TW202016063A - Compound, liquid crystal composition, and liquid crystal display element - Google Patents

Abstract

Provided is a polar compound having high chemical stability, high ability to orient liquid crystal molecules, high solubility with respect to a liquid crystal composition, and a high voltage holding ratio of a liquid crystal display element. This compound is represented by formula (1). R1 is hydrogen or an alkyl which may be substituted; ring A1 and ring A2 are phenylenes, or the like which may be substituted; a is 0-4; Z1 is an alkylene or the like which may be single-bonded or substituted; R2 is an alkyl which may be substituted; at least one hydrogen among ring A2 and Sp0 may be substituted by formula (1-a); Sp0, and Sp2-Sp5 are alkylenes which may be single-bonded or substituted; M1-M4 are hydrogen, fluorine, or the like; R3 is an alkyl having 1-10 carbon atoms; and X1 is -OH, or the like.

Description

Compound, liquid crystal composition and liquid crystal display element

The invention relates to a compound, a liquid crystal composition and a liquid crystal display element. In more detail, the present invention relates to a compound having both a polymerizable group such as methacryloxy and two polymerizable groups substituted with polar groups such as -OH groups, etc. A liquid crystal composition having a positive or negative dielectric anisotropy and a liquid crystal display element including the composition or a part of its cured product.

If the liquid crystal display elements are classified based on the operation mode of the liquid crystal molecules, they can be classified as phase change (PC), twisted nematic (TN), super twisted nematic (STN), Electrically controlled birefringence (ECB), optically compensated bend (OCB), in-plane switching (IPS), vertical alignment (VA), fringe field switching (fringe field) switching (FFS), field-induced photo-reactive alignment (FPA) and other modes. In addition, if based on the driving method of the device, it can be classified into a passive matrix (PM) and an active matrix (AM). PM is classified as static, multiplex, etc., AM is classified as thin film transistor (TFT), metal-insulator-metal (MIM), etc. Furthermore, TFTs can be classified into amorphous silicon and polycrystal silicon. The latter is classified into a high-temperature type and a low-temperature type according to manufacturing steps. If the classification based on the light source is performed, it can be classified into a reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both natural light and backlight.

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

1）可縮短於液晶顯示元件中注入組成物的時間

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

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

The optical anisotropy of the composition is related to the contrast of the device. Depending on the mode of the device, it is necessary that the optical anisotropy is 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 device is designed to maximize the contrast. The appropriate value of the product depends on the type of operation mode. In TN and other mode devices, this value is about 0.45 μm. In the VA mode device, the value ranges from about 0.30 μm to about 0.40 μm, and in the IPS mode or FFS mode device, the value ranges from about 0.20 μm to about 0.30 μm. In these cases, it is preferable for the element with a small cell gap to have a composition with large optical anisotropy. The large dielectric constant anisotropy of the composition contributes to a low threshold voltage of the device, low power consumption and high contrast. Therefore, it is preferable that the positive or negative dielectric constant anisotropy is large. A large specific resistance of the composition contributes to a large voltage retention ratio and a large contrast ratio of the device. Therefore, in the initial stage, a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable. It is preferably 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. The stability of the composition to ultraviolet light and heat is related to the life of the device. When the stability is high, the life of the device is long. Such characteristics are preferable for AM devices used in liquid crystal projectors, liquid crystal televisions, and the like.

In a polymer sustained alignment (PSA) type liquid crystal display element, a liquid crystal composition containing a polymer is used. First, the composition to which a small amount of polymerizable compound is added is injected into the device. Here, a polymerizable compound having a plurality of polymerizable groups is generally used. Next, a voltage is applied between the substrates holding the element, and the composition is irradiated with ultraviolet rays. The polymerizable compound is polymerized to form 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 the response time of the device is shortened and the afterimage of the image is improved. Devices with modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA can expect such effects of polymers.

In general liquid crystal display devices, the vertical alignment of liquid crystal molecules is achieved by polyimide alignment films. On the other hand, as a liquid crystal display element having no alignment film, there has been proposed a mode in which a polar compound is added to a liquid crystal composition to align liquid crystal molecules. First, the composition to which a small amount of polar compound and a small amount of polymerizable compound are added is injected into the device. As the polymerizable compound, a polymerizable compound having a plurality of polymerizable groups is generally used. Here, the liquid crystal molecules are aligned by the action of the polar compound. Next, a voltage is applied between the substrates holding the element, and the composition is irradiated with ultraviolet rays. Here, the polymerizable compound polymerizes and stabilizes the alignment of 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 the response time of the device is shortened and the afterimage of the image is improved. Furthermore, in an element without an alignment film, a step of forming an alignment film is not necessary. Since there is no alignment film, there is no case where the resistance of the element decreases due to the interaction between the alignment film and the composition. An element having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA can expect such an effect using a combination of a polar compound and a polymer.

Hitherto, in a liquid crystal display device that does not have an alignment film, as a compound having both the role of a polar compound and the role of a polymerizable compound, a polymerizable polar compound has been synthesized (for example, Patent Document 1 and Patent Document 2). Patent Document 2 describes a polymerizable compound (S-1) having multiple polar groups and multiple polymerizable groups.

[現有技術文獻] [專利文獻]

[Prior Art Literature] [Patent Literature]

[Patent Literature 1] International Publication No. 2016/129490 [Patent Literature 2] International Publication No. 2017/209161

[Problems 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 due to ultraviolet irradiation, and a large voltage retention rate when used in a liquid crystal display element At least one of them, and has high solubility in the liquid crystal composition. The second subject is to provide a liquid crystal composition that contains the compound and satisfies a high nematic phase upper temperature, a low nematic phase lower temperature, a low viscosity, appropriate optical anisotropy, and positive or negative dielectric constants At least one of characteristics such as high anisotropy, high 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 device with wide temperature range, short response time, high transmittance, large voltage retention, low threshold voltage, large contrast, long life, good vertical alignment, etc. At least one. [Means to solve the problem]

式（1）中， R¹ 為氫或碳數1至15的烷基，該R¹ 中，至少一個-CH₂ -可經-O-或-S-取代，至少一個-(CH₂ )₂ -可經-CH=CH-或-C≡C-取代，至少一個氫可經氟或氯取代； 環A¹ 及環A² 獨立地為1,2-伸環丙基、1,3-伸環丁基、1,3-伸環戊基、1,4-伸環己基、1,4-伸環庚基、1,4-伸環己烯基、1,4-伸苯基、萘-2,6-二基、十氫萘-2,6-二基、1,2,3,4-四氫萘-2,6-二基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基、或吡啶-2,5-二基，該環A¹ 及環A² 中，至少一個氫可經氟、氯、碳數1至10的烷基、碳數2至10的烯基、碳數1至9的烷氧基、或碳數2至9的烯氧基取代，至少一個氫可經氟或氯取代； a為0、1、2、3、或4； Z¹ 獨立地為單鍵或碳數1至6的伸烷基，該Z¹ 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，至少一個氫可經氟或氯取代； Sp⁰ 、Sp² 、Sp³ 、及Sp⁴ 獨立地為單鍵或碳數1至15的伸烷基，該Sp⁰ 、Sp² 、Sp³ 、及Sp⁴ 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，至少一個氫可經氟或氯取代； M¹ 、及M² 獨立地為氫、氟、氯、碳數1至5的烷基、或者至少一個氫經氟或氯取代的碳數1至5的烷基； R² 為碳數1至10的烷基，該R² 中，至少一個-CH₂ -可經-O-或-S-取代，至少一個-(CH₂ )₂ -可經-CH=CH-或-C≡C-取代，至少一個氫可經氟或氯取代； X¹ 獨立地為-OH、-NH₂ 、-OR⁴ 、-N(R⁴ )₂ 、-COOH、-SH、或-Si(R⁴ )₃ ； -OR⁴ 、-N(R⁴ )₂ 、及-Si(R⁴ )₃ 中， R⁴ 為氫或碳數1至10的烷基，該R⁴ 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； 環A² 或Sp⁰ 中，至少一個氫經式（1-a）所表示的基取代；

式（1-a）中， Sp⁵ 為單鍵或碳數1至10的伸烷基，該Sp⁵ 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，至少一個氫可經氟或氯取代； M³ 、及M⁴ 獨立地為氫、氟、氯、碳數1至5的烷基、或者至少一個氫經氟或氯取代的碳數1至5的烷基； R³ 為碳數1至10的烷基，該R³ 中，至少一個-CH₂ -可經-O-或-S-取代，至少一個-(CH₂ )₂ -可經-CH=CH-或-C≡C-取代，至少一個氫可經氟或氯取代。 [發明的效果]The present invention relates to a compound represented by formula (1), a liquid crystal composition containing the compound, and a liquid crystal display element including a polymer obtained by polymerizing the composition and/or at least a part of the composition.

In formula (1), R ¹ is hydrogen or an alkyl group having 1 to 15 carbon atoms. In this R ¹ , at least one -CH ₂ -may be substituted with -O- or -S-, and at least one -(CH ₂ ) ₂ -May be substituted by -CH=CH- or -C≡C-, at least one hydrogen may be substituted by fluorine or chlorine; Ring A ¹ and Ring A ^{2 are} independently 1,2-cyclopropyl, 1,3-extend Cyclobutyl, 1,3-cyclopentyl, 1,4-cyclohexyl, 1,4-cycloheptyl, 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, or pyridine-2,5-diyl, in ring A ¹ and ring A ² , at least one hydrogen can be Chlorine, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkoxy group having 1 to 9 carbon atoms, or alkenoxy group having 2 to 9 carbon atoms, at least one hydrogen may be substituted by fluorine or chlorine Substitution; a is 0, 1, 2, 3, or 4; Z ^{1 is} independently a single bond or an alkylene group having 1 to 6 carbon atoms. In Z ¹ , at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH- or -C≡C-, at least one hydrogen may be substituted by fluorine or chlorine Substitution; Sp ⁰ , Sp ² , Sp ³ , and Sp ^{4 are} independently a single bond or an alkylene group having 1 to 15 carbon atoms, and at least one of the Sp ⁰ , Sp ² , Sp ³ , and Sp ⁴ -CH ₂ -Can be substituted with -O-, -CO-, -COO-, -OCO-, or -OCOO-, at least one -(CH ₂ ) ₂ -Can be substituted with -CH=CH- or -C≡C-, at least One hydrogen may be substituted by fluorine or chlorine; M ¹ and M ^{2 are} independently hydrogen, fluorine, chlorine, C 1-5 alkyl group, or at least one hydrogen substituted by fluorine or chlorine C 1-5 alkyl group R ² is an alkyl group having 1 to 10 carbon atoms. In R ² , at least one -CH ₂ -may be substituted by -O- or -S-, and at least one -(CH ₂ ) ₂ -may be substituted by -CH= CH- or -C≡C- substitution, at least one hydrogen may be substituted by fluorine or chlorine; X ^{1 is} independently -OH, -NH ₂ , -OR ⁴ , -N(R ⁴ ) ₂ , -COOH, -SH, Or -Si(R ⁴ ) ₃ ; -OR ⁴ , -N(R ⁴ ) ₂ , and -Si(R ⁴ ) ₃ , R ⁴ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and in R ⁴ , At least one -CH ₂ -may be substituted by -O-, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH-, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; Ring A ² or In Sp ⁰ , at least one hydrogen is substituted with the group represented by formula (1-a);

