon atoms; R ¹ is an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, or an alkoxy group with 1 to 9 carbon atoms; Z ¹ and Z ² are independently a single bond or -(CH ₂ ) 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. In the alkyl group, at least one -CH ₂ - may be substituted by -O-; R ⁵ is hydrogen or an alkyl group having 1 to 5 carbon atoms. For example, the polymerizable polar compound described in item 1 or 2 of the patent application is represented by any one of formula (1-38) to formula (1-49),

In Formula (1-38) to Formula (1-49), R ¹ is an alkyl group with 1 to 10 carbon atoms; Z ¹ and Z ² are independently a single bond or -(CH ₂ ) ₂ -; Y ¹ , Y ^2. Y ³ , Y ⁴ , Y ⁵ , and Y ⁶ are independently hydrogen, fluorine, methyl, or ethyl; Sp ¹ and Sp ⁴ are independently a single bond or an alkylene group having 1 to 5 carbon atoms, and the In the alkylene group, at least one -CH ₂ - may be substituted by -O-; R ⁵ is hydrogen, methyl, or ethyl. For example, the polymerizable polar compound described in item 1 or 2 of the patent application is represented by any one of formula (1-50) to formula (1-55),

In Formula (1-50) to Formula (1-55), R ¹ is an alkyl group with 1 to 10 carbon atoms; Z ¹ and Z ² are independently a single bond or -(CH ₂ ) ₂ -; Y ¹ , Y ^2. Y ³ , Y ⁴ , Y ⁵ , and Y ⁶ are independently hydrogen, fluorine, methyl, or ethyl; Sp ¹ and Sp ⁴ are independently a single bond or an alkylene group with 1 to 5 carbon atoms, so In the alkylene group, at least one -CH ₂ - may be substituted by -O-. A liquid crystal composition containing at least one polymerizable polar compound as described in any one of items 1 to 8 of the patent application. The liquid crystal composition described in claim 9, which contains 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 with 1 to 10 carbon atoms or an alkenyl group with 2 to 10 carbon atoms. Among the alkyl groups and alkenyl groups, at least one is -CH ₂ -can be substituted by -O-, and among these groups, at least one hydrogen can be substituted by fluorine; Ring B ¹ , Ring B ² , Ring B ³ , and Ring B ⁴ are independently 1,4-cyclohexyl, 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 is independently a single bond, -COO-, -CH ₂ CH ₂ -, -CH=CH-, or -C≡C-. The liquid crystal composition described in item 9 or 10 of the patent application, which contains at least one compound selected from the group of compounds represented by formula (5) to formula (7),

In formula (5) to formula (7), R ¹³ is an alkyl group with 1 to 10 carbon atoms or an alkenyl group with 2 to 10 carbon atoms. Among the alkyl groups and alkenyl groups, at least one -CH ₂ - can be passed through - _O - _{substituted ,} in the above group _{, at} ^least _one hydrogen can be substituted by _fluorine ; , 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-dioxan-2,5-diyl, pyrimidine-2,5-diyl, or 1,4-phenylene with at least one hydrogen substituted by fluorine; Z ¹⁴ , Z ¹⁵ , and Z ¹⁶ Independently single 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 described in claim 9 or 10, which contains at least one compound selected from the group of compounds represented by formula (8),

In formula (8), R ¹⁴ is an alkyl group with 1 to 10 carbon atoms or an alkenyl group with 2 to 10 carbon atoms. Among the alkyl groups and alkenyl groups, at least one -CH ₂ - can be substituted by -O-, so In the above-mentioned groups, at ^{least one} hydrogen can be substituted by 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 are independently hydrogen or fluorine; i is 1, 2, 3, or 4. The liquid crystal composition described in claim 9 or 10, which contains at least one compound selected from the group of compounds represented by formula (11) to formula (19),

In Formula (11) to Formula (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. Among the alkyl groups and alkenyl groups, At least one -CH ₂ - can be substituted by -O-, in the group, 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 is independently 1,4-cyclohexylene, 1,4-cyclohexenyl, 1,4-phenylene, tetrahydropyran-2,5-diyl, decalin-2,6 -Diyl, or 1,4-phenylene with at least one hydrogen substituted by fluorine; ring E ⁵ and ring E ⁶ are independently 1,4-cyclohexylene, 1,4-cyclohexenyl, 1, 4-phenylene, tetrahydropyran-2,5-diyl, or decalin-2,6-diyl; Z ¹⁸ , Z ¹⁹ , Z ²⁰ , and Z ²¹ are independently single bonds, -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 are independently fluorine or chlorine; S ¹¹ is hydrogen or methyl; X is -CHF- or -CF ₂ -; j, k, m, n, p, q, r, and s is 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 described in claim 9 or 10, 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, and 1,3-dioxanyl. Alk-2-yl, pyrimidin-2-yl, or pyridin-2-yl, in these rings, at least one hydrogen can be passed through halogen, alkyl group with 1 to 12 carbon atoms, alkoxy group with 1 to 12 carbon atoms, Or at least 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, at least one hydrogen in these rings Can be substituted by halogen, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, or 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 single bond or an alkylene group with 1 to 10 carbon atoms. In the alkylene group, 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 )-, these groups in, 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 extension having 1 to 10 carbon atoms. Alkyl group, in the alkylene group, at least one -CH ₂ - can be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ - can be substituted by -CH=CH - or -C≡C-substituted, in these groups, at least one hydrogen can 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. The liquid crystal composition as described in item 14 of the patent application, wherein in formula (20), P ¹¹ , P ¹² , and P ¹³ are independently selected from formula (P-1) to formula (P-5). A group in the group of polymerizable groups represented,

In formulas (P-1) to formula (P-5), M ¹¹ , M ¹² , and M ¹³ are independently hydrogen, fluorine, an alkyl group with 1 to 5 carbon atoms, or at least one hydrogen substituted with a halogen. Alkyl groups from 1 to 5. The liquid crystal composition according to claim 14, 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 in the group,

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 with 1 to 10 carbon atoms. Among the alkylene groups, at least one -CH ₂ - can be passed through -O-, -COO-, -OCO -, or -OCOO-substituted, at least one -CH ₂ CH ₂ - can be substituted by -CH=CH- or -C≡C-, among these groups, at least one hydrogen can be substituted by fluorine or chlorine; P ¹¹ , P ¹² , and P ¹³ are independently a group selected from the group of polymerizable groups represented by formula (P-1) to formula (P-3),

In formulas (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 with a halogen. Alkyl groups from 1 to 5. The liquid crystal composition described in claim 9 or 10, which contains a polymerizable compound selected from the group consisting of a polymerizable compound different from the compound represented by formula (1) or formula (20), a polymerization initiator, and a polymerization inhibitor. , at least one of the group consisting of optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, pigments, and defoaming agents. A liquid crystal display element containing a liquid crystal composition selected from the liquid crystal composition described in any one of items 9 to 17 of the patent application, and a liquid crystal composition as described in any one of items 9 to 17 of the patent application. At least one of the group consisting of at least a part of the liquid crystal composition polymerized.