TWI753222B - Compound, liquid crystal composition and liquid crystal display element - Google Patents

Abstract

The present invention provides a polar compound having high chemical stability, high ability to align liquid crystal molecules, high solubility in a liquid crystal composition, and high voltage holding ratio of a liquid crystal display element. A compound represented by formula (1).

Description

Compound, liquid crystal composition and liquid crystal display element

The present invention relates to a compound, a liquid crystal composition and a liquid crystal display element. Furthermore, in detail, it relates to a compound having a plurality of polymerizable groups such as methacryloyloxy groups and polar groups such as -OH groups in combination, and a liquid crystal including the compound and having positive or negative dielectric anisotropy. A composition, and a liquid crystal display element including a cured product of the composition or a part thereof.

Liquid crystal display elements can be classified into phase change (PC), twisted nematic (TN), super twisted nematic (STN), electrical 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 element, it can be classified into a passive matrix (PM) and an active matrix (AM). PM is classified into static, multiplex, etc., AM is classified into thin film transistor (TFT), metal insulator metal (MIM), and the like. Further, TFTs can be classified into amorphous silicon and polycrystal silicon. The latter are classified into high temperature type and low temperature type according to the manufacturing steps. When classified based on the light source, it can be classified into a reflective type using natural light, a transmissive type using a backlight, and a transflective type using both natural light and backlight.

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

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

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

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

In general liquid crystal display elements, the vertical alignment of liquid crystal molecules can be achieved by a polyimide alignment film. On the other hand, as a liquid crystal display element without an alignment film, a mode in which a polar compound is added to a liquid crystal composition to align liquid crystal molecules is proposed. First, a composition containing a small amount of polar compound and a small amount of polymerizable compound is injected into the element. As the polymerizable compound, a polymerizable compound having a plurality of polymerizable groups is usually used. Here, the liquid crystal molecules are aligned by the action of the polar compound. Next, a voltage was applied between the substrates sandwiching the element, and the composition was irradiated with ultraviolet rays. Here, the polymerizable compound is polymerized to stabilize the alignment of the liquid crystal molecules. If this composition is used, the alignment of the liquid crystal molecules can be controlled by the polar compound and the polymer, so that the response time of the element is shortened, and the afterimage of the image is improved. Furthermore, the step of forming an alignment film is not required in a device without an alignment film. Since there is no alignment film, the resistance of the device will not decrease due to the interaction between the alignment film and the composition. Such effects resulting from the combination of polar compounds and polymers can be expected in elements having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

In liquid crystal display elements that do not have an alignment film, a polymerizable polar compound has been synthesized as a compound that has both the function of a polar compound and the function of a polymerizable compound (for example, Patent Document 1, Patent Document 2, and Patent Document 3). Patent Document 2 describes a polymerizable compound (S-1) having a plurality of polar groups and a plurality of polymerizable groups.

[現有技術文獻] [專利文獻]

[Prior Art Document] [Patent Document]

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

[The problem to be solved by the invention] The first object of the present invention is to provide a compound having high chemical stability, high ability to align liquid crystal molecules, high polymerization reactivity by ultraviolet irradiation, and high voltage holding ratio when used in a liquid crystal display element At least one of them, and has high solubility in liquid crystal compositions. The second problem is to provide a liquid crystal composition including the compound, which satisfies the requirements of high upper limit temperature of nematic phase, low minimum temperature of nematic phase, low viscosity, suitable optical anisotropy, positive or negative 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, which has a wide usable temperature range, short response time, high transmittance, high voltage holding ratio, low threshold voltage, high contrast ratio, long life, good vertical alignment, etc. at least one of the characteristics. [Means of Solving Problems]

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 a part of the composition.

式（1-a）、式（1-b）、及式（1-c）中， Sp³ 及Sp⁴ 獨立地為單鍵或碳數1至15的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-、-OCO-、或-OCOO-取代，至少一個-(CH₂ )₂ -可經-CH=CH-或-C≡C-取代，該些基中，至少一個氫可經氟或氯取代； R³ 為氫、碳數1至10的烷基、碳數1至9的烷氧基、或碳數1至9的烷氧基烷基； X¹ 獨立地為-OH、-NH₂ 、-N(R⁴ )₂ 、-COOH、-SH、或-Si(R⁴ )₃ ； -N(R⁴ )₂ 、及-Si(R⁴ )₃ 中， R⁴ 為氫或碳數1至10的烷基，該烷基中，至少一個-CH₂ -可經-O-取代，至少一個-(CH₂ )₂ -可經-CH=CH-取代，該些基中，至少一個氫可經氟或氯取代。 [發明的效果]In formula (1), Ring A ¹ and Ring A ² are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,5-diyl , naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl base, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, Alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyloxy having 2 to 9 carbons, in which at least one hydrogen may be substituted by Fluorine or chlorine substitution; a is 0, 1, 2, or 3; Z ¹ is a single bond or an alkylene group having 1 to 10 carbon atoms, in the alkylene group, at least one -CH ₂ - may be through -O-, -CO-, -COO-, -OCO-, or -OCOO- substituted, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen Can be substituted by fluorine or chlorine; Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 15 carbon atoms, in the alkylene group, at least one -CH ₂ - can be replaced by -O-, -CO-, -COO-, -OCO-, or -OCOO- substituted, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by fluorine or Chlorine-substituted; M ¹ , M ² , M ³ , and M ⁴ are independently hydrogen, fluorine, chlorine, alkyl with 1 to 5 carbons, or alkane with 1 to 5 carbons in which at least one hydrogen is substituted with fluorine or chlorine group; R ¹ 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, among these groups, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by fluorine or chlorine; R ² is selected from formula (1-a), formula (1-b) ), and the base in the base represented by formula (1-c);

In formula (1-a), formula (1-b), and formula (1-c), Sp ³ and Sp ⁴ are independently a single bond or an alkylene group having 1 to 15 carbon atoms, and in the alkylene group, At least one -CH ₂ - can be substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, and at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡ C-substituted, among these groups, at least one hydrogen can be substituted by fluorine or chlorine; R ³ is hydrogen, alkyl with 1 to 10 carbons, alkoxy with 1 to 9 carbons, or alkoxy with 1 to 9 carbons alkoxyalkyl; X ¹ is independently -OH, -NH ₂ , -N(R ⁴ ) ₂ , -COOH, -SH, or -Si(R ⁴ ) ₃ ; -N(R ⁴ ) ₂ , and In -Si(R ⁴ ) ₃ , R ⁴ is hydrogen or an alkyl group having 1 to 10 carbon atoms, in the alkyl group, at least one -CH ₂ - may be substituted by -O-, and at least one -(CH ₂ ) ₂ - Can be substituted with -CH=CH-, and in these groups, at least one hydrogen can be substituted with fluorine or chlorine. [Effect of invention]

The first advantage of the present invention is to provide a compound having high chemical stability, high ability to align liquid crystal molecules, high polymerization reactivity by ultraviolet irradiation, and large voltage holding ratio when used in liquid crystal display elements At least one of them, and has high solubility in liquid crystal compositions. The second advantage is to provide a liquid crystal composition comprising the compound, which satisfies the requirements of high upper limit temperature of nematic phase, low lower limit temperature of nematic phase, low viscosity, suitable optical anisotropy, 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, which has a wide temperature range, short response time, high transmittance, high voltage holding ratio, low threshold voltage, large contrast ratio, long life, good vertical alignment, etc. at least one of the characteristics.

How to use the terms in this specification is as follows. The terms "liquid crystal compound", "liquid crystal composition", and "liquid crystal display element" may be abbreviated as "compound", "composition" and "element", respectively. "Liquid crystal compound" is a compound having a liquid crystal phase such as nematic phase and smectic phase, and a compound that does not have a liquid crystal phase but is added for the purpose of adjusting the physical properties of the composition such as upper limit temperature, lower limit temperature, viscosity, dielectric anisotropy, etc. The general term for the compounds. The compound usually has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod-like. The "polymerizable compound" is a compound added for the purpose of producing a polymer in the composition. The liquid crystal compound having an alkenyl group is not a polymerizable compound in its meaning. The "polar compound" assists the alignment of liquid crystal molecules through the interaction of polar groups with the surface of the substrate. A "liquid crystal display element" is a general term for a liquid crystal display panel, a liquid crystal display module, and the like.

The liquid crystal composition is usually prepared by mixing a plurality of liquid crystal compounds. To this composition, 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 defoamers. Even when an additive is added, the ratio (content) of the liquid crystal compound in the liquid crystal composition is represented by the weight percentage (% by weight) based on the weight of the liquid crystal composition not containing the additive. The ratio (addition amount) of the additive in the liquid crystal composition is represented by the weight percentage (% by weight) based on the weight of the liquid crystal composition not containing the additive. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total weight of the liquid crystal compound. Parts per million (ppm) by weight are also sometimes used. The exception is that 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 "clearing point" is the transition temperature between the liquid crystal phase and the isotropic phase in the liquid crystal compound. The "lower limit temperature of the liquid crystal phase" is the transition temperature of the solid-liquid crystal phase (smectic phase, nematic phase) in the liquid crystal compound. The "upper limit temperature of the nematic phase" is the transition temperature between the nematic phase and the isotropic phase in the mixture of the liquid crystal compound and the mother liquid crystal or the liquid crystal composition, and may be simply referred to as the "upper limit temperature". The "lower limit temperature of the nematic phase" is sometimes simply referred to as the "lower limit temperature". The expression "increase the dielectric anisotropy" or "large the dielectric anisotropy" means that the absolute value of the value is increased or large. "Large voltage retention ratio" means that the device has a large voltage retention ratio not only at room temperature, but also at a temperature close to the upper limit temperature in the initial stage, and after using the device for a long time, not only at room temperature, but also at It also has a large voltage holding ratio at a temperature close to the upper limit temperature. In a composition or element, characteristics may be investigated before and after a time-dependent change test (including an accelerated deterioration test). The expression "high solubility in a liquid crystal composition" means that the solubility is high in any of the compositions containing a liquid crystal compound at room temperature. The composition used in the evaluation was used as a standard.

The compound represented by formula (1) may be abbreviated as "compound (1)" in some cases. The compound (1) refers to one compound represented by the formula (1), a mixture of two compounds, or a mixture of three or more compounds. This rule also applies to at least one compound or the like selected from the group of compounds represented by formula (2). The symbols A ¹ , B ¹ , C ¹ , etc. surrounded by hexagons correspond to ring A ¹ , ring B ¹ , ring C ¹ , etc., respectively. The hexagon represents a six-membered ring such as a cyclohexane ring or a benzene ring, or a condensed ring such as a naphthalene ring. A straight line crossing one side of the hexagon indicates that any hydrogen on the ring may be substituted by groups such as -Sp ¹ -P ¹ . Subscripts such as f, g, h, 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", "independently" is not used because the subject is singular.

In the chemical formula of the compound, the notation of the terminal group R ¹¹ is used for a plurality of compounds, but the groups represented by R ¹¹ in these compounds may be respectively 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 tokens. In compound (8), when i is 2, two rings D ¹ exist. In this compound, the two groups represented by the two rings D ¹ may be the same or different. When i is greater than 2, it also applies to any two rings D ¹ . This rule also applies to other tokens.

The expression "at least one 'A'" means that the number of 'A's is arbitrary. The expression "at least one 'A' may be substituted with 'B'" includes the case of 'A' itself which is not substituted with 'B', the case of one 'A' substituted with 'B', the case of two or more 'A' In the case of substitution with 'B', among these, the position of 'A' substituted with 'B' is arbitrary. The rule that the substitution position is arbitrary also applies to the expression "at least one 'A' is substituted with 'B'". The expression "at least one A may be substituted by B, C, or D" is meant to include the case where A is unsubstituted, the case where at least one A is substituted by B, the case where at least one A is substituted by C, and the case where at least one A is substituted by D The case of substitution further includes the case where a plurality of A is substituted with at least two of B, C, and D. For example, an alkyl group in which at least one -CH ₂ - (or -CH ₂ CH ₂ -) may be substituted with -O- (or -CH=CH-) includes alkyl, alkenyl, alkoxy, alkoxyalkane group, alkoxyalkenyl, alkenyloxyalkyl. Furthermore, it is not good that two consecutive -CH ₂ - are substituted by -O- and become -OO-. In an alkyl group and the like, it is also unfavorable 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 having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in the alkyl and alkenyl groups, at least one -CH ₂ - may be substituted by -O- , in these groups, at least one hydrogen may be substituted by fluorine". In this expression, "in these bases" can be interpreted as a sentence. In this expression, "the groups" refer to alkyl, alkenyl, alkoxy, alkenyloxy, and the like. That is, "these bases" means all the bases described before the term "in these bases". This common-sense interpretation also applies to other terms.

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

The present invention includes the following items and the like.