In formula (1-a), Sp ⁵ is a single bond or an alkylene group having 1 to 10 carbon atoms. In this Sp ⁵ , at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-,- OCO- or -OCOO- substitution, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH- or -C≡C-, at least one hydrogen may be substituted by fluorine or chlorine; M ³ and M ^{4 are} independent Ground is hydrogen, fluorine, chlorine, C 1-5 alkyl, or at least one hydrogen is substituted with fluorine or chlorine, C 1-5 alkyl; R ³ is C 1-10 alkyl, the R ^{In 3} , at least one -CH ₂ -may be substituted by -O- or -S-, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH- or -C≡C-, and at least one hydrogen may be substituted by fluorine Or chlorine substitution. [Effect of invention]

The first advantage of the present invention is to provide a compound that has high chemical stability, high ability to align liquid crystal molecules, high polymerization reactivity caused by ultraviolet irradiation, and a large voltage retention rate in the case of being used in a liquid crystal display element At least one of them, and has high solubility in the liquid crystal composition. The second advantage is to provide a liquid crystal composition that contains the compound and satisfies a high nematic phase upper temperature, a low nematic phase lower temperature, a low viscosity, an appropriate optical anisotropy, and positive or negative dielectric constants. At least one of characteristics such as high anisotropy, high 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 device with wide temperature range, short response time, high transmittance, large voltage retention, low threshold voltage, large contrast, long life, good vertical alignment, etc. At least one.

How to use the terms in this specification is as follows. Sometimes the terms "liquid crystal compound", "liquid crystal composition", and "liquid crystal display element" are simply referred to as "compound", "composition", and "element", respectively. "Liquid crystal compound" is a compound having a nematic phase and a smectic phase equivalent liquid crystal phase, and although it does not have a liquid crystal phase, but for the purpose of adjusting the physical properties of the composition such as the upper limit temperature, the lower limit temperature, viscosity, and dielectric anisotropy The general term for the compound added for the purpose. This compound usually has a six-membered ring such as 1,4-cyclohexyl or 1,4-phenylene, and its molecular structure is rod-like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. The liquid crystal compound having an alkenyl group is not a polymerizable compound in terms of its meaning. "Polar compounds" help the alignment of liquid crystal molecules through the interaction of polar groups with the surface of the substrate. "Liquid crystal display element" is a general term for liquid crystal display panels and liquid crystal display modules.

The liquid crystal composition is usually prepared by mixing a plurality of liquid crystal compounds. In this composition, for the purpose of further adjusting the 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. The ratio (content) of the liquid crystal compound in the liquid crystal composition is expressed by the weight percentage (weight %) based on the weight of the liquid crystal composition not containing the additive even when the additive is added. The ratio (addition amount) of the additives in the liquid crystal composition is expressed by the weight percentage (weight %) based on the weight of the liquid crystal composition not containing the additives. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total weight of the liquid crystal compound. Sometimes parts per million by weight (ppm) are also used. The ratio of the polymerization initiator and the polymerization inhibitor in the liquid crystal composition is exceptionally expressed based on the weight of the polymerizable compound.

The "transparent point" is the transition temperature of the liquid crystal phase-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 and nematic equal) in the liquid crystal compound. The "upper limit temperature of the nematic phase" is the transition temperature of the nematic phase-isotropic phase in the mixture of the liquid crystal compound and the mother liquid crystal or the liquid crystal composition, and is sometimes simply referred to as the "upper limit temperature". Sometimes the "lower limit temperature of the nematic phase" is simply referred to as the "lower limit temperature". The expression "increasing the dielectric constant anisotropy" or "large dielectric constant anisotropy" means that the absolute value of the value increases or increases. The so-called "large voltage retention rate" means that the device has a large voltage retention rate not only at room temperature in the initial stage, but also at a temperature close to the upper limit temperature, and after long-term use of the device, not only at room temperature It also has a large voltage retention rate at a temperature close to the upper limit temperature. In the composition or element, the characteristics are sometimes studied before and after the time-dependent change test (including accelerated deterioration test). The expression "high solubility in the liquid crystal composition" means that the solubility is high with respect to any composition containing the liquid crystal compound at normal temperature, but as the composition, it can be used in the following examples The composition whose solubility is evaluated is used as a standard.

In some cases, the compound represented by formula (1) is simply referred to as "compound (1)". The compound (1) refers to a compound represented by formula (1), a mixture of two compounds, or a mixture of three or more compounds. This rule also applies to at least one compound selected from the group of compounds represented by formula (2). Symbols such as A ¹ , B ¹ , and C ¹ surrounded by hexagons correspond to rings A ¹ , B ¹ , and C ¹ , respectively. The hexagon represents a six-membered ring such as a cyclohexane ring or a benzene ring, or a condensed ring such as a naphthalene ring. A straight line that crosses one side of the hexagon indicates that any hydrogen on the ring may be substituted with a group such as -Sp ¹ -P ¹ . Subscripts such as f, g, and h indicate the number of substituted groups. When the subscript is 0, there is no such substitution. In the expression "ring A and ring C are independently X, Y, or Z", since there are multiple subjects, "independently" is used. When the subject is "ring A is", since the subject is single, "independently" is not used.

In the chemical formula of the compound, the symbol of the terminal group R ¹¹ is used in various compounds, but the groups represented by R ¹¹ in these compounds may be the same or different. For example, R in the compound (2) in the case where ¹¹ is ethyl, R compound (3) ¹¹ can be ethyl, propyl and the like may also be other groups. The rule also applies to other signs. In compound (8), when i is 2, there are two rings D ¹ . 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 is also applicable to any two rings D ¹ . The rule also applies to other signs.

The expression "at least one "A"" means that the number of "A" is arbitrary. The expression "at least one'A' may be substituted by'B'" includes the case of'A' itself not substituted by'B', the case of one'A' substituted by'B', and more than two'A' sutras In the case of'B' substitution, in these cases, the position of'A' substituted with'B' is arbitrary. The rule that the position of substitution is arbitrary also applies to the expression "at least one'A' is replaced by'B'". The expression "at least one A may be substituted with B, C, or D" means including the case where A is unsubstituted, at least one A is substituted with B, at least one A is substituted with C, and at least one A is substituted with D In the case of substitution, and in the case where at least two of A, B, C, and D are substituted. For example, at least one -CH _2- (or -CH ₂ CH ₂ -) alkyl group which may be substituted with -O- (or -CH=CH-) includes alkyl, alkenyl, alkoxy, alkoxy Alkyl, alkoxyalkenyl, alkenyloxyalkyl. Furthermore, the situation where two consecutive -CH ₂ -are replaced by -O- to become -OO- is not good. -CH like to, alkyl, methyl moiety (-CH ₂ -H) of ₂ - substituted -O- -OH case also becomes poor.

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. In the alkyl group and alkenyl group, at least one -CH ₂ -may be substituted with -O- In these groups, at least one hydrogen may be substituted with fluorine". In this expression, "these bases" can be interpreted according to the sentence. In this expression, "these groups" refer to alkyl, alkenyl, alkoxy, alkenyloxy, and the like. That is, "these bases" means all bases described before the term "these bases". This common sense explanation also applies to other terms.

Halogen refers to fluorine, chlorine, bromine, or iodine. The preferred halogen is fluorine or chlorine. Further, the preferred halogen is fluorine. In the liquid crystal compound, the alkyl group is linear or branched, and does not include a cyclic alkyl group. In general, linear alkyl groups are preferred to branched alkyl groups. These cases are also the same for terminal groups such as alkoxy groups and alkenyl groups. Regarding the three-dimensional configuration related to 1,4-cyclohexyl, in order to increase the upper limit temperature of the nematic phase, the trans configuration is superior to the cis configuration. 2-Fluoro-1,4-phenylene refers to the following two divalent groups. In the chemical formula, fluorine can go to the left (L) or to the right (R). This rule also applies to the left and right asymmetric divalent groups generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl.

The invention includes the following items.

式（1）中， R¹ 為氫或碳數1至15的烷基，該R¹ 中，至少一個-CH₂ -可經-O-或-S-取代，至少一個-(CH₂ )₂ -可經-CH=CH-或-C≡C-取代，至少一個氫可經氟或氯取代； 環A¹ 及環A² 獨立地為1,2-伸環丙基、1,3-伸環丁基、1,3-伸環戊基、1,4-伸環己基、1,4-伸環庚基、1,4-伸環己烯基、1,4-伸苯基、萘-2,6-二基、十氫萘-2,6-二基、1,2,3,4-四氫萘-2,6-二基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基、或吡啶-2,5-二基，該環A¹ 及環A² 中，至少一個氫可經氟、氯、碳數1至10的烷基、碳數2至10的烯基、碳數1至9的烷氧基、或碳數2至9的烯氧基取代，至少一個氫可經氟或氯取代； a為0、1、2、3、或4； Z¹ 獨立地為單鍵或碳數1至6的伸烷基，該Z¹ 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，至少一個氫可經氟或氯取代； Sp⁰ 、Sp² 、Sp³ 、及Sp⁴ 獨立地為單鍵或碳數1至15的伸烷基，該Sp⁰ 、Sp² 、Sp³ 、及Sp⁴ 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，至少一個氫可經氟或氯取代； M¹ 、及M² 獨立地為氫、氟、氯、碳數1至5的烷基、或者至少一個氫經氟或氯取代的碳數1至5的烷基； R² 為碳數1至10的烷基，該R² 中，至少一個-CH₂ -可經-O-或-S-取代，至少一個-(CH₂ )₂ -可經-CH=CH-或-C≡C-取代，至少一個氫可經氟或氯取代； X¹ 獨立地為-OH、-NH₂ 、-OR⁴ 、-N(R⁴ )₂ 、-COOH、-SH、或-Si(R⁴ )₃ ； -OR⁴ 、-N(R⁴ )₂ 、及-Si(R⁴ )₃ 中， R⁴ 為氫或碳數1至10的烷基，該R⁴ 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； 環A² 或Sp⁰ 中，至少一個氫經式（1-a）所表示的基取代；

式（1-a）中， Sp⁵ 為單鍵或碳數1至10的伸烷基，該Sp⁵ 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，至少一個氫可經氟或氯取代； M³ 、及M⁴ 獨立地為氫、氟、氯、碳數1至5的烷基、或者至少一個氫經氟或氯取代的碳數1至5的烷基； R³ 為碳數1至10的烷基，該R³ 中，至少一個-CH₂ -可經-O-或-S-取代，至少一個-(CH₂ )₂ -可經-CH=CH-或-C≡C-取代，至少一個氫可經氟或氯取代。Item 1. A compound represented by formula (1).