Item 1. A compound represented by formula (1);

式（1-a）、式（1-b）、及式（1-c）中， Sp³ 及Sp⁴ 獨立地為單鍵或碳數1至15的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-、-OCO-、或-OCOO-取代，至少一個-(CH₂ )₂ -可經-CH=CH-或-C≡C-取代，該些基中，至少一個氫可經氟或氯取代； R³ 為氫、碳數1至10的烷基、碳數1至9的烷氧基、或碳數1至9的烷氧基烷基； X¹ 獨立地為-OH、-NH₂ 、-N(R⁴ )₂ 、-COOH、-SH、或-Si(R⁴ )₃ ； -N(R⁴ )₂ 、及-Si(R⁴ )₃ 中， R⁴ 為氫或碳數1至10的烷基，該烷基中，至少一個-CH₂ -可經-O-取代，至少一個-(CH₂ )₂ -可經-CH=CH-取代，該些基中，至少一個氫可經氟或氯取代。In formula (1), Ring A ¹ and Ring A ² are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,5-diyl , naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl base, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, Alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyloxy having 2 to 9 carbons, in which at least one hydrogen may be substituted by Fluorine or chlorine substitution; a is 0, 1, 2, or 3; Z ¹ is a single bond or an alkylene group having 1 to 10 carbon atoms, in the alkylene group, at least one -CH ₂ - may be through -O-, -CO-, -COO-, -OCO-, or -OCOO- substituted, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen Can be substituted by fluorine or chlorine; Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 15 carbon atoms, in the alkylene group, at least one -CH ₂ - can be replaced by -O-, -CO-, -COO-, -OCO-, or -OCOO- substituted, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by fluorine or Chlorine-substituted; M ¹ , M ² , M ³ , and M ⁴ are independently hydrogen, fluorine, chlorine, alkyl with 1 to 5 carbons, or alkane with 1 to 5 carbons in which at least one hydrogen is substituted with fluorine or chlorine group; R ¹ 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, among these groups, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by fluorine or chlorine; R ² is selected from formula (1-a), formula (1-b) ), and the base in the base represented by formula (1-c);

In formula (1-a), formula (1-b), and formula (1-c), Sp ³ and Sp ⁴ are independently a single bond or an alkylene group having 1 to 15 carbon atoms, and in the alkylene group, At least one -CH ₂ - can be substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, and at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡ C-substituted, among these groups, at least one hydrogen can be substituted by fluorine or chlorine; R ³ is hydrogen, alkyl with 1 to 10 carbons, alkoxy with 1 to 9 carbons, or alkoxy with 1 to 9 carbons alkoxyalkyl; X ¹ is independently -OH, -NH ₂ , -N(R ⁴ ) ₂ , -COOH, -SH, or -Si(R ⁴ ) ₃ ; -N(R ⁴ ) ₂ , and In -Si(R ⁴ ) ₃ , R ⁴ is hydrogen or an alkyl group having 1 to 10 carbon atoms, in the alkyl group, at least one -CH ₂ - may be substituted by -O-, and at least one -(CH ₂ ) ₂ - Can be substituted with -CH=CH-, and in these groups, at least one hydrogen can be substituted with fluorine or chlorine.

Item 2. The compound according to Item 1, wherein in formula (1), Z ¹ is a single bond, -(CH ₂ ) ₂ -, -(CH ₂ ) ₄ -, -CH=CH-, -C≡C -, -COO-, -OCO-, _-CF2O- , _-OCF2- , _-CH2O- , _-OCH2- , or -CF=CF-.

Item 3. The compound according to Item 1 or Item 2, wherein in formula (1), Ring A ¹ and Ring A ² are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1 ,4-phenylene, naphthalene-1,5-diyl, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5- Diyl, in these rings, at least one hydrogen may be fluorine, chlorine, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkoxy having 2 to 9 carbons 9 is substituted with an alkenyloxy group, and in these groups, at least one hydrogen may be substituted with 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);

式（1-a）、式（1-b）、及式（1-c）中， Sp³ 及Sp⁴ 獨立地為單鍵或碳數1至15的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-、-OCO-、或-OCOO-取代，至少一個-(CH₂ )₂ -可經-CH=CH-或-C≡C-取代，該些基中，至少一個氫可經氟取代； R³ 為氫、碳數1至7的烷基、碳數1至6的烷氧基、或碳數1至6的烷氧基烷基； X¹ 獨立地為-OH、-NH₂ 、或-SH。In formula (1-1) to formula (1-4), ring A ¹ , ring A ² , ring A ³ , and ring A ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexene 1,4-phenylene, naphthalene-1,5-diyl, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2 ,5-diyl, in these rings, at least one hydrogen can be fluorine, alkyl with 1 to 10 carbons, alkenyl with 2 to 10 carbons, alkoxy with 1 to 9 carbons, or carbon number 2 Alkenyloxy substitution to 9, in these groups, at least one hydrogen can be substituted by fluorine; Z ¹ , Z ² , and Z ³ are independently a single bond, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C-, -COO-, -OCO-, -CF2O-, _-OCF2- , _-CH2O- , _-OCH2- , or -CF ⁼ CF- _; Sp1 and ^Sp2 independently is a single bond or an alkylene group having 1 to 10 carbon atoms, in the alkylene group, at least one -CH ₂ - can be substituted by -O-, -COO-, or -OCO-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH-, among these groups, at least one hydrogen may be substituted by fluorine; M ¹ , M ² , M ³ , and M ⁴ are independently hydrogen, fluorine, and alkyl groups 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 ¹ is hydrogen, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkane group having 1 to 6 carbon atoms. Oxyalkyl, in these groups, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by fluorine; R ² 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 ³ and Sp ⁴ are independently a single bond or an alkylene group having 1 to 15 carbon atoms, and in the alkylene group, At least one -CH ₂ - can be substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, and at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡ C-substituted, among these groups, at least one hydrogen may be substituted by fluorine; R ³ is hydrogen, alkyl with 1 to 7 carbons, alkoxy with 1 to 6 carbons, or alkoxy with 1 to 6 carbons ylalkyl; X ¹ is independently -OH, -NH ₂ , or -SH.

Item 5. The compound of any one of Items 1 to 4, which is represented by any one of Formula (1-5) to Formula (1-7);

式（1-a）、及式（1-b）中， Sp³ 及Sp⁴ 獨立地為單鍵或碳數1至10的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-、-OCO-、或-OCOO-取代，至少一個-(CH₂ )₂ -可經-CH=CH-或-C≡C-取代，該些基中，至少一個氫可經氟取代； R³ 為氫、碳數1至7的烷基、碳數1至6的烷氧基、或碳數1至6的烷氧基烷基； X¹ 獨立地為-OH、-NH₂ 、或-SH。In formula (1-5) to formula (1-7), ring A ¹ , ring A ² , ring A ³ , and ring A ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexene group, 1,4-phenylene, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl, in these rings, at least one hydrogen can be through fluorine, Substituted with an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; Z ¹ , Z ² , and Z ³ are independently a single bond, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C-, -CH ₂ O-, or -OCH ₂ -; Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, the In the alkylene, at least one -CH ₂ - can be substituted by -O-, and at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH-; R ¹ is hydrogen, an alkyl group having 1 to 5 carbon atoms, An alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 1 to 4 carbon atoms; R ² is a group selected from the groups represented by formula (1-a) and formula (1-b);

In formula (1-a) and formula (1-b), Sp ³ and Sp ⁴ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ -may be Substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, these radicals In, at least one hydrogen can be substituted by fluorine; R ³ is hydrogen, alkyl with 1 to 7 carbons, alkoxy with 1 to 6 carbons, or alkoxyalkyl with 1 to 6 carbons; X ¹ is independent is -OH, _-NH2 , or -SH.

Item 6. The compound of any one of Items 1 to 5, which is represented by any one of Formula (1-8) to Formula (1-25);

In formula (1-8) to formula (1-25), R ¹ is hydrogen, methyl, ethyl, propyl, or -CH ₂ OCH ₃ ; R ³ 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; Z ¹ and Z ² are independently a single bond, -(CH ₂ ) ₂ -, or -CH=CH-; Sp ¹ , Sp ² , Sp ³ , and Sp ⁴ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be substituted by -O-; Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ , Y ⁸ , Y ⁹ , Y ¹⁰ , Y ¹¹ , and Y ¹² are independently hydrogen, fluorine, or an alkyl group having 1 to 5 carbons.

Item 7. The compound of any one of Items 1 to 6, which is represented by any one of Formula (1-26) to Formula (1-43);

In formula (1-26) to formula (1-43), Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , and Y ⁶ are independently hydrogen, fluorine, methyl, or ethyl; R ³ 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; 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 having 1 to 10 carbons, and in the alkylene, at least one -CH ₂ - may be substituted by -O-.

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

Item 9. The liquid crystal composition according to Item 8, comprising 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 having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in the alkyl and alkenyl groups, at least one -CH ₂ - may be substituted by -O-, in these groups, at least one hydrogen may be substituted by fluorine; Ring B ¹ , Ring B ² , Ring B ³ , and Ring B ⁴ are independently 1,4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, or pyrimidine-2,5-diyl; Z ¹¹ , Z ¹² , and Z ¹³ is independently a single bond, -COO-, -CH ₂ CH ₂ -, -CH=CH-, or -C≡C-.

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

In formulas (5) to (7), R ¹³ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in the alkyl and alkenyl groups, at least one -CH ₂ - may be through -O -Substituted, in these groups, at least one hydrogen may be substituted by fluorine; X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ , or -OCF ₂ CHFCF ₃ ; Ring C ¹ , Ring C ² , and Ring C ³ are independently 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is substituted with fluorine; Z ¹⁴ , Z ¹⁵ , and Z ¹⁶ are independently Ground is 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 11. The liquid crystal composition according to any one of Items 8 to 10, which contains at least one compound selected from the group of compounds represented by formula (8);

In formula (8), R ¹⁴ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Among the alkyl and alkenyl groups, at least one -CH ₂ - may be substituted by -O-, and these In the base, at least one hydrogen can be substituted by fluorine; X ¹² is -C≡N or -C≡CC≡N; Ring D ¹ is 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran -2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is substituted with fluorine; Z ¹⁷ is a single bond, -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, or -C≡C-; L ¹³ and L ¹⁴ is independently hydrogen or fluorine; i is 1, 2, 3, or 4.

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

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, and among the alkyl and alkenyl groups, at least One -CH ₂ - can be substituted by -O-, in these groups, at least one hydrogen can be substituted by fluorine, and R ¹⁷ can also be hydrogen or fluorine; Ring E ¹ , Ring E ² , Ring E ³ , and Ring E ⁴ is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, decalin-2,6- Diyl, or 1,4-phenylene in which at least one hydrogen is substituted with fluorine; Ring E ⁵ and Ring E ⁶ are independently 1,4-cyclohexylene, 1,4-cyclohexenyl, 1,4 -phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl; Z ¹⁸ , Z ¹⁹ , Z ²⁰ , and Z ²¹ are independently a single bond, -COO- , _-OCO- , _-CH2O- , _-OCH2- , _-CF2O- , _{-OCF2- , -CH2CH2- , -CF2OCH2CH2-} , _{or -OCF2CH2CH 2-} ; L ¹⁵ and L ¹⁶ are independently fluorine or chlorine; S ¹¹ is hydrogen or methyl; X is -CHF- or -CF ₂ -; j, k, m, n, p, q, r, and s are independently 0 or 1, and the sum of k, m, n, and p is 1 or 2, the sum of q, r, and s is 0, 1, 2, or 3, and t is 1, 2, or 3.

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

In formula (20), ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxanyl Alkyl-2-yl, pyrimidin-2-yl, or pyridin-2-yl, in these rings, at least one hydrogen may be replaced by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, 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, in these rings, at least one hydrogen may be substituted by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is substituted by halogen; Z ²² and Z ²³ are independently mono A 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-, or -OCO-, and at least one -CH ₂ CH ₂ - may be substituted by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )-, or -C(CH ₃ )=C(CH ₃ )-, in which , at least one hydrogen can be substituted by fluorine or chlorine; P ¹¹ , P ¹² , and P ¹³ are independently polymerizable groups; Sp ¹¹ , Sp ¹² , and Sp ¹³ are independently a single bond or an alkylene having 1 to 10 carbon atoms 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 may be substituted with fluorine or chlorine; u is 0, 1, or 2; f, g, and h are independently 0, 1, 2, 3, or 4 , and the sum of f, g, and h is 1 or more.

Item 14. The liquid crystal composition according to Item 13, wherein in formula (20), P ¹¹ , P ¹² , and P ¹³ are independently represented by formulas (P-1) to (P-5) a group in the group of polymerizable groups;

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

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

式（P-1）至式（P-3）中， M¹¹ 、M¹² 、及M¹³ 獨立地為氫、氟、碳數1至5的烷基、或至少一個氫經鹵素取代的碳數1至5的烷基。In formula (20-1) to formula (20-7), L ³¹ , L ³² , L ³³ , L ³⁴ , L ³⁵ , L ³⁶ , L ³⁷ , and L ³⁸ are independently hydrogen, fluorine, or methyl; Sp ¹¹ , Sp ¹² , and Sp ¹³ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be via -O-, -COO-, -OCO- , or -OCOO- substituted, at least one -CH ₂ CH ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by fluorine or chlorine; P ¹¹ , P ¹² , and P ¹³ is independently a group selected from the group of polymerizable groups represented by formula (P-1) to formula (P-3),

In formula (P-1) to formula (P-3), M ¹¹ , M ¹² , and M ¹³ are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or a carbon number in which at least one hydrogen is substituted by halogen 1 to 5 alkyl groups.

Item 16. The liquid crystal composition according to any one of items 8 to 15, comprising a polymerizable compound, a polymerization initiator, a polymerization inhibitor, a polymerizable compound different from the compound represented by the formula (1) or the formula (20), At least one of the group of optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, pigments, and antifoaming agents.

Item 17. A liquid crystal display element comprising a product selected from the group consisting of the liquid crystal composition described in any one of items 8 to 16 and at least a part of the liquid crystal composition described in any one of items 8 to 16 polymerized at least one of the groups.

The present invention also includes the following items. (a) Further containing at least two kinds of additives such as polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, pigments, and antifoaming agents the liquid crystal composition. (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 the compound (1) and the compound (20) to the liquid crystal composition. (d) A liquid crystal composite prepared by polymerizing the polymerizable composition. (e) A polymer-stabilized alignment-type device containing the liquid crystal composite. (f) preparing a polymerizable composition by adding compound (1) and compound (20), and a polymerizable compound different from compound (1) or compound (20) to the liquid crystal composition, by using the A polymer-stabilized alignment-type element prepared from a polymerizable composition.

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

1. The aspect of compound (1) The compound (1) of the present invention is characterized by having a mesogen moiety composed of at least one ring, at least one polar group, and two or more polymerizable groups, and is characterized by being polymerizable on the side opposite to the polar group in particular base. 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 bond manner. One of the applications is an additive for a liquid crystal composition used in a liquid crystal display element, and in this application, the compound (1) is added for the purpose of controlling the alignment of liquid crystal molecules. Such an additive is preferably chemically stable under the condition of being sealed in the element, and has a high ability to align liquid crystal molecules, a high voltage holding ratio when used in a liquid crystal display element, and a high solubility in a liquid crystal composition. Compound (1) satisfies such characteristics to a large extent, and has a large solubility in liquid crystal compositions that cannot be achieved with conventional compounds, and by using this compound (1), compared with the case of using conventional compounds, A device excellent in long-term stability can be easily obtained in a state in which the orientation or voltage retention is maintained at the same level or more.

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

Ring A ¹ and Ring A ² are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,5-diyl, naphthalene-2,6 -diyl, decalin-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3- Dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, carbon number 1 to 10 Alkyl, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyloxy having 2 to 9 carbons are substituted, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine.

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

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

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

Particularly preferred ring A ¹ and ring A ² are 1,4-cyclohexylene, 1,4-phenylene, 2-substituted 1,4-phenylene, 3-substituted 1,4-phenylene, or 2- and 3-position substituted 1,4-phenylene groups, the substituents are preferably hydrogen, fluorine, alkyl with 1 to 5 carbons, alkenyl with 2 to 5 carbons, or alkane with 1 to 4 carbons Oxy group, more preferably hydrogen, fluorine, methyl, or ethyl.

Ring A ¹ and Ring A ² are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene with at least one hydrogen substituted with fluorine, at least one hydrogen with carbon number 1 to 5 The chemical stability of the alkyl-substituted 1,4-phenylene, decalin-2,6-diyl, or tetrahydropyran-2,5-diyl compounds is high. Ring A ¹ and Ring A ² are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is substituted with fluorine , 1,4-phenylene substituted at least one hydrogen by an alkyl group having 1 to 5 carbon atoms, or 1,4-phenylene substituted at least one hydrogen by an alkenyl group having 2 to 5 carbon atoms in a liquid crystal composition High solubility in matter. Ring A ¹ and Ring A ² are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is substituted with an alkyl group having 1 to 2 carbon atoms. The ability of liquid crystal molecules to align is high. Ring A ¹ and Ring A ² are independently 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is substituted with an alkyl group having 1 to 5 carbon atoms, and at least one hydrogen is substituted with an alkyl group having 1 to 4 carbon atoms. Alkoxy-substituted 1,4-phenylene, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl compounds have high polymerization reactivity by ultraviolet irradiation

a is 0, 1, 2, or 3, preferably 0, 1, or 2, and particularly preferably 1 or 2.

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

Z ¹ is a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be via -O-, -CO-, -COO-, -OCO-, or -OCOO- Substitution, at least one -(CH ₂ ) ₂ - may be substituted with -CH=CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine.

Preferred Z ¹ is a single bond, -(CH ₂ ) ₂ -, -(CH ₂ ) ₄ -, -CH=CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O- , _-OCF2- , _-CH2O- , _-OCH2- , or -CF=CF-. More preferably Z ¹ is a single bond, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, or -CF=CF-. Further preferred Z ¹ is a single bond, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C-, -CH ₂ O-, or -OCH ₂ -, and particularly preferred Z ¹ is a single bond or -(CH ₂ ) ₂ -, the best Z ¹ is a single bond.

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

Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 15 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be through -O-, -CO-, -COO-, -OCO -, or -OCOO-, at least one -(CH ₂ ) ₂ - may be substituted with -CH=CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine.

The chemical stability of the compound in which Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 7 carbon atoms is high. A compound in which Sp ¹ and Sp ² are independently a C1-7 alkylene group or at least one _-CH2 --O-substituted group of a C1-7 alkylene group in a liquid crystal composition of high solubility.

More preferably Sp ¹ and Sp ² 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-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH-.

In terms of becoming a compound having more excellent solubility in the liquid crystal composition, it is particularly preferred that Sp ¹ is a single bond or an alkylene group having 1 to 5 carbon atoms, and in the alkylene group, at least one -CH ₂ - Can be substituted by -O-; Sp ² is a single bond or an alkylene group having 1 to 5 carbon atoms, and at least one -CH ₂ - of the alkylene group can be substituted by -O-, further preferably -CH ₂ -, - (CH ₂ ) ₂ -, or -(CH ₂ ) ₃ -.

M ¹ , M ² , M ³ , and M ⁴ are independently hydrogen, fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms wherein at least one hydrogen is substituted with fluorine or chlorine, and Preferably, it is hydrogen, fluorine, an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms in which at least one hydrogen is substituted by fluorine. More preferably, it is hydrogen.

R ¹ 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, among these groups, at least one -(CH ₂ ) ₂ - may be substituted with -CH=CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine.

Preferred R ¹ is hydrogen, alkyl with 1 to 5 carbons, alkoxy with 1 to 4 carbons, or alkoxyalkyl with 1 to 4 carbons, among these groups, at least one -(CH ₂ ) _2- may be substituted by -CH=CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted by fluorine or chlorine. Further preferred R ¹ is hydrogen, methyl, ethyl, butyl, methoxymethyl, methoxyethyl, ethoxymethyl, or ethoxyethyl. ^Particularly preferred R1 is hydrogen, methyl, or methoxymethyl.

The chemical stability of 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 is high. The compound in which R ¹ is an alkyl group having 1 to 15 carbons, an alkenyl group having 2 to 15 carbons, or an alkenyloxy group having 2 to 14 carbons has high solubility in the liquid crystal composition. The compound in which R ¹ is an alkyl group having 1 to 15 carbon atoms has a high ability to align liquid crystal molecules.

R ² is a group selected from groups represented by formula (1-a), formula (1-b), and formula (1-c).

Desirable R ² is the formula (1-a) or the formula (1-b). The compound in which R ² is the formula (1-a) has a high solubility in the liquid crystal composition. The compound in which R ² is the formula (1-a) or the formula (1-c) has a high ability to align liquid crystal molecules. R ² is the compound of formula (1-b), which has a high solubility in a liquid crystal composition and a high ability to align liquid crystal molecules.

Sp ³ and Sp ⁴ are independently a single bond or an alkylene group having 1 to 15 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be via -O-, -CO-, -COO-, -OCO- , or -OCOO- substituted, at least one -(CH ₂ ) ₂ - may be substituted with -CH=CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine.

Preferred Sp ³ and Sp ⁴ are single bonds, straight-chain alkylenes with 1 to 10 carbon atoms, or branched alkylenes with 3 to 10 carbons, and in these alkylenes, at least one -CH ₂ - Can be substituted by -O-, -CO-, or -COO-, 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 or chlorine. Further preferred Sp ³ and Sp ⁴ are a single bond, a straight-chain alkylene with 1 to 10 carbons, or a branched alkylene with 3 to 10 carbons, and in these alkylenes, at least one -CH ₂ - May be substituted with -O-, at least one -(CH ₂ ) ₂ - may be substituted with -CH=CH-, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine. Particularly preferred Sp ³ and Sp ⁴ are single bonds, straight-chain alkylene groups with 1 to 10 carbon atoms, or branched chain alkylene groups with 3 to 10 carbon atoms, and in these alkyl groups, at least one -CH ₂ - Can be substituted by -O-.

Compounds in which Sp ³ and Sp ⁴ are independently branched alkyl groups have high solubility in the liquid crystal composition. Compounds in which Sp ³ and Sp ⁴ are independently a linear alkyl group having 1 to 10 carbon atoms or a linear alkoxyalkyl group having 1 to 10 carbon atoms have a high ability to align liquid crystal molecules.

R ³ is hydrogen, an alkyl group having 1 to 10 carbons, an alkoxy group having 1 to 9 carbons, or an alkoxyalkyl group having 1 to 9 carbons.

Preferred R ³ is hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or alkoxyalkyl having 1 to 9 carbons. More preferable R ³ is hydrogen or an alkyl group having 1 to 4 carbon atoms, in terms of becoming a compound having more excellent solubility in the liquid crystal composition, high chemical stability, and high ability to align liquid crystal molecules.

X ¹ is -OH, -NH ₂ , -N(R ⁴ ) ₂ , -COOH, -SH, or -Si(R ⁴ ) ₃ . Desirable X ¹ is -OH, -NH ₂ , or -SH, and particularly preferred X ¹ is -OH in terms of becoming a compound having more excellent solubility in the liquid crystal composition. Here, R ⁴ is hydrogen or an alkyl group having 1 to 10 carbon atoms, in the alkyl group, at least one -CH ₂ - may be substituted by -O-, and at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH -Substituted, in these groups, at least one hydrogen may be replaced by fluorine or chlorine.

The compound in which X ¹ is -OH, -NH ₂ , or -SH has a high ability to align liquid crystal molecules. Compounds in which X ¹ is -OH have high chemical stability, high ability to align liquid crystal molecules, high voltage retention when used in liquid crystal display elements, and high solubility in liquid crystal compositions.

Examples of preferable compound (1) are compound (1-1) to compound (1-4) described in item 4. More preferable examples of compound (1) are compound (1-5) to compound (1-7) described in item 5. Further preferred examples of the compound (1) are the compounds (1-8) to (1-25) described in the item 6. Examples of the most preferable compound (1) are the compound (1-26) to the compound (1-43) described in item 7.

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

2-1. Generation of Bonding Group An example of a method for generating the bonding group in compound (1) is shown in the following scheme. In this scheme, MSG ¹ (or MSG ² ) is a monovalent organic group having at least one ring. The monovalent organic groups represented by a plurality of MSG ¹ (or MSG ² ) may be the same or different. Compound (1A) to compound (1H) correspond to compound (1) or an intermediate of compound (1).

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

(II) Generation of -COO- and -OCO- The carboxylic acid (24) is obtained by reacting compound (23) with n-butyllithium and then reacting with carbon dioxide. The carboxylic acid (24) was prepared in the presence of 1,3-dicyclohexylcarbodiimide (DCC) and 4-dimethylamino pyridine (DMAP). ) with an alcohol (25) derived from compound (21) to synthesize compound (1B) having -COO-. Compounds with -OCO- were also synthesized using this method.

(III) Production of -CF ₂ O- and -OCF ₂ - Compound ( 26 ) is obtained by sulfurizing compound ( 1B ) with Lawesson's reagent. Compound (1C) with -CF ₂ O- was synthesized by fluorination of compound (26) with hydrogen fluoride pyridine complex and N-bromosuccinimide (NBS). See M. Kuroboshi et al., "Chem. Lett." 1992, No. 827. Compound (1C) can also be synthesized by fluorination of compound (26) with (diethylamino)sulfur trifluoride (DAST). See WH Bunnelle et al., J. Org. Chem., 1990, vol. 55, p. 768. Compounds with -OCF ₂ - can also be synthesized by this method.

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

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

(VI) Generation of -C≡C- Compound (23) was reacted with 2-methyl-3-butyn-2-ol in the presence of catalysts of dichloropalladium and copper iodide, followed by deprotection under basic conditions to obtain compound (29). ). Compound (1F) is synthesized by reacting compound (29) with compound (22) in the presence of a catalyst of dichlorobis(triphenylphosphine)palladium and copper halide.

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

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

2-2. Formation of Ring A ¹ and Ring A ² About 1,2-cyclopropylidene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1 ,4-cycloheptene, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2, 3,4-Tetrahydronaphthalene-2,6-diyl, Tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, Pyrimidine-2,5-diyl , pyridine-2,5-diyl and other rings, starting materials are commercially available, or synthetic methods are widely known.