In formula (1), R ¹ is hydrogen or an alkyl group having 1 to 15 carbon atoms. In this R ¹ , at least one -CH ₂ -may be substituted with -O- or -S-, and at least one -(CH ₂ ) ₂ -May be substituted by -CH=CH- or -C≡C-, at least one hydrogen may be substituted by fluorine or chlorine; Ring A ¹ and Ring A ^{2 are} independently 1,2-cyclopropyl, 1,3-extend Cyclobutyl, 1,3-cyclopentyl, 1,4-cyclohexyl, 1,4-cycloheptyl, 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, or pyridine-2,5-diyl, in ring A ¹ and ring A ² , at least one hydrogen can be Chlorine, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkoxy group having 1 to 9 carbon atoms, or alkenoxy group having 2 to 9 carbon atoms, at least one hydrogen may be substituted by fluorine or chlorine Substitution; a is 0, 1, 2, 3, or 4; Z ^{1 is} independently a single bond or an alkylene group having 1 to 6 carbon atoms. In Z ¹ , at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH- or -C≡C-, at least one hydrogen may be substituted by fluorine or chlorine Substitution; Sp ⁰ , Sp ² , Sp ³ , and Sp ^{4 are} independently a single bond or an alkylene group having 1 to 15 carbon atoms, and at least one of the Sp ⁰ , Sp ² , Sp ³ , and Sp ⁴ -CH ₂ -Can be substituted with -O-, -CO-, -COO-, -OCO-, or -OCOO-, at least one -(CH ₂ ) ₂ -Can be substituted with -CH=CH- or -C≡C-, at least One hydrogen may be substituted by fluorine or chlorine; M ¹ and M ^{2 are} independently hydrogen, fluorine, chlorine, C 1-5 alkyl group, or at least one hydrogen substituted by fluorine or chlorine C 1-5 alkyl group R ² is an alkyl group having 1 to 10 carbon atoms. In R ² , at least one -CH ₂ -may be substituted by -O- or -S-, and at least one -(CH ₂ ) ₂ -may be substituted by -CH= CH- or -C≡C- substitution, at least one hydrogen may be substituted by fluorine or chlorine; X ^{1 is} independently -OH, -NH ₂ , -OR ⁴ , -N(R ⁴ ) ₂ , -COOH, -SH, Or -Si(R ⁴ ) ₃ ; -OR ⁴ , -N(R ⁴ ) ₂ , and -Si(R ⁴ ) ₃ , R ⁴ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and in R ⁴ , At least one -CH ₂ -may be substituted by -O-, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH-, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; Ring A ² or In Sp ⁰ , at least one hydrogen is substituted with the group represented by formula (1-a);

In formula (1-a), Sp ⁵ is a single bond or an alkylene group having 1 to 10 carbon atoms. In this Sp ⁵ , at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-,- OCO- or -OCOO- substitution, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH- or -C≡C-, at least one hydrogen may be substituted by fluorine or chlorine; M ³ and M ^{4 are} independent Ground is hydrogen, fluorine, chlorine, C 1-5 alkyl, or at least one hydrogen is substituted with fluorine or chlorine, C 1-5 alkyl; R ³ is C 1-10 alkyl, the R ^{In 3} , at least one -CH ₂ -may be substituted by -O- or -S-, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH- or -C≡C-, and at least one hydrogen may be substituted by fluorine Or chlorine substitution.

Item 2. The compound according to Item 1, wherein in formula (1), Z ^{1 is} independently a single bond, -(CH ₂ ) ₂ -, -(CH ₂ ) ₄ -, -CH=CH-, -C ≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, or -CF=CF-; Ring A ¹ and Ring A ^{2 are} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1, 3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in the ring A ¹ and ring A ² , at least one hydrogen can pass fluorine, chlorine , An alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, or an alkenoxy group having 2 to 9 carbon atoms, at least one hydrogen may be substituted by fluorine or chlorine ; In ring A ² or Sp ⁰ , at least one hydrogen is substituted by formula (1-a).

式（1-1）至式（1-8）中， R¹ 為碳數1至15的烷基、碳數2至15的烯基、碳數1至14的烷氧基、或碳數2～14的烯氧基，該R¹ 中，至少一個氫可經氟取代； 環A¹ 至環A⁵ 獨立地為1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、萘-2,6-二基、四氫吡喃-2,5-二基、或1,3-二噁烷-2,5-二基，該環A¹ 至環A⁵ 中，至少一個氫可經氟、碳數1至10的烷基、碳數2至10的烯基、碳數1至9的烷氧基、或碳數2至9的烯氧基取代，至少一個氫可經氟取代； b至e獨立地為0、1、2、3、或4，該些的合計為1、2、3、或4； Z¹ 至Z⁴ 獨立地為單鍵、-(CH₂ )₂ -、-CH=CH-、-C≡C-、-COO-、-OCO-、-CF₂ O-、-OCF₂ -、-CH₂ O-、-OCH₂ -、或-CF=CF-； Sp⁰ 至Sp⁸ 獨立地為單鍵或碳數1至7的伸烷基，該Sp⁰ 至Sp⁸ 中，至少一個-CH₂ -可經-O-、-COO-、或-OCO-取代，至少一個-(CH₂ )₂ -可經-CH=CH-取代，至少一個氫可經氟取代； M¹ 至M¹⁰ 獨立地為氫、氟、碳數1至5的烷基、或者至少一個氫經氟取代的碳數1至5的烷基； R² 至R⁶ 獨立地為碳數1至10的烷基，該R² 至R⁶ 中，至少一個-CH₂ -可經-O-取代； X¹ 獨立地為-OH、-NH₂ 、或-SH。Item 3. The compound according to Item 1 or Item 2, represented by any one of Formula (1-1) to Formula (1-8).

In formula (1-1) to formula (1-8), R ¹ is an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, or 2 carbon atoms -14-alkenyloxy group, at least one hydrogen in R ¹ may be substituted by fluorine; Ring A ¹ to Ring A ^{5 are} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1, 4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl, ring A ¹ to ring A ^{In 5} , at least one hydrogen may be substituted with fluorine, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenoxy having 2 to 9 carbons, At least one hydrogen may be substituted with fluorine; b to e are independently 0, 1, 2, 3, or 4, the total of these is 1, 2, 3, or 4; Z ¹ to Z ^{4 are} independently single bonds, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, Or -CF=CF-; Sp ⁰ to Sp ^{8 are} independently a single bond or an alkylene group having 1 to 7 carbon atoms, and among Sp ⁰ to Sp ⁸ , at least one -CH ₂ -may be passed through -O-, -COO -, or -OCO- substitution, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH-, at least one hydrogen may be substituted by fluorine; M ¹ to M ^{10 are} independently hydrogen, fluorine, carbon number 1 to An alkyl group of 5, or an alkyl group of 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine; R ² to R ^{6 are} independently an alkyl group of 1 to 10 carbon atoms, and at least one of R ² to R ^6- CH ₂ -may be substituted with -O-; X ^{1 is} independently -OH, -NH ₂ , or -SH.

式（1-9）至式（1-16）中， R¹ 為碳數1至10的烷基、碳數2至10的烯基、或碳數1至9的烷氧基； 環A¹ 至環A⁵ 獨立地為1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、萘-2,6-二基、四氫吡喃-2,5-二基、或1,3-二噁烷-2,5-二基，該環A¹ 至環A⁵ 中，至少一個氫可經氟、碳數1至5的烷基、碳數2至5的烯基、或碳數1至4的烷氧基取代； b至e獨立地為0、1、2、3、或4，該些的合計為1、2、3、或4； Z¹ 至Z⁴ 獨立地為單鍵、-(CH₂ )₂ -、-CH=CH-、-C≡C-、-CH₂ O-、或-OCH₂ -； Sp⁰ 至Sp⁸ 獨立地為單鍵或碳數1至5的伸烷基，該Sp⁰ 至Sp⁸ 中，至少一個-CH₂ -可經-O-取代，至少一個-(CH₂ )₂ -可經-CH=CH-取代； M¹ 至M¹⁰ 獨立地為氫、氟、碳數1至5的烷基、或至少一個氫經氟取代的碳數1至5的烷基； R² 為碳數1至3的烷基； R³ 至R⁶ 獨立地為碳數1至10的烷基、或碳數1至9的烷氧基。Item 4. The compound according to any one of Items 1 to 3, represented by any one of Formula (1-9) to Formula (1-16).

In formula (1-9) to formula (1-16), R ¹ is a C 1-10 alkyl group, a C 2-10 alkenyl group, or a C 1-9 alkoxy group; Ring A ¹ To Ring A ^{5 is} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5 -Diyl, or 1,3-dioxane-2,5-diyl, in the ring A ¹ to ring A ⁵ , at least one hydrogen can be through fluorine, C 1-5 alkyl, C 2 to Alkenyl group of 5, or alkoxy group having 1 to 4 carbons; b to e are independently 0, 1, 2, 3, or 4, the total of these is 1, 2, 3, or 4; Z ¹ Up to Z ^{4 is} independently a single bond, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C-, -CH ₂ O-, or -OCH ₂ -; Sp ⁰ to Sp ^{8 are} independently single A bond or an alkylene group having 1 to 5 carbon atoms. In Sp ⁰ to Sp ⁸ , at least one -CH ₂ -may be substituted with -O-, and at least one -(CH ₂ ) ₂ -may be substituted with -CH=CH- ; M ¹ to M ^{10 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is substituted with fluorine; R ² is an alkyl group having 1 to 3 carbons ; R ³ to R ^{6 are} independently C 1-10 alkyl or C 1-9 alkoxy.