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

In formula (1), R ² is formula (1-a), Sp ³ is -CH ₂ -, M ¹ , M ² , M ³ , and M ⁴ are hydrogen, R ¹ is methyl, and X ¹ is -OH The compound (1-61) can be synthesized by the following method. Compound (54) is obtained by reacting compound (53) with formaldehyde in the presence of 1,4-diazabicyclo[2.2.2]octane (1,4-diazabicyclo[2.2.2]octane, DABCO). ). Compound (55) is obtained by reacting compound (54) with 3,4-dihydro-2H-pyran in the presence of pyridinium p-toluenesulfonate (Pyridinium p-Toluenesulfonate, PPTS). Compound (56) is obtained by hydrolyzing compound (55) using lithium hydroxide. Compound (59) is obtained by reacting diol (57) synthesized by a known method with compound (58) in the presence of DCC and DMAP. Compound (1-61) can be derived by reacting compound (59) with compound (56) in the presence of DCC and DMAP to obtain compound (60), followed by deprotection using PPTS.

In formula (1), R ² is formula (1-a), Sp ³ is -(CH ₂ ) ₂ -, M ¹ , M ² , M ³ , and M ⁴ are hydrogen, R ¹ is methyl, and X ¹ The compound (1-63) which is -OH can be synthesized by the following method. Compound (62) is obtained by allowing phosphorus tribromide to act on compound (1-61). Next, compound (1-63) can be derived by allowing indium to act on compound (62) and then reacting with formaldehyde.

In formula (1), R ² is formula (1-a), Sp ³ is -CH ₂ O(CH ₂ ) ₂ -, M ¹ , M ² , M ³ , and M ⁴ are hydrogen, and R ¹ is methyl The compound (1-64) in which X ¹ is -OH can be synthesized by the following method. Compound (1-64) can be derived by reacting trifluoromethanesulfonic anhydride (Tf ₂ O) and triethylamine (Et ₃ N) with compound (1-61) and then reacting with ethylene glycol.

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

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

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

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

As the content of component B increases, the dielectric anisotropy of the composition decreases, but the viscosity decreases. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the content of the component B is preferably as large as possible. The content of Component B is preferably 30% by weight or more, more preferably 40% by weight or more, based on 100% by weight of the liquid crystal composition, and the upper limit is not particularly limited, but is, for example, 99.95% by weight.

Component C is a compound having fluorine, chlorine or a fluorine-containing group at at least one terminal. Composition C has a large positive dielectric anisotropy. Preferable examples of component C include compound (5-1) to compound (5-16), compound (6-1) to compound (6-116), compound (7-1) to compound (7-59) ). In the compound of component C, R ¹³ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in the alkyl and alkenyl groups, at least one -CH ₂ - may be substituted by -O-, at least _{One hydrogen} may be substituted with fluorine _; X11 is fluorine, chlorine, _-OCF3 , _-OCHF2 , _-CF3 , _-CHF2 , ^-CH2F , _-OCF2CHF2 , or _-OCF2CHFCF3 .

Component C has a positive dielectric anisotropy and has very good stability to heat, light, and the like, and is therefore suitable for use in the preparation of compositions for modalities such as IPS, FFS, and OCB. The content of Component C relative to 100% by weight of the liquid crystal composition is preferably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, and more preferably in the range of 40% by weight to 95% by weight . When adding Component C to a composition having a negative dielectric anisotropy, the content of Component C is preferably 30 wt % or less with respect to 100 wt % of the liquid crystal composition. By adding component C, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the device can be adjusted.

Component D is a compound (8) whose single terminal group is -C≡N or -C≡CC≡N. Component (D) has a cyano group and therefore has a positive larger dielectric anisotropy. Preferred examples of component D include compound (8-1) to compound (8-64). In the compound of component D, R ¹⁴ is an alkyl group having ₁ to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. One hydrogen may be replaced by fluorine; X ¹² is -C≡N or -C≡CC≡N.

Since the dielectric anisotropy of Component D is positive and its value is large, it is mainly used when preparing a composition for modes such as TN. By adding this component D, the dielectric anisotropy of the composition can be increased. Component D has the effect of expanding the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. Component D is also useful for adjusting the voltage-transmittance curve of the element.

The content of Component D relative to 100% by weight of the liquid crystal composition is suitably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, and more preferably in the range of 40% by weight to 95% by weight . When the component D is added to a composition having negative dielectric anisotropy, the content of the component D is preferably 30% by weight or less with respect to 100% by weight of the liquid crystal composition. By adding component D, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the device can be adjusted.

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

The dielectric anisotropy of the component E is negative and large. Component E is suitable for use in the preparation of compositions for modalities such as IPS, VA, and PSA. As the content of component E increases, the dielectric anisotropy of the composition increases negatively, but the viscosity increases. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the smaller the content, the better. Considering that the dielectric anisotropy is about -5, the content of Component E relative to 100 wt % of the liquid crystal composition is preferably 40 wt % or more in order to perform sufficient voltage driving.

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

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

By appropriate combination of the above-mentioned component B, component C, component D and component E, the following liquid crystal composition can be prepared, which satisfies the requirements of high upper limit temperature, low minimum temperature, low viscosity, suitable optical anisotropy, positive or negative At least one of the characteristics of large dielectric anisotropy, large specific resistance, high stability to ultraviolet rays, high stability to heat, and large elastic constant.

3-2. Additives The liquid crystal composition is prepared by a known method. For example, a method in which the components are mixed and heated to be dissolved in each other is exemplified. Additives may be added to the composition according to the application. Examples of additives are polymerizable compounds other than compound (1), polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, pigments, antifoaming agents, and the like. Such additives are well known to those skilled in the art and are described in the literature.

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

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

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

Preferred Ring F or Ring I is cyclohexyl, cyclohexenyl, phenyl, fluorophenyl, difluorophenyl, 1-naphthyl, or 2-naphthyl. Further 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 may be changed to halogen, alkyl having 1 to 12 carbons , an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted by halogen.

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

In formula (20), Z ²² and Z ²³ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be through -O-, -CO-, - COO-, or -OCO- substituted, at least one -CH ₂ CH ₂ - may be via -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )-, or -C(CH ₃ )=C(CH ₃ )-substituted, in these groups, at least one hydrogen may be substituted with 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-. Further preferable Z ²² or Z ²³ is a single bond.

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

In formula (P-1) to formula (P-5), M ¹¹ , M ¹² , and M ¹³ are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or a carbon number in which at least one hydrogen is substituted by halogen 1 to 5 alkyl groups. In order to improve reactivity, preferable M ¹¹ , M ¹² , or M ¹³ is hydrogen or methyl. Further preferred M ¹¹ is hydrogen or methyl, and further 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, and in the alkylene group, at least one -CH ₂ - may be via -O-, - COO-, -OCO-, or -OCOO- substituted, at least one -CH ₂ CH ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by fluorine or chlorine . Preferred Sp ¹¹ , Sp ¹² , or Sp ¹³ are single bonds.

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

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

Preferable examples of compound (20) are compound (20-1) to compound (20-7) described in Item 15, and more preferable examples are compound (20-8) to compound (20-11). Further 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, R ³² , R ³³ , and R ³⁴ At least one of which is an alkyl group with 1 to 5 carbon atoms; v, and x are independently 0 or 1; t and u are independently an integer from 1 to 10, and t+v and x+u are respectively a maximum of 10; L ³¹ and L ³⁶ is 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 at the time of polymerization, the amount of the remaining polymerizable compound can be reduced. Examples of photo-radical polymerization initiators include TPO, 1173, and 4265 in the Darocur series of BASF, and 184, 369, and 500 in the Irgacure series. , 651, 784, 819, 907, 1300, 1700, 1800, 1850, and 2959.

Additional examples of photo-radical polymerization initiators are 4-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(4-butoxystyryl)-5-trichloro Methyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzophenazine, benzophenone/Michler's ketone mixture, hexaarylbiimidazole/ mercaptobenzimidazole mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, benzil dimethyl ketal, 2-methyl-1-[4 -(Methylthio)phenyl]-2-morpholinopropan-1-one, 2,4-diethylxanthone/methyl p-dimethylaminobenzoate mixture, benzophenone/ Methyl triethanolamine mixture.

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

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

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

Antioxidants are effective for 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 (Irganox) 1010, Irganox (Irganox) 1035, Irganox (Irganox) 3114 and Irganox (Irganox) 1098 (trade name; BASF (BASF) company). The ultraviolet absorber is effective in preventing the lowering of the upper limit temperature. Preferable examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives, and the like, and specific examples include the following compounds (AO-3) and compounds (AO-4) ); Tinuvin 329, Tinuvin P, Tinuvin 326, Tinuvin 234, Tinuvin 213, Tinuvin 400, Tinuvin 328 and Tinuvin 99-2 (trade names; BASF Corporation); and 1,4-diazabicyclo[2.2.2]octane (DABCO).

Light stabilizers such as sterically hindered amines are preferred for maintaining a large voltage holding ratio. Preferred examples of the light stabilizer include the following compound (AO-5), compound (AO-6), compound (AO-7), compound (AO-8), and compound (AO-9) ; Tinuvin 144, Tinuvin 765, Tinuvin 770DF, Tinuvin 780 (trade name; BASF); LA-52, LA-57 , LA-77Y, and LA-77G (trade name; ADEKA). A thermal stabilizer is also effective in maintaining a large voltage holding ratio, and as a preferable example, Irgafos 168 (trade name; BASF) can be mentioned. Dichroic dyes such as azo-based dyes, anthraquinone-based dyes, and the like are added to the composition in order to be suitable for a guest host (GH) mode device. Antifoaming agents are effective in preventing foaming. Preferred examples of the defoaming agent are dimethyl silicone oil, methyl phenyl silicone oil, and the like.

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 1 to 20 alkyl groups. In compound (AO-2) and compound (AO-5), R ⁴² is an alkyl group having 1 to 20 carbon atoms. In compound (AO-5), R ⁴³ is hydrogen, methyl or O ⁽ oxygen radical); ring G ¹ is 1,4-cyclohexylene or 1,4-phenylene; compound (AO-7) and compound (AO-8), ring G ² is 1,4-cyclohexylene, 1,4-phenylene, or 1,4-phenylene with at least one hydrogen substituted by fluorine; compound (AO-5 ), compound (AO-7), and compound (AO-8), z is 1, 2, or 3.

4. Liquid crystal display element The liquid crystal composition can be suitably used for a liquid crystal display element which has operation modes such as PC, TN, STN, OCB, and PSA, and is driven by an active matrix method. This composition can also be suitably used for a liquid crystal display element which has operation modes such as PC, TN, STN, OCB, VA, and IPS and is driven by a passive matrix method. These elements can also be applied to any type of reflection type, transmission type and semi-transmission type.

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

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

In this sequence, polar compounds are aligned on the substrate due to the interaction of polar groups with the substrate surface. The polar compound aligns liquid crystal molecules. When a plurality of polar groups are present, the interaction with the substrate surface is further enhanced, 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. Accompanying this alignment, the polymerizable compound is also aligned. In this state, the polymerizable compound is polymerized by the ultraviolet rays, and thus a polymer that maintains the alignment is produced. Due to the effect of the polymer, the alignment of the liquid crystal molecules is further stabilized, so that the response time of the device is shortened. The afterimage of the image is caused by the poor operation of the liquid crystal molecules, so the afterimage is also improved by the effect of the polymer. Compound (1) is polymerizable, and is therefore 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 having 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, so there is a case where a polymerizable compound without a polar group is not necessary. [Example]

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

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

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

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

High Performance Liquid Chromatography (HPLC) analysis: Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used for the measurement. For the column, YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle diameter 5 μm) manufactured by YMC (Stand) was used. The precipitate is used by appropriately mixing acetonitrile and water. As a detector, an ultraviolet (Ultraviolet, UV) detector, a refractive index (Reflective Index, RI) detector, a corona detector (CORONA detector), etc. are used suitably. In the case of using a UV detector, the detection wavelength was set to 254 nm. The sample was dissolved in acetonitrile to prepare a 0.1% by weight solution, and 1 μL of this solution was introduced into the sample chamber. As a recorder, C-R7Aplus manufactured by Shimadzu Corporation was used.

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

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

Measurement method: The measurement of the characteristic was carried out by the following method. Most of these methods are methods described in the JEITA standard (JEITA·ED-2521B) reviewed and formulated by the Japan Electronics and Information Technology Industries Association (JEITA) or modified methods. A thin film transistor (TFT) was not mounted in the TN element used for the measurement.

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

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

Crystals are denoted as C. When distinguishing the kind of crystal, it is represented by C ₁ and C ₂ , respectively. Denote the smectic phase as S and the nematic phase as N. Among the smectic phases, when the smectic A phase, the smectic B phase, the smectic C phase, or the smectic F phase are distinguished, they are represented as S _A , S _B , S _C , or _SF , respectively. Liquid (isotropic) is denoted I. The transition temperature is expressed as "C 50.0 N 100.0 I", for example. It means that the transition temperature from crystalline to nematic phase is 50.0°C, and the transition temperature from nematic phase to liquid is 100.0°C.

(3) Upper limit temperature of nematic phase (T _NI or NI; °C) The sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope, and heated at a rate of 1 °C/min. The temperature at which a part of the sample changes from a nematic phase to an isotropic liquid is measured. The upper limit temperature of the nematic phase is sometimes abbreviated as "upper limit temperature". When the sample is a mixture of compound (1) and mother liquid crystal, it is represented by the symbol 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) Minimum temperature of nematic phase (TC; ° _C ) Samples having nematic phase were stored in freezers at 0°C, -10°C, -20°C, -30°C, and -40°C for 10 days After that, the liquid crystal phase was observed. For example, when the sample is in the state of a nematic phase at -20°C and changes to a crystalline or smectic phase at -30°C, the T _C is described as ≦-20°C. The lower limit temperature of the nematic phase is sometimes abbreviated as "lower limit temperature".

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

(6) Optical anisotropy (refractive index anisotropy; measured at 25°C; Δn) The measurement was performed using light having a wavelength of 589 nm with an Abbe refractometer with a polarizing plate attached to the eyepiece. After rubbing the surface of the main mold in one direction, drop the sample onto the main mold. The refractive index (n∥) was measured when the direction of the polarized light was parallel to the direction of rubbing. The refractive index (n⊥) was measured when the direction of the polarized light was perpendicular to the direction of rubbing. The value of optical anisotropy (Δn) is calculated according to the formula of Δn=n∥-n⊥.

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

The method for measuring properties may be different between a sample with positive dielectric anisotropy and a sample with negative dielectric anisotropy. The measurement method when the dielectric anisotropy is positive is described in items (8a) to (12a). The case where the dielectric anisotropy is negative is described in the items (8b) to (12b).

(8a) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s) Positive dielectric anisotropy: measured according to the method described in "Molecular Crystals and Liquid Crystals", No. 259, p. 37 (1995) by M. Imai et al. . The sample was placed in a TN device with a twist angle of 0 degrees and a gap (cell gap) between two glass substrates of 5 μm. A voltage was applied to the element stepwise in the range of 16 V to 19.5 V in steps of 0.5 V. After the voltage was not applied for 0.2 seconds, the voltage was repeatedly applied under the conditions of only one square wave (square pulse; 0.2 seconds) and no application (2 seconds). The peak current (peak current) and peak time (peak time) of the transient current (transient current) generated by the application were measured. The value of rotational viscosity was obtained from these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al. The value of the dielectric anisotropy required for the calculation was obtained by the method described below using the element for which the rotational viscosity was measured.

(8b) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s) Negative dielectric anisotropy: Measured according to the method described in M. Imai et al., "Molecular Crystals and Liquid Crystals" No. 259, p. 37 (1995) . The sample was placed in a VA element with a gap (cell gap) between two glass substrates of 20 μm. A voltage was applied to the element stepwise by 1 volt in the range of 39 volts to 50 volts. After the voltage was not applied for 0.2 seconds, the voltage was repeatedly applied under the conditions of only one square wave (square pulse; 0.2 seconds) and no application (2 seconds). The peak current (peak current) and peak time (peak time) of the transient current (transient current) generated by the application were measured. The value of rotational viscosity was obtained from these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al. The dielectric anisotropy required for this calculation is the value measured in the following section of the dielectric anisotropy.

(9a) Dielectric anisotropy (Δε; measured at 25°C) Positive dielectric anisotropy: The sample was placed in a TN element with a gap (cell gap) between two glass substrates of 9 μm and a twist angle of 80 degrees. A sine wave (10 V, 1 kHz) was applied to this element, and after 2 seconds, the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecules was measured. A sine wave (0.5 V, 1 kHz) was applied to this element, and 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 of 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 constants (ε∥ and ε⊥) were measured as follows. 1) Determination of dielectric constant (ε∥): A solution of octadecyltriethoxysilane (0.16 ml) in ethanol (20 ml) was coated on a fully cleaned glass substrate. After rotating the glass substrate with a spinner, it heated at 150° C. for 1 hour. The sample was placed in a VA element having a distance (cell gap) between two glass substrates of 4 μm, and the element was sealed with an adhesive cured by ultraviolet rays. A sine wave (0.5 V, 1 kHz) was applied to this element, and the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecules was measured after 2 seconds. 2) Determination of dielectric constant (ε⊥): apply a polyimide solution on the fully cleaned glass substrate. After the glass substrate was fired, the obtained alignment film was subjected to a rubbing treatment. The sample was injected into a TN device with a gap (cell gap) between two glass substrates of 9 μm and a twist angle of 80 degrees. A sine wave (0.5 V, 1 kHz) was applied to this element, and 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: An LCR meter HP4284A manufactured by Agilent Technologies Inc. was used for the measurement. The sample was placed in a horizontal alignment element with an interval (cell gap) of 20 μm between two glass substrates. An electric charge of 0 volt to 20 volts was applied to this element, and the electrostatic capacitance and the applied voltage were measured. Using equations (2.98) and (2.101) in the "Handbook of Liquid Crystal Devices" (Nikkan Kogyo Shimbun) on page 75, the measured electrostatic capacitance (C) and the value of the applied voltage (V) were fitted (fitting), The values of K ₁₁ and K ₃₃ are obtained according to the formula (2.99). Next, in equation (3.18) on page 171, K ₂₂ is calculated using the values of K ₁₁ and K ₃₃ obtained just now. The elastic constant K is represented by the average value of K ₁₁ , K ₂₂ and K ₃₃ obtained in the above-described manner.

(10b) Elastic constants (K ₁₁ and K ₃₃ ; measured at 25° C.; pN) Negative dielectric anisotropy: EC-1 type elastic produced by Toyo Technica Co., Ltd. was used for the measurement Constant measurer. The sample was placed in a vertical alignment element with a gap (cell gap) of 20 μm between two glass substrates. An electric charge of 20 volts to 0 volts was applied to this element, and the electrostatic capacitance and the applied voltage were measured. Use equations (2.98) and (2.101) in "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun) on page 75 to fit the values of electrostatic capacitance (C) and applied voltage (V), and use equation (2.100) Obtain the value of the elastic constant.

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

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

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

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

(13) Voltage holding ratio The polymerizable compound was polymerized by irradiating ultraviolet rays using black light and F40T10/BL (peak wavelength: 369 nm) manufactured by EyeGraphics Co., Ltd. The element was charged by applying a pulse voltage (1 V, 60 microseconds) at 60°C. The decaying voltage was measured with a high-speed voltmeter for a period of 16.7 seconds, and the area A between the voltage curve and the horizontal axis in a unit cycle was obtained. Area B is the area without attenuation. Voltage retention is expressed as the 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%), marketed from Japan Alcohol Trading) (shares).

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

Step 1 Compound (T-1) (40 g), triethylamine (33.7 ml) and DMF (3000 ml) were put into a reactor and cooled to 0°C. Compound (T-2) (23.2 g) was added thereto, returned to room temperature and stirred for 12 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with brine, and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=1:1) to obtain Compound (T-3) (2.7 g; 5%).

Step 2 Compound (T-3) (5.0 g), compound (T-4) (4.2 g), DMAP (1.2 g), and dichloromethane (55.0 ml) were put into a reactor, and cooled to 0°C. A solution of DCC (5.8 g) in dichloromethane (30.0 ml) was slowly added dropwise thereto, returned to room temperature and stirred for 12 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with 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=9:1) to obtain Compound (T-5) (5.0 g; 58%). In addition, THP represents a tetrahydropyranyl group.

Step 3 Compound (T-5) (5.0 g), pyridinium p-toluenesulfonate (PPTS) (1.5 g), tetrahydrofuran (THF) (25.0 ml), and methanol (25.0 ml) were put into a reactor , and stirred at 50 °C for 4 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=2:1). Further, it was purified by recrystallization from heptane to obtain compound (1-2-1) (2.7 g; 67%).

The NMR analysis values of the obtained compound (1-2-1) are as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.23 (s, 1H), 6.07 (s, 1H), 5.80 (d, J=1.1Hz, 1H), 5.53 (t, J=1.6Hz, 1H), 4.79-4.65 (m, 2H), 4.32 (d, J=6.8Hz, 2H), 2.30 (t, J=6.6Hz, 1H), 2.09-2.00 (m, 4H), 1.93 (s, 3H ), 1.85-1.76 (m, 4H), 1.43-1.31 (m, 4H), 1.19-1.07 (m, 6H). Transition temperature: C 119 I. (polymerization initiation temperature: 123°C)

[Synthesis example 2] Synthesis of compound (1-2-16)

Step 1 Compound (T-6) (156.2 g) synthesized by a known method and THF (1770 ml) were put into a reactor, and cooled to 0°C. 10% hydrochloric acid (884 ml) was added dropwise thereto and stirred at room temperature. The reaction mixture was poured into water, neutralized with potassium carbonate, 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=1:1) to obtain Compound (T-7) (123.6 g; 95%).

Step 2 Compound (T-7) (123.6 g), 3,4-dihydro-2H-pyran (60.2 ml), and dichloromethane (1000 ml) were put into a reactor, and cooled to 0°C. Thereto was added pyridinium p-toluenesulfonate (PPTS) (13.8 g), returned to room temperature and stirred. The reaction mixture was poured into sodium bicarbonate water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=4:1) to obtain Compound (T-8) (116.0 g; 68%).

Step 3 Lithium aluminum hydride (8.6 g) and THF (500 ml) were placed in the reactor and cooled to -10°C. A solution of Compound (T-8) (116.0 g) in THF (660 ml) was slowly added thereto, returned to room temperature and stirred. The reaction mixture was poured into water, the insoluble matter was separated by filtration, and then the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=1:1) to obtain Compound (T-9) (86.2 g; 74%).

Step 4 Using Compound (T-9) (81.2 g) and Compound (T-10) (26.5 ml) as starting materials, Compound (T-11) (86.2 g; 87 was obtained by the same method as in the second step of Synthesis Example 1) %).

Step 5 Using the compound (T-11) (55.0 g) as a raw material, the compound (T-12) (40.6 g; 95%) was obtained by the same method as the third step of Synthesis Example 1.

Step 6 Using the compound (T-12) (5.0 g) as a raw material, the compound (T-13) (6.5 g; 82%) was obtained by the same method as the second step of Synthesis Example 1.

Step 7 Using the compound (T-13) (6.5 g) as a raw material, the compound (1-2-16) (4.6 g; 87%) was obtained by the same method as the third step of Synthesis Example 1.

The NMR analysis values of the obtained compound (1-2-16) are as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.25 (s, 1H), 6.07 (s, 1H), 5.83 (s, 1H), 5.52 (s, 1H), 4.74-4.64 (m, 1H) ), 4.34 (d, J=6.6Hz, 2H), 4.22 (t, J=6.7Hz, 2H), 2.25 (t, J=6.6Hz, 1H), 2.07-1.98 (m, 2H), 1.93 (s , 3H), 1.83-1.69 (m, 6H), 1.62-1.53 (m, 2H), 1.41-1.26 (m, 3H), 1.18-0.88 (m, 8H). Transition temperature: C 66.8 I. (from polymerization Start temperature: 102℃)

[Synthesis example 3] Synthesis of compound (1-2-17)

Step 1 Trifluoromethanesulfonic anhydride (50.0 g) and dichloromethane (160 ml) were put into the reactor and cooled to 0°C. A solution of compound (T-14) (20.6 g) in dichloromethane (160 ml) and a solution of triethylamine (17.9 g) in dichloromethane (160 ml) were slowly added dropwise thereto, and stirred at 0°C 60 minutes. The reaction mixture was slowly added dropwise to ethylene glycol (330 ml) and stirred at room temperature for 12 hours. The solvent was distilled off from the reaction mixture under reduced pressure, and the residue was extracted with chloroform. The obtained organic layer was washed with sodium bicarbonate 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=1:2) to obtain Compound (T-15) (13.5 g; 48%).

Step 2 Compound (T-16) (19.5 g; 95%) was obtained by the same method as in the second step of Synthesis Example 2 using Compound (T-15) (13.5 g) as a raw material.

Step 3 Compound (T-16) (19.5 g), tetrabutylammonium bromide (2.6 g), tetrahydrofuran (THF) (97 ml) and water (97 ml) were put into a reactor. Lithium hydroxide monohydrate was slowly added dropwise thereto, and stirred at room temperature for 24 hours. Toluene (100 ml) was added to the reaction mixture, followed by extraction with water. 1 N hydrochloric acid (168 ml) was slowly added dropwise to the obtained aqueous layer, followed by extraction with tert-butyl methyl ether. 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-17) (13.6 g, yield 74%).

Step 4 Compound (T-18) (7.2 g; 83%) was obtained by the same method as in the second step of Synthesis Example 1 using Compound (T-12) (5.0 g) as a raw material.

Step 5 Using the compound (T-18) (7.2 g) as a raw material, the compound (1-2-17) (5.0 g; 84%) was obtained by the same method as the third step of Synthesis Example 1.