式（1-17）至式（1-53）中， R¹ 為碳數1～10的烷基、碳數2～10的烯基、或碳數1～9的烷氧基； Z¹ 至Z³ 獨立地為單鍵或-(CH₂ )₂ -； Sp⁰ 、Sp¹ 、Sp² 、Sp⁵ 、Sp⁶ 、及Sp⁷ 獨立地為單鍵或碳數1至5的伸烷基，該Sp⁰ 、Sp¹ 、Sp² 、Sp⁵ 、Sp⁶ 、及Sp⁷ 中，至少一個-CH₂ -可經-O-取代； Y¹ 至Y¹¹ 獨立地為氫、氟、碳數1至5的烷基、碳數2至5的烯基、或碳數1至4的烷氧基； R² 為碳數1至10的烷基、或碳數1至9的烷氧基； R³ 、R⁴ 、及R⁵ 獨立地為碳數1至3的烷基； M¹ 及M² 獨立地為氫、氟、碳數1至5的烷基、或至少一個氫經氟取代的碳數1至5的烷基。Item 5. The compound according to any one of Items 1 to 4, represented by any one of Formula (1-17) to Formula (1-53).

In formula (1-17) to formula (1-53), R ¹ is a C 1-10 alkyl group, a C 2-10 alkenyl group, or a C 1-9 alkoxy group; Z ¹ to Z ^{3 is} independently a single bond or -(CH ₂ ) ₂ -; Sp ⁰ , Sp ¹ , Sp ² , Sp ⁵ , Sp ⁶ , and Sp ^{7 are} independently a single bond or an alkylene group having 1 to 5 carbon atoms, In the Sp ⁰ , Sp ¹ , Sp ² , Sp ⁵ , Sp ⁶ , and Sp ⁷ , at least one -CH ₂ -may be substituted with -O-; Y ¹ to Y ^{11 are} independently hydrogen, fluorine, and carbon number 1 to 5 alkyl group, alkenyl group having 2 to 5 carbon atoms, or alkoxy group having 1 to 4 carbon atoms; R ² is alkyl group having 1 to 10 carbon atoms, or alkoxy group having 1 to 9 carbon atoms; R ³ , R ⁴ and R ^{5 are} independently an alkyl group having 1 to 3 carbon atoms; M ¹ and M ^{2 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 with fluorine 1 to 5 alkyl groups.

式（1-54）至式（1-88）中， R¹ 為碳數1～10的烷基； Z¹ 及Z² 獨立地為單鍵或-(CH₂ )₂ -； Y¹ 至Y¹¹ 獨立地為氫、氟、甲基、或乙基； Sp⁰ 、Sp¹ 、Sp² 、Sp⁵ 、Sp⁶ 、及Sp⁷ 獨立地為單鍵或碳數1至5的伸烷基，該Sp⁰ 、Sp¹ 、Sp² 、Sp⁵ 、Sp⁶ 、及Sp⁷ 中，至少一個-CH₂ -可經-O-取代； R² 為碳數1～10的烷基； M¹ 及M² 獨立地為氫、氟、碳數1至5的烷基、或至少一個氫經氟取代的碳數1至5的烷基。Item 6. The compound according to any one of Items 1 to 5, represented by any one of Formula (1-54) to Formula (1-88).

In formula (1-54) to formula (1-88), R ¹ is an alkyl group having 1 to 10 carbon atoms; Z ¹ and Z ^{2 are} independently a single bond or -(CH ₂ ) ₂ -; Y ¹ to Y ^{11 is} independently hydrogen, fluorine, methyl, or ethyl; Sp ⁰ , Sp ¹ , Sp ² , Sp ⁵ , Sp ⁶ , and Sp ^{7 are} independently single bonds or alkylene groups having 1 to 5 carbon atoms, the In Sp ⁰ , Sp ¹ , Sp ² , Sp ⁵ , Sp ⁶ , and Sp ⁷ , at least one -CH ₂ -may be substituted with -O-; R ² is an alkyl group having 1 to 10 carbon atoms; M ¹ and M ² It is independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine.

Item 7. A liquid crystal composition containing at least one compound according to any one of Items 1 to 6.

式（2）至式（4）中， R¹¹ 及R¹² 獨立地為碳數1至10的烷基或碳數2至10的烯基，該R¹¹ 及R¹² 中，至少一個-CH₂ -可經-O-取代，至少一個氫可經氟取代； 環B¹ 、環B² 、環B³ 、及環B⁴ 獨立地為1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、2,5-二氟-1,4-伸苯基、或嘧啶-2,5-二基； Z¹¹ 、Z¹² 、及Z¹³ 獨立地為單鍵、-COO-、-CH₂ CH₂ -、-CH=CH-、或-C≡C-。Item 8. The liquid crystal composition according to Item 7, containing 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 at least one of -CH ₂ in R ¹¹ and R ¹² -May be substituted by -O-, 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-cyclohexyl, 1,4-phenylene , 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, or pyrimidine-2,5-diyl; Z ¹¹ , Z ¹² , and Z ^{13 are} independently Single bond, -COO-, -CH ₂ CH ₂ -, -CH=CH-, or -C≡C-.

式（5）至式（7）中， R¹³ 為碳數1至10的烷基或碳數2至10的烯基，該R¹³ 中，至少一個-CH₂ -可經-O-取代，至少一個氫可經氟取代； X¹¹ 為氟、氯、-OCF₃ 、-OCHF₂ 、-CF₃ 、-CHF₂ 、-CH₂ F、-OCF₂ CHF₂ 、或-OCF₂ CHFCF₃ ； 環C¹ 、環C² 、及環C³ 獨立地為1,4-伸環己基、1,4-伸苯基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基、或至少一個氫經氟取代的1,4-伸苯基； Z¹⁴ 、Z¹⁵ 、及Z¹⁶ 獨立地為單鍵、-COO-、-OCO-、-CH₂ O-、-OCH₂ -、-CF₂ O-、-OCF₂ -、-CH₂ CH₂ -、-CH=CH-、-C≡C-、或-(CH₂ )₄ -； L¹¹ 及L¹² 獨立地為氫或氟。Item 9. The liquid crystal composition according to Item 7 or Item 8, which contains at least one compound selected from the group of compounds represented by Formula (5) to Formula (7).

In formula (5) to formula (7), R ¹³ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in this R ¹³ , at least one -CH ₂ -may be substituted with -O-, At least one hydrogen may be substituted with 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-cyclohexyl, 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 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.

式（8）中， R¹⁴ 為碳數1至10的烷基或碳數2至10的烯基，該R¹⁴ 中，至少一個-CH₂ -可經-O-取代，至少一個氫可經氟取代； X¹² 為-C≡N或-C≡C-C≡N； 環D¹ 為1,4-伸環己基、1,4-伸苯基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基、或至少一個氫經氟取代的1,4-伸苯基； Z¹⁷ 為單鍵、-COO-、-OCO-、-CH₂ O-、-OCH₂ -、-CF₂ O-、-OCF₂ -、-CH₂ CH₂ -、或-C≡C-； L¹³ 及L¹⁴ 獨立地為氫或氟； i為1、2、3、或4。Item 10. The liquid crystal composition according to any one of Items 7 to 9, 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. In R ¹⁴ , at least one -CH ₂ -may be substituted by -O-, and at least one hydrogen may be substituted by Fluorine substitution; X ¹² is -C≡N or -C≡CC≡N; Ring D ¹ is 1,4-cyclohexyl, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or 1,4-phenylene with at least one hydrogen substituted by fluorine; Z 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.

式（11）至式（19）中， R¹⁵ 、R¹⁶ 、及R¹⁷ 獨立地為碳數1至10的烷基或碳數2至10的烯基，該R¹⁵ 、R¹⁶ 、及R¹⁷ 中，至少一個-CH₂ -可經-O-取代，該些基中，至少一個氫可經氟取代，而且R¹⁷ 亦可為氫或氟； 環E¹ 、環E² 、環E³ 、及環E⁴ 獨立地為1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、四氫吡喃-2,5-二基、十氫萘-2,6-二基、或至少一個氫經氟取代的1,4-伸苯基； 環E⁵ 及環E⁶ 獨立地為1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、四氫吡喃-2,5-二基、或十氫萘-2,6-二基； Z¹⁸ 、Z¹⁹ 、Z²⁰ 、及Z²¹ 獨立地為單鍵、-COO-、-OCO-、-CH₂ O-、-OCH₂ -、-CF₂ O-、-OCF₂ -、-CH₂ CH₂ -、-CF₂ OCH₂ CH₂ -、或-OCF₂ CH₂ CH₂ -； L¹⁵ 及L¹⁶ 獨立地為氟或氯； S¹¹ 為氫或甲基； X為-CHF-或-CF₂ -； j、k、m、n、p、q、r、及s獨立地為0或1，k、m、n、及p的和為1或2，q、r、及s的和為0、1、2、或3， t為1、2、或3。Item 11. The liquid crystal composition according to any one of Items 7 to 10, containing 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 the R ¹⁵ , R ¹⁶ , and R ^{In 17} , at least one -CH ₂ -may be substituted with -O-, in these groups, at least one hydrogen may be substituted with fluorine, and R ¹⁷ may also be hydrogen or fluorine; ring E ¹ , ring E ² , ring E ³ , And ring E ^{4 is} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, tetrahydropyran-2,5-diyl, decahydronaphthalene- 2,6-diyl, or 1,4-phenylene with at least one hydrogen substituted with fluorine; ring E ⁵ and ring E ^{6 are} independently 1,4-cyclohexyl, 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 single bonds , -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ OCH ₂ CH ₂ -, or -OCF ₂ CH ₂ CH ₂ -; L ¹⁵ and L ^{16 are} independently fluorine or chlorine; S ¹¹ is hydrogen or methyl; X is -CHF- or -CF ₂ -; j, k, m, n, p, q, r, and s are independently 0 or 1, the sum of k, m, n, and p is 1 or 2, the sum of q, r, and s is 0, 1, 2, or 3, and t is 1, 2, Or 3.