The NMR analysis values of the obtained compound (1-2-17) are as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.31 (s, 1H), 6.07 (s, 1H), 5.87 (s, 1H), 5.52 (s, 1H), 4.74-4.64 (m, 1H) ), 4.28-4.17 (m, 4H), 3.81-3.74 (m, 2H), 3.66-3.61 (m, 2H), 2.21 (t, J=6.1Hz, 1H), 2.07-1.98 (m, 2H), 1.93 (s, 3H), 1.84-1.69 (m, 6H), 1.63-1.53 (m, 2H), 1.41-1.25 (m, 3H), 1.18-0.88 (m, 8H). Transition temperature: C 46.0 S _A 62.2 I. (polymerization initiation temperature: 105°C)

[Synthesis Example 4] Synthesis of Compound (1-2-18)

Step 1 Using Compound (T-14) (14.6 g) and diethylene glycol (400 g) as raw materials, the same method as in the first step of Synthesis Example 4 was used to obtain Compound (T-19) (14.8 g; 58%) .

Step 2 Compound (T-20) (19.8 g; 95%) was obtained by the same method as in the second step of Synthesis Example 4 using Compound (T-19) (14.8 g) as a raw material.

Step 3 Compound (T-21) (15.3 g; 83%) was obtained by the same method as in the third step of Synthesis Example 4 using Compound (T-20) (19.8 g) as a raw material.

Step 4 Using the compound (T-21) (6.0 g) and the compound (T-12) (4.3 g) as starting materials, the compound (T-22) (6.1 g; 76 was obtained by the same method as in the second step of Synthesis Example 1) %).

Step 5 Using the compound (T-22) (6.1 g) as a raw material, the compound (1-2-18) (3.3 g; 64%) was obtained by the same method as in the third step of Synthesis Example 1.

The NMR analysis values of the obtained compound (1-2-18) are as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.32 (s, 1H), 6.09 (s, 1H), 5.91 (s, 1H), 5.54 (s, 1H), 4.74-4.69 (m, 1H) ), 4.27 (s, 2H), 4.22 (t, J=6.9Hz, 2H), 3.76-3.64 (m, 8H), 2.34-2.33 (m, 1H), 2.06-2.03 (m, 2H), 1.95 ( s, 3H), 1.84-1.69 (m, 6H), 1.61-1.56 (m, 4H), 1.38-1.33 (m, 3H), 1.55-0.94 (m, 7H). Transition temperature: C 41.8 S _B 57.7 I .(polymerization start temperature: 109℃)

[Synthesis example 5] Synthesis of compound (1-2-59)

Step 1 Compound (T-23) (30.0 g), triphenylphosphine (70.0 g), imidazole (34.9 g) and toluene (450 ml) were put into a reactor and cooled to 0°C. Thereto, iodine was slowly added dropwise, and the mixture was stirred at 0°C for 2 hours. After the insoluble matter was separated by filtration from the reaction mixture, the obtained organic layer was washed with water, heptane (500 ml) was added thereto, and the mixture was stirred at room temperature for 30 minutes. After the insoluble matter was separated by filtration from the mixture, the solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:toluene=2:1) to obtain Compound (T-24) (45.7 g) ; 87%).

Step 2 Sodium hydride (21.8 g) and tetrahydrofuran (800 ml) were placed in the reactor. Thereto was added dropwise triethyl phosphonoacetate (106.8 g) in tetrahydrofuran (240 ml), and stirred at room temperature for 1 hour. A solution of compound (T-24) (61.0 g) in tetrahydrofuran (360 ml) was added dropwise thereto, and stirred under reflux with heating for 6 hours. The reaction mixture was poured into water, and extracted with ethyl acetate. The obtained organic layer was washed with brine, and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and placed in the reactor with water (610 ml). Potassium carbonate (65.8 g) and paraformaldehyde (28.6 g) were added thereto, and the mixture was heated and stirred at 80° C. for 6 hours. The reaction mixture was poured into water, and extracted with ethyl acetate. It was stirred with heating under reflux for 6 hours. The reaction mixture was poured into water, and 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-25) (21.9 g; 40%).

Step 3 Compound (T-26) (12.7 g; 66%) was obtained by the same method as in the third step of Synthesis Example 4 using Compound (T-25) (21.9 g) as a raw material.

Step 4 Using Compound (T-26) (5.1 g) and Compound (T-12) (5.0 g) as starting materials, Compound (T-27) (7.8 g; 96 was obtained by the same method as in the second step of Synthesis Example 1) %).

Step 5 Using the compound (T-27) (7.4 g) as a raw material, the compound (1-2-59) (4.0 g; 59%) was obtained by the same method as the third step of Synthesis Example 1.

The NMR analysis values of the obtained compound (1-2-59) are as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.25 (d, J=1.0Hz, 1H), 6.07 (s, 1H), 5.67 (s, 1H), 5.52 (t, J=1.3Hz, 1H), 4.74-4.64 (m, 1H), 4.20 (t, J=6.9Hz, 2H), 3.82-3.74 (m, 2H), 3.70-3.62 (m, 2H), 2.54 (t, J=5.65Hz , 2H), 2.40 (d, J=7.4Hz, 2H), 2.07-1.98 (m, 2H), 1.93 (s, 3H), 1.90-1.83 (m, 1H), 1.82-1.70 (m, 6H), 1.62-1.54 (m, 2H), 1.41-1.25 (m, 3H), 1.18-0.88 (m, 8H). Transition temperature: C 109 I. (polymerization initiation temperature: 122°C)

[Synthesis example 6] Synthesis of compound (1-3-42)

Step 1 Using Compound (T-28) (4.5 g) and Compound (T-12) (2.2 g) as starting materials, the same method as in the second step of Synthesis Example 1 was used to obtain Compound (T-29) (5.4 g; 88 %).

Step 2 Using the compound (T-29) (5.4 g) as a raw material, the compound (1-3-42) (2.7 g; 58%) was obtained by the same method as the third step of Synthesis Example 1.

The NMR analysis values of the obtained compound (1-3-42) are as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.26-7.23 (m, 2H), 7.18 (d, J=7.7Hz, 1H), 7.16-7.12 (m, 3H), 7.09-7.05 (m , 4H), 6.35 (s, 1H), 6.27 (s, 1H), 5.85 (s, 1H), 5.75 (s, 1H), 4.34 (t, J=7.15Hz, 2H), 4.26 (t, J= 6.45Hz, 2H), 2.96-2.92 (m, 4H), 2.75 (t, J=7.65Hz, 2H), 2.69 (q, J=7.55Hz, 2H), 2.59 (q, J=7.55Hz, 2H) , 2.11-2.05 (m, 5H), 1.24 (t, J=7.55Hz, 3H), 1.11 (t, J=7.55Hz, 3H). Polymerization onset temperature: 142℃

[Synthesis Example 7] Synthesis of compound (1-3-44)

Step 1 Using Compound (T-28) (5.6 g) and Compound (T-17) (4.2 g) as starting materials, Compound (T-30) (6.3 g; 77 was obtained by the same method as in the second step of Synthesis Example 1) %).

Step 2 Using the compound (T-30) (6.3 g) as a raw material, the compound (1-3-44) (3.3 g; 60%) was obtained by the same method as the third step of Synthesis Example 1.

The NMR analysis values of the obtained compound (1-3-44) are as follows. ¹ H-NMR: chemical shift δ (ppm; CDCl ₃ ): 7.28-7.25 (m, 2H), 7.22-7.15 (m, 3H), 7.12-7.07 (m, 4H), 6.38 (s, 1H), 6.35 (s, 1H), 5.92 (s, 1H), 5.78 (s, 1H), 4.28-4.26 (m, 4H), 3.81-3.79 (m, 2H), 3.67 (t, J=4.25Hz, 2H), 3.02-2.93 (m, 4H), 2.77 (t, J=7.85Hz, 2H), 2.71 (q, J=7.55Hz, 2H), 2.61 (q, J=7.55Hz, 2H), 2.11-2.08 (m , 5H), 1.26 (t, J=7.55Hz, 3H), 1.14 (t, J=7.55Hz, 3H). Polymerization initiation temperature: 143℃

[Synthesis Example 8] Synthesis of compound (1-3-46)

Step 1 Using Compound (T-31) (4.5 g) and Compound (T-17) (2.2 g) as raw materials, the same method as in the second step of Synthesis Example 1 was used to obtain Compound (T-32) (5.4 g; 88 %).

Step 2 Using the compound (T-32) (5.4 g) as a raw material, the compound (1-3-46) (2.7 g; 58%) was obtained by the same method as the third step of Synthesis Example 1.

The NMR analysis values of the obtained compound (1-3-46) are as follows. ¹ H-NMR: chemical shift δ (ppm; CDCl ₃ ): 7.23-7.20 (m, 6H), 7.14-7.11 (m, 2H), 7.06-7.03 (m, 3H), 6.33 (d, J=10.7Hz , 2H), 5.90-5.89 (m, 1H), 5.75-5.74 (m, 1H), 4.26-4.23 (m, 4H), 3.79-3.76 (m, 2H), 3.65-3.63 (m, 2H), 2.99 (s, 4H), 2.76-2.70 (m, 2H), 2.61-2.56 (m, 2H), 2.27-2.26 (m, 1H), 2.10-2.08 (m, 5H), 1.01-1.08 (m, 3H) . Polymerization start temperature: 180℃

[Synthesis Example 9] Synthesis of compound (1-3-62)

Step 1 Under nitrogen atmosphere, compound (T-33) (13.6 g), compound (T-34) (2.2 g), tetrakis(triphenylphosphine)palladium (4.8 g), potassium carbonate (22.8 g), bromide Tetrabutyl ammonium bromide (TBAB) (2.7 g), toluene (300 ml), and Solmix (300 ml) were put into the reactor and heated to reflux. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The organic layer produced together was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (toluene) and recrystallization to obtain Compound (T-35) (21.5 g; yield 86%).

Step 2 Under nitrogen atmosphere, compound (T-35) (2.0 g), diisopropylamine (35 ml), tetrahydrofuran (10 ml), copper(I) iodide (0.05 g), palladium acetate (0.08 g) were added , tert-butyldimethyl(2-propynyloxy)silane (4.2 ml), and stirring under reflux for 2 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The organic layer produced together was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (volume ratio, heptane:ethyl acetate=4:1) to obtain Compound (T-36) (1.4 g; 54%).

Step 3 Under a nitrogen atmosphere, compound (T-36) (17.3 g) and tetrahydrofuran (200 ml) were added and cooled to -30°C, and potassium tert-butoxide (3.6 g) was added thereto. After stirring for 1 hour, a solution of compound (T-37) (10.0 g) and tetrahydrofuran (50 ml) was added dropwise. After warming to room temperature and stirring, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The organic layer produced together was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (volume ratio, heptane:ethyl acetate=9:1) to obtain Compound (T-38) (7.6 g; 56%).

Step 4 Under nitrogen, compound (T-38) (7.6 g), Pd/C (0.38 g), toluene (80 ml), Solmix (80 ml) were added, and under hydrogen, Stirring was carried out at room temperature until no hydrogen was absorbed. After removing Pd/C, it was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=4:1) to obtain compound (T-39) (7.1 g; 92%).

Step 5 Under nitrogen atmosphere, compound (T-39) (7.1 g), formic acid (35.5 ml), TBAB (0.88 g), toluene (100 ml) were added, and stirred at room temperature for 7 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The organic layer produced together was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (volume ratio, heptane:ethyl acetate=4:1) to obtain Compound (T-40) (5.1 g; 96%).

Step 6 Under nitrogen atmosphere, compound (T-40) (5.1 g), 3,4-dihydro-2H-pyran (2.4 g), and dichloromethane (30 ml) were put into the reactor, cooled to 0°C. Thereto was added pyridinium p-toluenesulfonate (PPTS) (0.35 g), returned to room temperature and stirred. The reaction mixture was poured into sodium bicarbonate water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=2:1) to obtain Compound (T-41) (4.9 g; 97%).

Step 7 Lithium aluminum hydride (0.25 g) and THF (25 ml) were placed in the reactor and cooled to -10°C. A solution of compound (T-41) (4.6 g) in THF (50 ml) was slowly added thereto, returned to room temperature and stirred. The reaction mixture was poured into water, the insoluble matter was separated by filtration, and then the aqueous layer was extracted with ethyl acetate. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=2:1) to obtain Compound (T-42) (3.1 g; 63%).

Step 8 Using Compound (T-42) (3.1 g) and Compound (T-10) (0.7 g) as starting materials, Compound (T-43) (3.5 g; 98 was obtained in the same manner as in the second step of Synthesis Example 1) %).

Step 9 Using compound (T-43) (3.5 g) as a raw material, the reaction was carried out in the same manner as in the third step of Synthesis Example 1, followed by esterification in the same manner as in the second step of Synthesis Example 1, and further with Compound (1-3-62) (1.9 g; 70%) was obtained by the same reaction as in the third step of Synthesis Example 1.

The NMR analysis values of the obtained compound (1-3-62) are as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.26-7.23 (m, 4H), 7.18-7.13 (m, 2H), 7.09-7.03 (m, 1H), 6.38 (s, 1H), 6.10 (s, 1H), 5.87 (s, 1H), 5.55 (s, 1H), 4.80-4.76 (m, 1H), 4.29-4.26 (m, 4H), 3.82-3.79 (m, 2H), 3.67 (t , J=4.3Hz, 2H), 2.77 (t, J=7.9Hz, 2H), 2.71-2.69 (m, 2H), 2.61 (q, J=7.50Hz, 2H), 2.25-2.22 (m, 1H) , 2.12-2.05 (m, 4H), 1.96-1.92 (m, 5H), 1.64-1.59 (m, 2H), 1.47-1.34 (m, 3H), 1.19-1.09 (m, 5H). Polymerization onset temperature : 168℃

[Synthesis Example 9] Synthesis of compound (1-3-66)

Step 1 Using Compound (T-44) (3.0 g) and Compound (T-17) (1.7 g) as raw materials, the same method as in the second step of Synthesis Example 1 was used to obtain Compound (T-45) (4.0 g; 92 %).

Step 2 A solution of compound (T-45) (0.5 g) in tetrahydrofuran (5.0 ml) was cooled to 0°C. Tetrabutylammonium fluoride (TBAF) (0.76 ml) was added dropwise thereto, and the mixture was stirred for 10 hours while warming up 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, toluene:ethyl acetate=4:1) to obtain Compound (T-46) (0.3 g; 74%).

Step 3 Using the compound (T-46) (11.0 g) as a raw material, the compound (1-3-66) (6.6 g; 78%) was obtained by the same method as the second step and the third step of Synthesis Example 1.

The NMR analysis values of the obtained compound (1-3-66) are as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.23-7.21 (m, 6H), 7.13-7.12 (m, 2H), 7.06-7.04 (m, 3H), 6.56 (s, 1H), 6.12 (s, 1H), 6.07 (s, 1H), 5.57-5.56 (m, 1H), 4.36 (s, 1H), 4.21 (t, J=6.4Hz, 2H), 3.81-3.78 (m, 2H), 3.68 (t, J=4.2Hz, 4H), 2.97 (s, 4H), 2.75 (t, J=7.7Hz, 2H), 2.58 (q, J=7.5Hz, 2H), 2.14-2.12 (m, 1H ), 2.09-2.03 (m, 2H), 1.96 (s, 3H), 1.09 (t, J=7.6Hz, 3H). Polymerization initiation temperature: 123℃

[Synthesis Example 10] Synthesis of compound (1-3-45)

Step 1 Using Compound (T-47) (4.0 g) and Compound (T-17) (2.9 g) as starting materials, Compound (T-48) (6.3 g) was obtained by the same method as in the second step of Synthesis Example 1; Quantitative ).

Step 2 Using the compound (T-48) (6.3 g) as a raw material, the compound (1-3-45) (3.5 g; 64%) was obtained by the same method as the third step of Synthesis Example 1.

The NMR analysis values of the obtained compound (1-3-45) are as follows. ¹ H-NMR: chemical shift δ (ppm; CDCl ₃ ): 7.25-7.23 (m, 2H), 7.18-7.13 (m, 3H), 7.10-7.07 (m, 3H), 7.03-6.97 (m, 2H) , 6.34 (s, 1H), 6.33 (s, 1H), 5.92 (s, 1H), 5.78 (s, 1H), 4.29-4.26 (m, 4H), 3.82-3.79 (m, 2H), 3.68-3.66 (m, 2H), 3.00-2.98 (m, 4H), 2.78 (t, J=15.3Hz, 2H), 2.52 (q, J=7.5Hz, 2H), 2.13-2.07 (m, 5H), 1.08 ( t, J=7.6Hz, 3H). Polymerization initiation temperature: 179℃

[Comparative Example 1] Compatibility Comparison As a comparative compound, the following compound (S-1) was selected. This compound is synthesized according to a known method.

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 compatibility in the liquid crystal composition of the compound (1-2-6) and the comparative compound (S-1) was compared. The composition (i) containing the following compounds (i-1) to (i-9) was used for evaluation

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

The compound (1-2-17), the compound (1-3-42), the compound (1-3-66) or the comparative compound (S-1) was added to the mother liquid crystal (i) at a ratio of 2% by weight sample made in. After the sample was left to stand at -20°C for 3 days, it was visually observed, and the case where the nematic phase was maintained was represented by ○, and the case where crystals or smectic phases were precipitated was represented by x.

Table 2. Compatibility

As a result of comparing the solubility, the compound described in the present application can maintain the nematic phase at -20°C even if 2 wt % is added to the mother liquid crystal. % at -20 ° C to precipitate crystals. The reason for this is presumably because the compound of the present application has polymerizable groups at both ends, so that the affinity in the liquid crystal composition is improved. Therefore, the compound of the present application can be said to be an excellent compound with good compatibility.

The following compound (1-1-1) to compound (1-4-24) can be synthesized with reference to the method described in the synthesis example or the section "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 steric configuration related to 1,4-cyclohexylene is trans. The number in parentheses after the symbol corresponds to the number of the compound. The symbol (-) refers to other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is the weight percentage (% by weight) based on the weight of the liquid crystal composition. Finally, characteristic values of the liquid crystal composition are summarized. The characteristics were measured according to the methods described above, and the measured values (not extrapolated) were directly recorded.

[Example 1 of use] 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-O1 (3-1) 5% 3-HHB-3 (3-1) 14% 3-HHB-F (6-1) 4% 2-HHB(F)-F (6-2) 7% 3-HHB(F)-F (6-2) 7% 5-HHB(F)-F (6-2) 7% 3-HHB(F,F)-F (6-3) 5% 3-HHEB-F (6-10) 4% 5-HHEB-F (6-10) 4% 2-HB-C (8-1) 5% 3-HB-C (8-1) 12%

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

NI=95.8℃; η=16.9 mPa･s; Δn=0.108; Δε=4.8.

[Use example 2] 3-HH-4 (2-1) 12% 7-HB-1 (2-5) 3% 5-HB-O2 (2-5) 6% 5-HBB(F)B-2 (4-5) 6% 5-HBB(F)B-3 (4-5) 6% 3-HB-CL (5-2) 10% 3-HHB(F,F)-F (6-3) 3% 3-HBB(F,F)-F (6-24) 30% 5-HBB(F,F)-F (6-24) 24%

The following compound (1-3-42) was added to the composition at a ratio of 1.5% by weight.

NI=75.5℃; η=20.9 mPa･s; Δn=0.117; Δε=5.7.

[Use example 3] 1V2-HH-1 (2-1) 3% 1V2-HH-3 (2-1) 4% 7-HB(F,F)-F (5-4) 3% 2-HHB(F)-F (6-2) 10% 3-HHB(F)-F (6-2) 9% 5-HHB(F)-F (6-2) 9% 2-HBB-F (6-22) 5% 3-HBB-F (6-22) 5% 5-HBB-F (6-22) 3% 2-HBB(F)-F (6-23) 9% 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 (1-2-16) was added to the composition in a ratio of 2% by weight.

NI=84.7℃; η=25.0 mPa･s; Δn=0.112; Δε=5.7.

[Use example 4] 2-HH-3 (2-1) 4% 3-HH-4 (2-1) 12% 1O1-HBBH-5 (4-1) 3% 5-HB-CL (5-2) 16% 3-HHB-F (6-1) 4% 3-HHB-CL (6-1) 3% 4-HHB-CL (6-1) 4% 3-HHB(F)-F (6-2) 9% 4-HHB(F)-F (6-2) 10% 5-HHB(F)-F (6-2) 9% 7-HHB(F)-F (6-2) 8% 5-HBB(F)-F (6-23) 4% 3-HHBB(F,F)-F (7-6) 2% 4-HHBB(F,F)-F (7-6) 3% 5-HHBB(F,F)-F (7-6) 3% 3-HH2BB(F,F)-F (7-15) 3% 4-HH2BB(F,F)-F (7-15) 3%

The following compound (1-2-17) was added to the composition at a ratio of 0.5% by weight.

NI=113.1℃; η=18.6 mPa･s; Δn=0.090; Δε=3.7.

[Use example 5] V-HBB-2 (3-4) 10% 1O1-HBBH-4 (4-1) 4% 1O1-HBBH-5 (4-1) 4% 3-HHB(F,F)-F (6-3) 9% 3-H2HB(F,F)-F (6-15) 8% 4-H2HB(F,F)-F (6-15) 8% 5-H2HB(F,F)-F (6-15) 9% 3-HBB(F,F)-F (6-24) 10% 5-HBB(F,F)-F (6-24) 18% 3-H2BB(F,F)-F (6-27) 12% 5-HHBB(F,F)-F (7-6) 3% 3-HH2BB(F,F)-F (7-15) 3% 5-HHEBB-F (7-17) 2%

The following compound (1-3-44) was added to the composition in a ratio of 2% by weight.

NI=106.9℃; η=32.3 mPa･s; Δn=0.122; Δε=8.2.

[Use example 6] 5-HBBH-3 (4-1) 3% 3-HB(F)BH-3 (4-2) 3% 5-HB-F (5-2) 12% 6-HB-F (5-2) 9% 7-HB-F (5-2) 7% 2-HHB-OCF3 (6-1) 7% 3-HHB-OCF3 (6-1) 7% 4-HHB-OCF3 (6-1) 7% 5-HHB-OCF3 (6-1) 5% 3-HHB(F,F)-OCF2H (6-3) 4% 3-HHB(F,F)-OCF3 (6-3) 5% 3-HH2B-OCF3 (6-4) 4% 5-HH2B-OCF3 (6-4) 4% 3-HH2B(F)-F (6-5) 3% 3-HBB(F)-F (6-23) 10% 5-HBB(F)-F (6-23) 10%

The following compound (1-2-18) was added to the composition at a ratio of 1.5% by weight.

NI=85.3℃; η=14.9 mPa･s; Δn=0.092; Δε=4.5.

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

The following compound (1-2-59) was added to the composition in a ratio of 4% by weight.

NI=78.5℃; η=23.4 mPa･s; Δn=0.109; Δε=8.7.

[Use example 8] V2-HHB-1 (3-1) 6% 3-HB-CL (5-2) 5% 5-HB-CL (5-2) 5% 3-HHB-OCF3 (6-1) 4% 5-HHB(F)-F (6-2) 5% 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) 10% 3-HBEB(F,F)-F (6-39) 5%

The following compound (1-3-45) was added to the composition at a ratio of 2.5% by weight.

NI=73.1℃; η=24.8 mPa･s; Δn=0.099; Δε=8.1.

[Use example 9] 3-HH-4 (2-1) 10% 3-HH-5 (2-1) 5% 3-HB-O2 (2-5) 11% 3-HHB-1 (3-1) 9% 3-HHB-O1 (3-1) 4% 5-HB-CL (5-2) 16% 7-HB(F,F)-F (5-4) 3% 2-HHB(F)-F (6-2) 7% 3-HHB(F)-F (6-2) 7% 5-HHB(F)-F (6-2) 7% 3-HHB(F,F)-F (6-3) 7% 3-H2HB(F,F)-F (6-15) 7% 4-H2HB(F,F)-F (6-15) 7%

The following compound (1-3-62) was added to the composition at a ratio of 5% by weight.

NI=73.2℃; η=15.5 mPa･s; Δn=0.073; Δε=3.1.

[Example 10 of use] 3-HH-4 (2-1) 9% 3-HH-5 (2-1) 10% 3-HHB-3 (3-1) 11% 5-HB-CL (5-2) 4% 7-HB(F)-F (5-3) 8% 2-HHB(F,F)-F (6-3) 5% 3-HHB(F,F)-F (6-3) 4% 3-HHEB-F (6-10) 8% 5-HHEB-F (6-10) 8% 3-HHEB(F,F)-F (6-12) 10% 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 (1-3-64) was added to the composition at a ratio of 0.5% by weight.

NI=84.4℃; η=21.2 mPa･s; Δn=0.070; Δε=5.8.

[Example 11 of use] 3-HH-VFF (2-1) 5% 5-HH-VFF (2-1) 25% 2-BTB-1 (2-10) 10% 3-HHB-1 (3-1) 4% VFF-HHB-1 (3-1) 8% VFF2-HHB-1 (3-1) 11% 3-H2BTB-2 (3-17) 5% 3-H2BTB-3 (3-17) 4% 3-H2BTB-4 (3-17) 4% 3-HB-C (8-1) 18% 1V2-BEB(F,F)-C (8-15) 6%

The following compound (1-3-65) was added to the composition in a ratio of 1% by weight.

NI=81.0℃; η=11.1 mPa･s; Δn=0.130; Δε=6.6.

[Example 12 of use] 2-HH-5 (2-1) 4% 3-HH-4 (2-1) 10% 5-B(F)BB-2 (3-8) 5% 5-HB-CL (5-2) 7% 3-HHB(F,F)-F (6-3) 6% 3-HHEB(F,F)-F (6-12) 11% 4-HHEB(F,F)-F (6-12) 3% 5-HHEB(F,F)-F (6-12) 4% 3-HBB(F,F)-F (6-24) 18% 5-HBB(F,F)-F (6-24) 15% 2-HBEB(F,F)-F (6-39) 4% 3-HBEB(F,F)-F (6-39) 4% 5-HBEB(F,F)-F (6-39) 4% 3-HHBB(F,F)-F (7-6) 5%

The following compound (1-3-8) was added to the composition in a ratio of 3% by weight.