式（20）中， 環F及環I獨立地為環己基、環己烯基、苯基、1-萘基、2-萘基、四氫吡喃-2-基、1,3-二噁烷-2-基、嘧啶-2-基、或吡啶-2-基，該環F及環I中，至少一個氫可經鹵素、碳數1至12的烷基、碳數1至12的烷氧基、或至少一個氫經鹵素取代的碳數1至12的烷基取代； 環G為1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、萘-1,2-二基、萘-1,3-二基、萘-1,4-二基、萘-1,5-二基、萘-1,6-二基、萘-1,7-二基、萘-1,8-二基、萘-2,3-二基、萘-2,6-二基、萘-2,7-二基、菲-2,7-二基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基、或吡啶-2,5-二基，該環G中，至少一個氫可經鹵素、碳數1至12的烷基、碳數1至12的烷氧基、或至少一個氫經鹵素取代的碳數1至12的烷基取代； Z²² 及Z²³ 獨立地為單鍵或碳數1至10的伸烷基，該Z²² 及Z²³ 中，至少一個-CH₂ -可經-O-、-CO-、-COO-、或-OCO-取代，至少一個-CH₂ CH₂ -可經-CH=CH-、-C(CH₃ )=CH-、-CH=C(CH₃ )-、或-C(CH₃ )=C(CH₃ )-取代，至少一個氫可經氟或氯取代； P¹¹ 、P¹² 、及P¹³ 獨立地為聚合性基； Sp¹¹ 、Sp¹² 、及Sp¹³ 獨立地為單鍵或碳數1至10的伸烷基，該Sp¹¹ 、Sp¹² 、及Sp¹³ 中，至少一個-CH₂ -可經-O-、-COO-、-OCO-、或-OCOO-取代，至少一個-CH₂ CH₂ -可經-CH=CH-或-C≡C-取代，至少一個氫可經氟或氯取代； u為0、1、或2； f、g、及h獨立地為0、1、2、3、或4，而且f、g、及h的和為1以上。Item 12. The liquid crystal composition according to any one of Item 7 to Item 11, containing 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-dioxan Alk-2-yl, pyrimidin-2-yl, or pyrid-2-yl, in ring F and ring I, at least one hydrogen can be halogen, alkyl having 1 to 12 carbons, alkyl having 1 to 12 carbons Oxygen, or at least one hydrogen is substituted by halogen substituted alkyl having 1 to 12 carbons; ring G is 1,4-cyclohexyl, 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, tetra Hydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in the ring G, At least one hydrogen may be substituted with halogen, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or at least one hydrogen is substituted with a halogen substituted alkyl group having 1 to 12 carbons; Z ²² and Z ^{23 are} independently The ground is a single bond or an alkylene group having 1 to 10 carbon atoms. In Z ²² and Z ²³ , at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, or -OCO-, 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 )- , At least one hydrogen may be substituted with fluorine or chlorine; P ¹¹ , P ¹² , and P ^{13 are} independently polymerizable groups; Sp ¹¹ , Sp ¹² , and Sp ^{13 are} independently single bonds or alkylene having 1 to 10 carbon atoms In the Sp ¹¹ , Sp ¹² , and Sp ¹³ , at least one -CH ₂ -may be substituted with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may be substituted -CH=CH- or -C≡C- substitution, 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.

式（P-1）至式（P-5）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。Item 13. The liquid crystal composition according to Item 12, wherein in formula (20), P ¹¹ , P ¹² , and P ^{13 are} independently selected from the group represented by formula (P-1) to formula (P-5) A group in a 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 carbons, or a carbon number in which at least one hydrogen is substituted with halogen 1 to 5 alkyl groups.

式（20-1）至式（20-7）中， L³¹ 、L³² 、L³³ 、L³⁴ 、L³⁵ 、L³⁶ 、L³⁷ 、及L³⁸ 獨立地為氫、氟、或甲基； Sp¹¹ 、Sp¹² 、及Sp¹³ 獨立地為單鍵或碳數1至10的伸烷基，該Sp¹¹ 、Sp¹² 、及Sp¹³ 中，至少一個-CH₂ -可經-O-、-COO-、-OCO-、或-OCOO-取代，至少一個-CH₂ CH₂ -可經-CH=CH-或-C≡C-取代，至少一個氫可經氟或氯取代； P¹¹ 、P¹² 、及P¹³ 獨立地為選自式（P-1）至式（P-3）所表示的聚合性基的群組中的基；

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。Item 14. The liquid crystal composition according to Item 12 or Item 13, wherein the polymerizable compound represented by formula (20) is selected from the polymerizable compounds represented by formula (20-1) to formula (20-7) At least one compound in the group.

In formula (20-1) to formula (20-7), L ³¹ , L ³² , L ³³ , L ³⁴ , L ³⁵ , L ³⁶ , L ³⁷ , and L ^{38 are} independently hydrogen, fluorine, or methyl; Sp ¹¹ , Sp ¹² , and Sp ^{13 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. Among Sp ¹¹ , Sp ¹² , and Sp ¹³ , at least one -CH ₂ -may be passed through -O-,- COO-, -OCO-, or -OCOO- substitution, at least one -CH ₂ CH ₂ -may be substituted by -CH=CH- or -C≡C-, at least one hydrogen may 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 with halogen 1 to 5 alkyl groups.

Item 15. The liquid crystal composition according to any one of Items 7 to 14, containing a polymerizable compound selected from the compound represented by Formula (1) or Formula (20), a polymerization initiator, and a polymerization inhibitor At least one of the group of agents, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, pigments, and defoamers.

Item 16. A liquid crystal display element containing at least a part selected from the liquid crystal composition according to any one of items 7 to 15 and the liquid crystal composition according to any one of items 7 to 15 to be polymerized At least one of the groups formed by the winners.

The present invention also includes the following items. (A) The liquid crystal composition further contains a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a pigment, an antifoaming agent, etc. At least two kinds of things. (B) A polymerizable composition is prepared by adding a polymerizable compound different from the compound (1) or the compound (20) to the liquid crystal composition. (C) A polymerizable composition prepared by adding compound (1) and compound (20) to the liquid crystal composition. (D) A liquid crystal composite prepared by polymerizing the polymerizable composition. (E) A polymer-stabilized alignment element containing the liquid crystal composite. (F) A polymer-stabilized alignment type device made by using a polymerizable composition by adding compound (1) and compound (20) to the liquid crystal composition And a polymerizable compound different from compound (1) or compound (20).

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 appearance of compound (1) The compound (1) of the present invention is characterized by having a mesogen moiety composed of at least one ring, two polar groups, and two or more polymerizable groups. The compound (1) is useful because the polar group interacts with the surface of the substrate such as glass (or metal oxide) by non-covalent bonding. One of the uses is an additive for a liquid crystal composition used in a liquid crystal display element. In this use, the compound (1) is added for the purpose of controlling the alignment of liquid crystal molecules. Such an additive is preferably chemically stable under the condition of being sealed in the element, has a high ability to align liquid crystal molecules, has a large voltage retention rate when used in a liquid crystal display element, and has a high solubility in a liquid crystal composition . The compound (1) satisfies this characteristic to a considerable extent. If it is the previous compound, it cannot be achieved, and the solubility in the liquid crystal composition is extremely large. By using the compound (1) and the case of using the previous compound In contrast, an element having excellent long-term stability can be easily obtained when the alignment and voltage retention are maintained to the same degree or more.

The preferred examples of the compound (1) will be described. The preferred examples of symbols such as R ¹ , A ¹ , and Sp ⁰ in the compound (1) are also applicable to the lower formula of the compound (1), for example, formula (1-1). In the compound (1), by appropriately combining the types of these groups, the characteristics can be adjusted arbitrarily. Since there is no big difference in the characteristics of the compounds, the compound (1) may contain ² H (deuterium), ¹³ C and other isotopes in a larger amount than natural abundance.

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

Preferred R ¹ is an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, or an alkenyl group having 2 to 14 carbon atoms. Among these groups, At least one hydrogen can be replaced by fluorine. Further preferable R ¹ is an alkyl group having 1 to 10 carbons, an alkenyl group having 2 to 10 carbons or an alkoxy group having 1 to 9 carbons. Particularly preferred R ¹ is an alkyl group having 1 to 10 carbon atoms.

The compound wherein R ¹ is an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 14 carbon atoms has high chemical stability. The compound wherein R ¹ is an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or an alkenyloxy group having 2 to 14 carbon atoms 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.

Ring A ¹ and Ring A ^{2 are} independently 1,2-cyclopropyl, 1,3-cyclobutyl, 1,3-cyclopentyl, 1,4-cyclohexyl, 1,4-extend Cycloheptyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, decalin-2,6-diyl, 1,2,3,4- Tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine- 2,5-diyl, in the ring A ¹ and ring A ² , at least one hydrogen can be through fluorine, chlorine, C 1-10 alkyl, C 2-10 alkenyl, C 1-9 Alkoxy, or alkenyloxy having 2 to 9 carbon atoms is substituted, and at least one hydrogen may be substituted with fluorine or chlorine.

Preferred ring A ¹ and ring A ² are 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran -2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen It may be substituted by fluorine, chlorine, C 1-10 alkyl, C 2-10 alkenyl, C 1-9 alkoxy, or C 2-9 alkenyl. At least one hydrogen can be replaced by fluorine or chlorine.

More preferred ring A ¹ and ring A ² are 1,4-cyclohexyl, 1,4-cyclohexenyl, 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 can be substituted by fluorine, alkyl with 1 to 10 carbons, and carbon with 2 to 10 Is substituted by an alkenyl group having 1 to 9 carbon atoms, or an alkenyl group having 2 to 9 carbon atoms, and in these groups, at least one hydrogen may be substituted with fluorine.

Further preferred ring A ¹ and ring A ² are 1,4-cyclohexyl, 1,4-cyclohexenyl, 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 can be fluorinated, alkyl with 1 to 5 carbons, and carbon with 2 to 5 Substituted by an alkenyl group of 1 to 4 carbon atoms.

Particularly preferred ring A ¹ and ring A ² are 1,4-cyclohexyl, 1,4-phenylene, 2-substituted 1,4-phenylene, 3-substituted 1,4-phenylene, or The 1,4-benzyl group is substituted at the 2 and 3 positions, and the substituent is preferably hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 4 carbon atoms. The alkoxy group is more preferably hydrogen, fluorine, methyl, or ethyl.

Ring A ¹ and Ring A ^{2 are} independently 1,3-cyclopentyl, 1,4-cyclohexyl, 1,4-cycloheptyl, 1,4-phenylene, and at least one hydrogen is substituted with fluorine 1,4-phenylene, 1,4-phenylene with at least one hydrogen substituted with an alkyl group having 1 to 5 carbon atoms, decalin-2,6-diyl, or tetrahydropyran-2, The 5-diyl compound has high chemical stability. Ring A ¹ and Ring A ^{2 are} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is substituted with fluorine 1. A compound in which at least one hydrogen is substituted with a C1-C5 alkyl group for 1,4-phenylene, or at least one hydrogen is substituted for an C2-C5 alkenyl group in a liquid crystal The solubility is high. The compound in which ring A ¹ and ring A ^{2 are} independently 1,4-cyclohexyl, 1,4-phenylene, and 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 substituted with at least one hydrogen by an alkyl group having 1 to 5 carbon atoms, and at least one hydrogen atom having 1 to 4 carbon atoms Polymerization of alkoxy substituted 1,4-phenylene, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl compounds caused by ultraviolet irradiation High reactivity.

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

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

Z ¹ is a single bond or an alkylene group having 1 to 6 carbon atoms. In this Z ¹ , at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, -OCO-, or -OCOO- . However, there is no case where adjacent -CH ₂ -is continuously substituted with 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.

Preferred Z ¹ is a single bond, -(CH ₂ ) ₂ -, -(CH ₂ ) ₄ -, -CH=CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O- , -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, or -CF=CF-. More preferably, Z ¹ is a single bond, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, or -CF=CF-. Further preferred Z ¹ is a single bond, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C-, -CH ₂ O-, or -OCH ₂ -, further preferred Z ¹ is a single bond Or -(CH ₂ ) ₂ -, particularly good Z ¹ is a single bond.

The compound having Z ¹ as a single bond has high chemical stability. The compound in which Z ¹ is a single bond, -(CH ₂ ) ₂ -, -CF ₂ O-, or -OCF ₂ -has a high solubility in the 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 due to ultraviolet irradiation.

Sp ⁰ , Sp ² , Sp ³ , and Sp ^{4 are} independently a single bond or an alkylene group having 1 to 15 carbon atoms. Of Sp ⁰ , Sp ² , Sp ³ , and Sp ⁴ , at least one -CH ₂ -may be Substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH- or -C≡C-, at least one hydrogen It can be replaced by fluorine or chlorine.

Preferably, Sp ⁰ , Sp ² , Sp ³ , and Sp ^{4 are} independently a single bond or an alkylene group having 1 to 7 carbon atoms. Of Sp ⁰ , Sp ² , Sp ³ , and Sp ⁴ , at least one -CH ₂ -May be substituted with -O-, -COO-, or -OCO-, at least one -(CH ₂ ) ₂ -may be substituted with -CH=CH-, and at least one hydrogen may be substituted with fluorine.

Sp ⁰ , Sp ² , Sp ³ , and Sp ⁴ independently have a single bond or a C 1 to C 7 alkylene-extending compound, and the chemical stability is high. Sp ⁰ , Sp ² , Sp ³ and Sp ^{4 are} independently a compound having at least one -CH ₂ -O-substituted group of C 1-7 alkylene group or C 1-7 alkylene group The solubility in the liquid crystal composition is large.

More preferably, Sp ⁰ , Sp ² , Sp ³ , and Sp ^{4 are} independently a single bond or an alkylene group having 1 to 5 carbon atoms. Among the Sp ⁰ , Sp ² , Sp ³ , and Sp ⁴ , at least one -CH ₂ -May be substituted with -O-, at least one-(CH ₂ ) ₂ -may be substituted with -CH=CH-.

In terms of becoming a compound having better solubility in the liquid crystal composition, particularly preferred Sp ⁰ is a single bond or an alkylene group having 1 to 5 carbon atoms. In this Sp ⁰ , at least one -CH ₂ -may be used. Substituted by -O-; particularly preferred Sp ² is a single bond or an alkylene group having 1 to 5 carbon atoms. In this Sp ² , at least one -CH ₂ -may be substituted by -O-, and further preferably -CH _2- ; Sp ⁴ and Sp ³ are -CH ₂ -.

M ¹ and M ^{2 are} independently hydrogen, fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine, preferably hydrogen, fluorine, The alkyl group having 1 to 5 carbon atoms, or the alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine, is more preferably a hydrogen compound in terms of polymerization reactivity caused by ultraviolet irradiation. .

R ² is an alkyl group having 1 to 10 carbon atoms. In this R ² , at least one -CH ₂ -may be substituted by -O- or -S-, and at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH- Or -C≡C- substitution, at least one hydrogen may be substituted by fluorine or chlorine. Preferably R ² is an alkyl group having 1 to 5 carbons. In this R ² , at least one -CH ₂ -may be substituted with -O-. In terms of becoming a compound having better solubility in a liquid crystal composition, high chemical stability, and high ability to align liquid crystal molecules, it is more preferable that R ² is an alkyl group having 1 to 4 carbon atoms. R ² is ethyl, propyl, or butyl.

X ^{1 is} independently -OH, -NH ₂ , -OR ³ , -N(R ³ ) ₂ , -COOH, -SH, or -Si(R ³ ) ₃ . In terms of becoming a compound having more excellent solubility in the liquid crystal composition, X ¹ is preferably -OH, -NH ₂ , or -SH, and particularly preferably X ¹ is -OH. Here, R ³ is hydrogen or an alkyl group having 1 to 10 carbon atoms. In this R ³ , at least one -CH ₂ -may be substituted with -O-, and at least one -(CH ₂ ) ₂ -may be substituted with -CH=CH -Substitution, at least one hydrogen may be substituted 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. The compound in which X ¹ is -OH has high chemical stability, high ability to align liquid crystal molecules, a large voltage retention rate when used in a liquid crystal display element, and a high solubility in a liquid crystal composition.

Among them, at least one hydrogen in ring A ² or Sp ⁰ is substituted by formula (1-a).

Sp ⁵ is a single bond or an alkylene group having 1 to 10 carbon atoms. In this Sp ⁵ , at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, -OCO-, or -OCOO- , At least one -(CH ₂ ) ₂ -may be substituted by -CH=CH- or -C≡C-, and at least one hydrogen may be substituted by fluorine or chlorine.

The compound with Sp ⁵ being a single bond or an alkylene group having 1 to 7 carbon atoms has high chemical stability. The compound in which Sp ⁵ is an alkylene group having 1 to 7 carbon atoms, or at least one -CH ₂ -substituted with -O- group of an alkylene group having 1 to 7 carbon atoms has high solubility in the liquid crystal composition.

More preferably, Sp ⁵ is a single bond or an alkylene group having 1 to 5 carbon atoms. In this Sp ⁵ , at least one -CH ₂ -may be substituted with -O-, and at least one -(CH ₂ ) ₂ -may be substituted with -CH =CH- replaced.

In terms of becoming a compound having better solubility in the liquid crystal composition, it is particularly preferred that Sp ⁵ is a single bond or an alkylene group having 1 to 5 carbon atoms. In Sp ⁵ , at least one -CH ₂ -may be used. Replaced by -O-.

M ³ and M ^{4 are} independently hydrogen, fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine, preferably hydrogen, fluorine, The alkyl group having 1 to 5 carbon atoms, or the alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine, is more preferably a hydrogen compound in terms of polymerization reactivity due to ultraviolet irradiation. .

R ³ is an alkyl group having 1 to 10 carbon atoms. In this R ³ , at least one -CH ₂ -may be substituted by -O- or -S-, and at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH- Or -C≡C- substitution, at least one hydrogen may be substituted by fluorine or chlorine, more preferably hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen having 1 to 5 carbons substituted by fluorine In terms of becoming a compound having extremely high polymerization reactivity due to ultraviolet irradiation, hydrogen, methyl or ethyl is more preferred.

Preferred examples of compound (1) are compound (1-1) to compound (1-8) described in item 3. More preferred examples of compound (1) are compound (1-9) to compound (1-16) described in item 4. Further preferred examples of the compound (1) are the compound (1-17) to the compound (1-53) described in item 5. Examples of the best compound (1) are the compound (1-54) to the compound (1-88) described in item 6.

2. Synthesis of Compound (1) The synthesis method of the compound (1) will be described. The compound (1) can be synthesized by appropriately combining organic synthetic chemistry methods. Compounds not described in the synthesis method can be obtained by "Organic Syntheses" (John Wiley & Sons, Inc), "Organic Reactions" (John Wiley & Sons Publishing) The company (John Wiley & Sons, Inc)), "Comprehensive Organic Synthesis" (Pergamon Press), "New Experimental Chemistry Lecture" (Maruzen), etc. synthesis.

2-1. Formation of bonding group An example of a method of generating a bonding group in the compound (1) is described in the following flow. In this scheme, MSG ¹ (or MSG ² ) is a monovalent organic group having at least one ring. The monovalent organic groups represented by multiple MSG ¹ (or MSG ² ) may be the same or different. Compound (1A) to compound (1G) correspond to compound (1) or an intermediate of compound (1).

(I) Single key generation The compound (1A) is synthesized by reacting the boric acid compound (21) with the compound (22) in the presence of carbonate and tetrakis(triphenylphosphine)palladium catalyst. This compound (1A) can also be synthesized by reacting compound (23) with n-butyllithium, followed by zinc chloride, and in the presence of dichlorobis(triphenylphosphine)palladium catalyst The compound (22) is reacted.

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

(III) Generation of -CF ₂ O- and -OCF ₂ -Compound (26) is obtained by vulcanizing compound (1B) using Lawesson's reagent. Compound (1C) with -CF ₂ O- was synthesized by fluorinating compound (26) with hydrogen fluoride pyridine complex and N-bromosuccinimide (NBS). Refer to "Chem. Lett." by M. Kuroboshi and others, 1992, Issue 827. Compound (1C) can also be synthesized by fluorinating compound (26) using (diethylamino) sulphur trifluoride (DAST). Refer to WH Bunnelle et al. "Journal of Organic Chemistry (J. Org. Chem.)" 1990, No. 55, p. 768. Compounds having -OCF ₂ -can also be synthesized by this method.

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

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

(VI) Generation of -C≡C- In the presence of a catalyst of palladium dichloride and copper iodide, after reacting compound (23) with 2-methyl-3-butyn-2-ol, deprotection is performed 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) Formation of -CH ₂ O- and -OCH ₂ -Compound (30) is obtained by reducing compound (27) with sodium borohydride. Bromination with hydrobromic acid yields compound (31). Compound (1G) is synthesized by reacting compound (25) with compound (31) in the presence of potassium carbonate. Compounds having -OCH ₂ -can also be synthesized by this method.

(VIII) Generation of -CF=CF- After the compound (23) is treated with n-butyllithium, tetrafluoroethylene is reacted to obtain the compound (32). After the compound (22) is treated with n-butyl lithium, the compound (1H) is synthesized by reacting with the compound (32).

2-2. Formation of ring A ¹ and ring A ² About 1,2-cyclopropyl, 1,3-cyclobutyl, 1,3-cyclopentyl, 1,4-cyclohexyl, 1 ,4-cycloheptyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, decalin-2,6-diyl, 1,2, 3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl , Pyridine-2,5-diyl and other rings, starting materials are commercially available, or synthetic methods are well known.