NI=79.4℃; η=22.1 mPa･s; Δn=0.106; Δε=8.2. [Industrial Availability]

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

none

none

Claims (17)

A compound represented by formula (1);

In formula (1), ring A ¹ and ring A ² are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,5-diyl , naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl base, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, Alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyloxy having 2 to 9 carbons, in which at least one hydrogen may be substituted by Fluorine or chlorine substitution; a is 0, 1, 2, or 3; Z ¹ is a single bond or an alkylene group having 1 to 10 carbon atoms, in the alkylene group, at least one -CH ₂ - may be through -O- , -CO-, -COO-, -OCO-, or -OCOO- substituted, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, among these groups, at least one Hydrogen can be substituted by fluorine or chlorine; Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 15 carbon atoms, and in the alkylene group, at least one -CH ₂ - can be replaced by -O-, -CO -, -COO-, -OCO-, or -OCOO- substituted, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by Fluorine or chlorine substituted; M ¹ , M ² , M ³ , and M ⁴ are independently hydrogen, fluorine, chlorine, alkyl having 1 to 5 carbons, or at least one hydrogen substituted with fluorine or chlorine having 1 to 5 carbons R ¹ is hydrogen, alkyl with 1 to 10 carbons, alkoxy with 1 to 9 carbons, or alkoxyalkyl with 1 to 9 carbons, among these groups, at least one -( CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by fluorine or chlorine; R ² is selected from formula (1-a), formula (1 -b), and a group in the group represented by formula (1-c);

In formula (1-a), formula (1-b), and formula (1-c), Sp ³ and Sp ⁴ are independently a single bond or an alkylene group having 1 to 15 carbon atoms, and in the alkylene group , at least one -CH ₂ - can be substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C ≡C-substituted, in these groups, at least one hydrogen can be substituted by fluorine or chlorine; R ³ is hydrogen, alkyl with 1 to 10 carbons, alkoxy with 1 to 9 carbons, or 1 to 9 carbons alkoxyalkyl; X ¹ is independently -OH, -NH ₂ , -N(R ⁴ ) ₂ , -COOH, -SH, or -Si(R ⁴ ) ₃ ; -N(R ⁴ ) ₂ , And in -Si(R ⁴ ) ₃ , R ⁴ is hydrogen or an alkyl group having 1 to 10 carbon atoms, in the alkyl group, at least one -CH ₂ - can be substituted by -O-, at least one -(CH ₂ ) ₂ - may be substituted with -CH=CH-, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine. The compound described in item 1 of the claimed scope, wherein in formula (1), Z ¹ is a single bond, -(CH ₂ ) ₂ -, -(CH ₂ ) ₄ -, -CH=CH-, -C≡ C-, -COO-, -OCO-, _-CF2O- , _-OCF2- , _-CH2O- , _-OCH2- , or -CF=CF-. The compound according to claim 1 or claim 2, wherein in formula (1), ring A ¹ and ring A ² are independently 1,4-cyclohexylene, 1,4-cyclohexenylene , 1,4-phenylene, naphthalene-1,5-diyl, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2, 5-diyl, in these rings, at least one hydrogen may be fluorine, chlorine, alkyl with 1 to 10 carbons, alkenyl with 2 to 10 carbons, alkoxy with 1 to 9 carbons, or alkoxy with 1 to 9 carbons 2 to 9 are substituted with alkenyloxy, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine. The compound described in item 1 or item 2 of the claimed scope, which is represented by any one of formula (1-1) to formula (1-4);

In formula (1-1) to formula (1-4), ring A ¹ , ring A ² , ring A ³ , and ring A ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexene 1,4-phenylene, naphthalene-1,5-diyl, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2 ,5-diyl, in these rings, at least one hydrogen can be fluorine, alkyl with 1 to 10 carbons, alkenyl with 2 to 10 carbons, alkoxy with 1 to 9 carbons, or carbon number 2 Alkenyloxy substitution to 9, in these groups, at least one hydrogen may be substituted by fluorine; Z ¹ , Z ² , and Z ³ are independently single bonds, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C-, -COO-, -OCO-, -CF2O-, _-OCF2- , _-CH2O- , _-OCH2- , or -CF ⁼ CF- _; Sp1 and ^Sp2 independently is 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-, -COO-, or -OCO-, and at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH-, in these groups, at least one hydrogen can be substituted by fluorine; M ¹ , M ² , M ³ , and M ⁴ are independently hydrogen, fluorine, and alkane having 1 to 5 carbon atoms R ¹ is hydrogen, an alkyl group with 1 to 7 carbons, an alkoxy group with 1 to 6 carbons, or an alkyl group with 1 to 6 carbons Alkoxyalkyl, in these groups, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by fluorine; R ² 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 ³ and Sp ⁴ are independently a single bond or an alkylene group having 1 to 15 carbon atoms, and in the alkylene group , at least one -CH ₂ - can be substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C ≡C-substituted, in these groups, at least one hydrogen can be substituted by fluorine; R ³ is hydrogen, alkyl with 1 to 7 carbons, alkoxy with 1 to 6 carbons, or alkane with 1 to 6 carbons ^Oxyalkyl ; X1 is independently -OH, _-NH2 , or -SH. The compound described in item 1 or item 2 of the claimed scope, which is represented by any one of formula (1-5) to formula (1-7);

In formula (1-5) to formula (1-7), ring A ¹ , ring A ² , ring A ³ , and ring A ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexene group, 1,4-phenylene, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl, in these rings, at least one hydrogen can be through fluorine, Substituted with an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; Z ¹ , Z ² , and Z ³ are independently a single bond, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C-, -CH ₂ O-, or -OCH ₂ -; Sp ¹ and Sp ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, so In the alkylene 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 ¹ is hydrogen, an alkyl group having 1 to 5 carbon atoms , an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 1 to 4 carbon atoms; R ² is a group selected from the groups represented by formula (1-a) and formula (1-b) ;

In formula (1-a) and formula (1-b), Sp ³ and Sp ⁴ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - Can be substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, these In the base, at least one hydrogen can be substituted by fluorine; R ³ is hydrogen, alkyl with 1 to 7 carbons, alkoxy with 1 to 6 carbons, or alkoxyalkyl with 1 to 6 carbons; X ¹ is independently -OH, _-NH2 , or -SH. The compound described in item 1 or item 2 of the claimed scope, which is represented by any one of formula (1-8) to formula (1-25);

In formula (1-8) to formula (1-25), R ¹ is hydrogen, methyl, ethyl, propyl, or -CH ₂ OCH ₃ ; R ³ 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; Z ¹ and Z ² are independently a single bond, -(CH ₂ ) ₂ -, or -CH=CH-; Sp ¹ , Sp ² , Sp ³ , and Sp ⁴ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be substituted by -O-; Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ , Y ⁸ , Y ⁹ , Y ¹⁰ , Y ¹¹ , and Y ¹² are independently hydrogen, fluorine, or an alkyl group having 1 to 5 carbons. The compound described in item 1 or item 2 of the claimed scope, which is represented by any one of formula (1-26) to formula (1-43);

In formula (1-26) to formula (1-43), Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , and Y ⁶ are independently hydrogen, fluorine, methyl, or ethyl; R ³ is Hydrogen, alkyl having 1 to 7 carbons, alkoxy having 1 to 6 carbons, or alkoxyalkyl having 1 to 6 carbons; 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 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be substituted by -O- . A liquid crystal composition, which contains at least one of the compounds described in any one of items 1 to 7 of the scope of the patent application, wherein the ratio of the compound relative to 100% by weight of the liquid crystal composition is 0.05% by weight % or more and 10% by weight or less. The liquid crystal composition according to item 8 of the claimed scope, comprising at least one compound selected from the group of compounds represented by formula (2) to formula (4);

In formula (2) to formula (4), R ¹¹ and R ¹² are independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in the alkyl and alkenyl groups, at least one -CH ₂ - may be substituted by -O-, among these groups, at least one hydrogen may be substituted by fluorine; Ring B ¹ , Ring B ² , Ring B ³ , and Ring B ⁴ are independently 1,4-cyclohexylene, 1 ,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, or pyrimidine-2,5-diyl; Z ¹¹ , Z ¹² , and Z ¹³ is independently a single bond, -COO-, -CH ₂ CH ₂ -, -CH=CH-, or -C≡C-. The liquid crystal composition according to item 8 or item 9 of the claimed scope, comprising at least one compound selected from the group of compounds represented by formula (5) to formula (7);

In formulas (5) to (7), R ¹³ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in the alkyl and alkenyl groups, at least one -CH ₂ - may be through - O-substituted, in these groups, at least one hydrogen can be substituted by fluorine; X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ , or -OCF ₂ CHFCF ₃ ; Ring C ¹ , Ring C ² , and Ring C ³ are independently 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl , 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is substituted with fluorine; Z ¹⁴ , Z ¹⁵ , and Z ¹⁶ independently a 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 according to item 8 or item 9 of the claimed scope, 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 having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Among the alkyl and alkenyl groups, at least one -CH ₂ - may be substituted by -O-, which In these groups, at least one hydrogen can be substituted by fluorine; X ¹² is -C≡N or -C≡CC≡N; Ring D ¹ is 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyridine Pyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or 1,4-phenylene in which at least one hydrogen is substituted with fluorine; Z ¹⁷ is a single bond, -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, or -C≡C-; L ¹³ and L ¹⁴ are independently hydrogen or fluorine; i is 1, 2, 3, or 4. The liquid crystal composition according to item 8 or item 9 of the claimed scope, which contains at least one compound selected from the group of compounds represented by formula (11) to formula (19);

In formulas (11) to (19), R ¹⁵ , R ¹⁶ , and R ¹⁷ are independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and among the alkyl and alkenyl groups, At least one -CH ₂ - can be substituted by -O-, in these groups, at least one hydrogen can be substituted by fluorine, and R ¹⁷ can also be hydrogen or fluorine; ring E ¹ , ring E ² , ring E ³ , and ring E ⁴ is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, decalin-2,6 -diyl, or 1,4-phenylene in which at least one hydrogen is substituted by fluorine; ring E ⁵ and ring E ⁶ are independently 1,4-cyclohexylene, 1,4-cyclohexenyl, 1,4 4-phenylene, tetrahydropyran-2,5-diyl, or decalin-2,6-diyl; Z ¹⁸ , Z ¹⁹ , Z ²⁰ , and Z ²¹ are independently a single bond, -COO _- , _-OCO- , _-CH2O- , _-OCH2- , _-CF2O- , _{-OCF2- , -CH2CH2-} , _-CF2OCH2CH2- , _{or -OCF2CH2} 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, and the sum of k, m, n, and p is 1 or 2, the sum of q, r, and s is 0, 1, 2, or 3, and t is 1, 2, or 3 . The liquid crystal composition according to claim 8 or claim 9, which contains at least one polymerizable compound represented by formula (20) other than the compound represented by formula (1);

In formula (20), ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxyl Alkyl-2-yl, pyrimidin-2-yl, or pyridin-2-yl, in these rings, at least one hydrogen may be replaced by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, Or at least one hydrogen is substituted by halogen-substituted alkyl group with carbon number from 1 to 12; Ring G is 1,4-cyclohexylene, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-1 ,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl , naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, phenanthrene-2,7-diyl, tetrahydropyran -2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen may be substituted by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is substituted by halogen; Z ²² and Z ²³ are independently mono A bond or an alkylene group having 1 to 10 carbon atoms, in the alkylene group, at least one -CH ₂ - can be substituted by -O-, -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 radicals wherein, 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 with 1 to 10 carbon atoms. Alkyl, in the alkylene, 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 may be substituted by fluorine or chlorine; u is 0, 1, or 2; f, g, and h are independently 0, 1, 2, 3, or 4, and the sum of f, g, and h is 1 or more. The liquid crystal composition according to claim 13, wherein in formula (20), P ¹¹ , P ¹² , and P ¹³ are independently represented by formulas (P-1) to (P-5) A group in the group of polymerizable groups;

In formula (P-1) to formula (P-5), M ¹¹ , M ¹² , and M ¹³ are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or a carbon number in which at least one hydrogen is substituted by halogen 1 to 5 alkyl groups. The liquid crystal composition according to claim 13, wherein the polymerizable compound represented by formula (20) is selected from the group of polymerizable compounds represented by formula (20-1) to formula (20-7) at least one compound in;

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

In formula (P-1) to formula (P-3), M ¹¹ , M ¹² , and M ¹³ are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or a carbon number in which at least one hydrogen is substituted by halogen 1 to 5 alkyl groups. The liquid crystal composition according to claim 8 or claim 9, which contains a polymerizable compound, a polymerization initiator, and a polymerization inhibitor selected from the group consisting of compounds represented by formula (1) or formula (20) , at least one of the group of optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, pigments, and defoamers. A liquid crystal display element comprising a liquid crystal composition selected from the group consisting of the liquid crystal composition described in any one of items 8 to 16 in the scope of the application, and the liquid crystal composition described in any one of items 8 to 16 in the scope of the application At least one of the group consisting of at least a part of the liquid crystal composition polymerized.