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

In formula (1), compounds (1-51) in which M ¹ and M ² are hydrogen and X ¹ is -OH can be synthesized by the following method. Compound (51) is reacted with p-toluenesulfonic acid monohydrate and triethylamine in the corresponding acetone solvent. Compound (53) is obtained by reacting compound (52) with tosyl chloride and pyridine in a methylene chloride solvent. The compound (53) is reacted with sodium iodide in a 2-butanone solvent to obtain the compound (54). The compound (56) is obtained by reacting the compound (54) with the compound (55) in the presence of sodium hydride in a DMF solvent, and further reacting with potassium carbonate and polyoxymethylene in the presence of water. In the presence of tetrabutyl ammonium bromide (TBAB), THF and water, the compound (56) is reacted with lithium hydroxide monohydrate, and the pH is adjusted to 4 using citric acid to obtain the compound (57 ). Compound (58) and compound (57) synthesized by a known method are reacted in a methylene chloride solvent in the presence of DCC and DMAP to obtain compound (59). After the compound (59) is obtained, PPTS is used in a mixed solvent of THF and methanol for deprotection, whereby the compound (1-51) can be derived.

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

The compound (1) is added to the composition for the purpose of controlling the alignment of liquid crystal molecules. The preferred ratio of the compound (1) to 100% by weight of the liquid crystal composition is 0.05% by weight or more in terms of easy alignment of liquid crystal molecules, etc., in terms of further prevention of display defects of the device, etc. It is preferably 10% by 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 in which both terminal groups are alkyl or the like. Component B has a small dielectric constant anisotropy. Preferred examples of component B include compound (2-1) to compound (2-11), compound (3-1) to compound (3-19), and compound (4-1) to compound (4- 7). In these compounds, R ¹¹ and R ^{12 are} independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Among the R ¹¹ and R ¹² , at least one -CH ₂ -may be substituted by -O- Substitution, at least one hydrogen may be substituted by fluorine.

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

As the content of component B is increased, the dielectric constant anisotropy of the composition becomes smaller, but the viscosity becomes smaller. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the content of the component B is preferably large. The content of component B is preferably 30% by weight or more and more preferably 40% by weight or more with respect to 100% by weight of the liquid crystal composition, and the upper limit is not particularly limited, and is, for example, 99.95% by weight.

Component C is a compound having fluorine, chlorine or a fluorine-containing group at at least one end. Component C has a large positive dielectric constant anisotropy. Preferred 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. In this R ¹³ , at least one -CH ₂ -may be substituted by -O-, and at least one hydrogen may be substituted by Fluorine substitution; X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ , or -OCF ₂ CHFCF ₃ .

The dielectric constant anisotropy of the component C is positive, and its stability to heat, light, etc. is very good. Therefore, it can be preferably used in the case of preparing a composition for modes such as IPS, FFS, and OCB. The content of component C relative to 100% by weight of the liquid crystal composition is suitably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, and further preferably in the range of 40% by weight to 95% by weight . When component C is added to a composition having a negative dielectric anisotropy, the content of component C is preferably 30% by weight or less relative to 100% by weight of the liquid crystal composition. By adding the 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) having a single terminal group -C≡N or -C≡CC≡N. Since component D has a cyano group, it has a larger positive dielectric constant anisotropy. As preferred examples of the component D, the compound (8-1) to the compound (8-64) may be mentioned. 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. In this R ¹⁴ , at least one -CH ₂ -may be substituted by -O-, and at least one hydrogen may be substituted by Fluorine substitution; -X ¹² is -C≡N or -C≡CC≡N.

The dielectric anisotropy of the component D is positive and its value is large, so it is mainly used in the case of preparing a composition for TN and other modes. By adding this component D, the dielectric anisotropy of the composition can be increased. Component D has the effects of expanding the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. The component D is also useful for adjusting the voltage-transmittance curve of the device.

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

Component E is compound (11) to compound (19). Component E has a large negative dielectric constant anisotropy. These compounds have a 2,3-difluoro-1,4-phenylene-like phenylene group substituted by two halogens (fluorine or chlorine). 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 at least one of R ¹⁵ , R ¹⁶ , and R ^17- CH ₂ -may be substituted with -O-, at least one hydrogen may be substituted with fluorine, and R ¹⁷ may also be hydrogen or fluorine.

The dielectric constant anisotropy of component E is negative and large. Component E can be preferably used in the case of preparing a composition for IPS, VA, PSA and other modes. As the content of component E is increased, the dielectric constant anisotropy of the composition becomes negative and becomes larger, but the viscosity becomes larger. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the content is preferably small. Considering that the dielectric anisotropy is about -5, in order to perform sufficient voltage driving, the content of component E relative to 100% by weight of the liquid crystal composition is preferably 40% by weight or more.

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

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

By appropriately combining the above-mentioned component B, component C, component D, and component E, a liquid crystal composition satisfying at least one of the following characteristics can be prepared: high upper limit temperature, low lower limit temperature, low viscosity, optical anisotropy Appropriate, positive or negative dielectric constants have high anisotropy, large specific resistance, high stability to ultraviolet rays, high stability to heat, and large elastic constants.

3-2. Additives The liquid crystal composition is prepared by a well-known method. For example, a method of mixing the above components and then dissolving them by heating can be cited. Additives may be added to this composition depending on 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, defoamers, 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 forming a polymer in the liquid crystal composition. When the liquid crystal composition is injected into the device, ultraviolet rays are irradiated while a voltage is applied between the electrodes to polymerize the compound (1), whereby a polymer can be formed. At this time, the compound (1) is immobilized in a state where its polar group interacts with the glass (or metal oxide) substrate surface in a non-covalent bonding 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 can be shortened.

Preferred examples of the polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), and vinyl ketone. Further preferred examples are compounds having at least one acryloyloxy group and compounds having at least one methacryloyloxy group. Further preferred examples also include compounds having both acryloxy and methacryloxy. Particularly preferred examples of the polymerizable compound include compound (20). Compound (20) is a compound different from compound (1). Compound (1) has a polar group. On the other hand, the compound (20) preferably has no polar group.

In formula (20), ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan Alk-2-yl, pyrimidin-2-yl, or pyrid-2-yl, in ring F and ring I, at least one hydrogen can be halogen, alkyl having 1 to 12 carbons, alkyl having 1 to 12 carbons The oxy group, or at least one hydrogen is substituted with a halogen-substituted C 1-12 alkyl group.

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. Particularly preferred ring F or ring I is phenyl.

In formula (20), ring G is 1,4-cyclohexyl, 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 this ring G, at least one hydrogen can be passed through halogen, alkyl having 1 to 12 carbon atoms , An alkoxy group having 1 to 12 carbon atoms, or at least one hydrogen is substituted with a halogen substituted alkyl group having 1 to 12 carbon atoms.

Preferred ring G is 1,4-cyclohexyl, 1,4-cyclohexenyl, 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 preferred ring G is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, or 2-fluoro-1,4-phenylene. Particularly preferred ring G is 1,4-phenylene or 2-fluoro-1,4-phenylene. The best ring G is 1,4-phenylene.

In the formula (20), Z ²² and Z ^{23 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. Of the Z ²² and Z ²³ , at least one -CH ₂ -may be passed through -O-, -CO- , -COO-, or -OCO-, at least one -CH ₂ CH ₂ -can be replaced by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )-, or -C (CH ₃ )=C(CH ₃ )-Substitution, at least one hydrogen may be substituted by fluorine or chlorine. Preferably Z ²² or Z ²³ is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, or -OCO-. Further preferred Z ²² or Z ²³ is a single bond.

In the compound (20), P ¹¹ , P ¹² , and P ^{13 are} independently polymerizable groups. P ¹¹ to P ¹³ are preferably a group selected from the group of polymerizable groups represented by formula (P-1) to formula (P-5). Further preferred P ¹¹ to P ¹³ are groups represented by formula (P-1), formula (P-2), or formula (P-3). Particularly preferred P ¹¹ to P ¹³ are groups represented by formula (P-1). The preferred group represented by the formula (P-1) is acryloxy (-OCO-CH=CH ₂ ) or methacryloxy (-OCO-C(CH ₃ )=CH ₂ ). The wavy line from formula (P-1) to formula (P-5) indicates the part where bonding is performed.

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 with halogen 1 to 5 alkyl groups. In order to improve the reactivity, M ¹¹ , M ¹² , or M ¹³ are preferably hydrogen or methyl. More preferably, M ¹¹ is hydrogen or methyl, and further preferably 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 among Sp ¹¹ , Sp ¹² , and Sp ¹³ , at least one -CH ₂ -may be Substituted by -O-, -COO-, -OCO-, or -OCOO-, at least one -CH ₂ CH ₂ -can be substituted by -CH=CH- or -C≡C-, at least one hydrogen can be substituted by fluorine or chlorine replace. Preferably, Sp ¹¹ , Sp ¹² , and Sp ¹³ are single bonds.

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

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

Preferred examples of the compound (20) are the compound (20-1) to the compound (20-7) described in Item 15 and the compound (20-8) to the compound (20-11) described later. 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 alkyl having 1 to 5 carbons, and R ³² , R ³³ , and R At least one of ³⁴ is an alkyl group having 1 to 5 carbon atoms; v, and x are independently 0 or 1; t and u are independently integers of 1 to 10, and t+v and x+u are each up to 10; L ³¹ to L ^{36 are} independently hydrogen or fluorine, and L ³⁷ and L ^{38 are} independently hydrogen, fluorine, or methyl.

The polymerizable compound in the composition can be rapidly polymerized by using a polymerization initiator such as a photo radical polymerization initiator. In addition, by optimizing the reaction conditions during polymerization, the amount of remaining polymerizable compound can be reduced. Examples of photo radical polymerization initiators include TPO, 1173, and 4265 in the Darocure series of BASF, and 184, 369, 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/Michelerone mixture, hexaarylbiimidazole/mercaptobenzimidazole Mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, benzyl dimethyl ketal, 2-methyl-1-[4-(methylthio )Phenyl]-2-morpholinylpropan-1-one, 2,4-diethylxanthone/methyl p-dimethylaminobenzoate mixture, benzophenone/methyltriethanolamine mixture .

After the photoradical polymerization initiator is added to the liquid crystal composition, ultraviolet rays are irradiated in a state where an electric field is applied, whereby polymerization can be performed. However, unreacted polymerization initiators or decomposition products of polymerization initiators may cause poor display of image afterimages and the like caused to the device. To prevent this, the photopolymerization may be carried out without adding a polymerization initiator. The preferred wavelength of the irradiated light is in the range of 150 nm to 500 nm. The preferred 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 to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are hydroquinone derivatives such as hydroquinone and methylhydroquinone, 4-tributylbutylcatechol, 4-methoxyphenol, and phenothiazine.

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

Antioxidants are effectively used to maintain a large voltage retention rate. Preferred examples of antioxidants include the following compounds (AO-1) and compounds (AO-2); Irganox 415, Irganox 565, Irganox 1010 , Yanganuo (Irganox) 1035, Yanganuo (Irganox) 3114, and Yanganuo (Irganox) 1098 (trade name; BASF). The ultraviolet absorber is effectively used to prevent the lowering of the upper limit temperature. Preferred examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives, etc. Specific examples include the following compounds (AO-3) and compounds (AO-4) ;Tinuvin 329,Tinuvin P,Tinuvin 326,Tinuvin 234,Tinuvin 213,Tinuvin 400,Emperor Tinuvin 328, and Tinuvin 99-2 (trade name; BASF); and 1,4-diazabicyclo[2.2.2]octane (DABCO).

Light stabilizers such as amines with steric hindrance are preferred to maintain a large voltage retention rate. Preferred examples of the light stabilizer include the following compounds (AO-5), compounds (AO-6), and compounds (AO-7); Tinuvin 144, Tinuvin (Tinuvin) 765, and Tinuvin 770DF (trade name; BASF); LA-77Y and LA-77G (trade name; ADEKA). Thermal stabilizers are also effective for maintaining a large voltage retention rate. As a good example, Irgafos 168 (trade name; BASF) can be cited. In order to be suitable for elements in the guest host (GH) mode, dichroic dyes such as azo pigments and anthraquinone pigments are added to the composition as needed. Defoamers are effective in preventing foaming. Preferred examples of antifoaming agents are dimethyl silicone oil, methylphenyl silicone oil, and the like.

In the compound (AO-1), R ⁴⁰ is a C 1-20 alkyl group, a C 1-20 alkoxy group, -COOR ⁴¹ , or -CH ₂ CH ₂ COOR ⁴¹ , where R ⁴¹ is a carbon Number 1 to 20 alkyl. In compound (AO-2) and compound (AO-5), R ⁴² is an alkyl group having 1 to 20 carbon atoms. Compound (AO-5) in, R ⁴³ is hydrogen, methyl or O ^· (oxygen radicals); ring G ¹ is 1,4-cyclohexylene or 1,4-phenylene; compound (AO-7) In the ring G ² is 1,4-cyclohexyl, 1,4-phenylene, or 1,4-phenylene where at least one hydrogen is substituted with fluorine; compound (AO-5) and compound (AO -7), z is 1, 2, or 3.

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

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

In a polymer-stable alignment element, the polymer contained in the composition aligns the liquid crystal molecules. Polar compounds help liquid crystal molecules align. That is, a polar compound can be used instead of the alignment film. An example of a method of manufacturing such an element is as follows. An element having two substrates called an array substrate and a color filter substrate is prepared. The substrate does not have an alignment film. At least one piece of the substrate has an electrode layer. The liquid crystal compound is mixed to prepare a liquid crystal composition. The compound (1) and other polymerizable compounds and polar compounds as needed are added to this composition. If necessary, additives may be further added. The composition is injected into the device. Light irradiation is performed with a voltage applied to this element. It is preferably ultraviolet light. The polymerizable compound is polymerized by light irradiation. By this polymerization, a composition including a polymer is produced, thereby producing a device having a PSA mode.

In this procedure, polar compounds are arranged on the substrate because the polar groups interact with the substrate surface. The polar compound aligns the liquid crystal molecules. When there are multiple polar groups, the interaction with the substrate surface becomes stronger, and alignment can be performed at a low concentration. When a voltage is applied, the alignment of the liquid crystal molecules is further promoted by the action of the electric field. According to this alignment, the polymerizable compound also performs alignment. In this state, the polymerizable compound is polymerized by ultraviolet rays, so that a polymer that maintains the alignment is generated. Due to the effect of the polymer, the alignment of the liquid crystal molecules is additionally stabilized, so the response time of the device is shortened. Since the afterimage of the image is a malfunction of the liquid crystal molecules, the afterimage is also improved by the effect of the polymer. Compound (1) is polymerizable, so it is consumed by polymerization. Compound (1) is also consumed by copolymerization with other polymerizable compounds. Therefore, although the compound (1) has a polar group, it is consumed, and thus a liquid crystal display element having a large voltage retention rate can be obtained. Furthermore, if a polymerizable polar compound is used, the effects of both the polar compound and the polymerizable compound can be achieved by one compound, and therefore, the polymerizable compound having no polar group may not be necessary. [Example]

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

1. Examples of compound (1) Unless otherwise stated, the reaction is carried out under 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 characteristics of the compound (1), liquid crystal compound, composition, and device were measured by the following method.

NMR analysis: For the measurement, DRX-500 manufactured by Bruker BioSpin was used. In the ¹ H-NMR measurement, the sample was dissolved in a deuterated solvent such as CDCl _3, and the measurement was performed under the conditions of 500 MHz and 16 times of accumulation at room temperature. Use tetramethylsilane as an internal standard. In the measurement of ¹⁹ F-NMR, CFCl _{3 was} used as an internal standard, and the measurement was performed 24 times in total. In the description of NMR spectroscopy, s refers to singlet, d refers to doublet, t refers to triplet, q refers to quartet, and quin refers to quintet (Quintet), sext means sixt (sextet), m means multiplet (multiplet), br means broad (broad).

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

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

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

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

Measurement method: The characteristic is measured by the following method. Most of these methods are the methods described in the JEITA standard (JEITA·ED-2521B) reviewed or formulated by the Japan Electronics and Information Technology Industries Association (JEITA) or modified methods. No thin film transistor (TFT) was installed in the TN device used for measurement.

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

(2) Transition temperature (℃) For the measurement, a scanning calorimeter Diamond DSC system manufactured by Perkin Elmer or a high-sensitivity differential scanning calorimeter X-DSC7000 manufactured by Hitachi High-Tech Science (shares) was used. The temperature of the sample is raised and lowered at a rate of 3°C/min, and the starting point of the endothermic peak or exothermic peak accompanying the phase change of the sample is determined by extrapolation, and the transition temperature is determined. The melting point of the compound and the polymerization initiation temperature are also measured using this device. Sometimes the temperature at which the compound transforms from a solid to a smectic phase and a nematic equal liquid crystal phase is simply referred to as "the lower limit temperature of the liquid crystal phase." Sometimes the temperature at which a compound changes from a liquid crystal phase to a liquid is simply called "transparent point."

Denote the crystal as C. In the case of distinguishing the types of crystals, they are represented as C ₁ and C ₂ respectively. Denote the smectic phase as S and the nematic phase as N. In the smectic phase, when the smectic A phase, the smectic B phase, the smectic C phase, or the smectic F phase is distinguished, they are expressed as S _A , S _B , S _C , or S _{F, respectively} . Denote the liquid (isotropic) as I. The transition temperature is expressed as "C 50.0 N 100.0 I", for example. This means that the temperature for the transition from crystal to nematic phase is 50.0°C, and the temperature for the transition from nematic phase to liquid is 100.0°C.

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

(4) lower limit temperature (T _C; ℃) nematic phase A sample having a nematic phase at 0 ℃, -10 ℃, -20 ℃ , -30 ℃, -40 ℃ freezer and storage of 10 days After that, observe the liquid crystal phase. For example, when the sample maintains a nematic phase at -20°C and changes to a crystal or a smectic phase at -30°C, T _{C is} described as ≦-20°C. Sometimes the lower limit temperature of the nematic phase is simply referred to as "lower limit temperature".

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

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

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

For samples with positive dielectric anisotropy and samples with negative dielectric anisotropy, the measurement method of the characteristics may be different. The measurement method when the dielectric anisotropy is positive is described in the items (8a) to (12a). When the dielectric constant anisotropy is negative, the measurement method is described in the items (8b) to (12b).

(8a) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s) Positive dielectric constant anisotropy: the measurement is based on M. Imai et al. "Molecular Crystals and Liquid Crystals (Molecular Crystals and Liquid Crystals)" (Vol. 259, 37 (1995)) method. The sample was placed in a TN device with a twist angle of 0 degrees and a gap (cell gap) of two glass substrates of 5 μm. The voltage is applied to the device in a range of 16 V to 19.5 V in steps of 0.5 V in steps. After no voltage was applied for 0.2 seconds, the voltage was applied repeatedly with only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application are measured. Based on these measured values and the calculation formula (8) on the 40-page paper of M. Imai et al., the value of rotational viscosity was obtained. The value of the dielectric anisotropy necessary for this calculation was obtained by using the method described below using the device for which the rotational viscosity was measured.

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

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

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

(10a) Elastic constant (K; measured at 25°C; pN) Positive dielectric constant anisotropy: In the measurement, an HPR 4284A LCR meter manufactured by Agilent Technologies was used. A sample was placed in a horizontal alignment element with a gap (cell gap) of two glass substrates of 20 μm. A charge of 0 to 20 volts was applied to the device, and the electrostatic capacitance and applied voltage were measured. Use the formula (2.98) and formula (2.101) in page 75 of the “Liquid Crystal Device Manual” (Nikkei Kombun) to fit the measured values of the electrostatic capacitance (C) and the applied voltage (V) according to formula (2.99) The values of K ₁₁ and K ₃₃ are obtained. Next, in the formula (3.18) on page 171, K ₂₂ is calculated using the values of K ₁₁ and K ₃₃ obtained previously. The elastic constant K is expressed as the average value of K ₁₁ , K ₂₂ and K ₃₃ obtained in this way.

(10b) Elastic constants (K ₁₁ and K ₃₃ ; measured at 25°C; pN) Negative dielectric constant anisotropy: In the measurement, the EC-1 type elasticity manufactured by TOYO Technica (shares) is used Constant tester. Place the sample in the vertical alignment element with a gap (cell gap) of 20 μm between the two glass substrates. A charge of 20 volts to 0 volts was applied to the device, and the electrostatic capacitance and applied voltage were measured. Use the formula (2.98) and formula (2.101) on page 75 of the “Liquid Crystal Device Manual” (Nikkei Kombun) to fit the values of the electrostatic capacitance (C) and the applied voltage (V), and obtain elasticity according to the formula (2.100) The value of the constant.

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

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

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

(12b) Response time (τ; measured at 25°C; ms) Negative dielectric anisotropy: For measurement, an LCD 5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source is set as a halogen lamp. The low-pass filter is set to 5 kHz. A sample was placed in a normally black mode PVA element with a gap (cell gap) of two glass substrates of 3.2 μm and a rubbing direction of antiparallel. The device was sealed with an adhesive hardened by ultraviolet rays. A voltage slightly exceeding the threshold voltage was applied to the device for 1 minute, and then a voltage of 5.6 V was applied while irradiating 23.5 mW/cm ² of ultraviolet light for 8 minutes. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to this element. At this time, the element is irradiated with light from the vertical direction, and the amount of light transmitted through the element is measured. When the light amount reaches the maximum, it is regarded as 100% transmittance, and when the light amount is the smallest, it is regarded as 0% transmittance. Response time is expressed as the time (fall time; millisecond) required for the transmission rate to change from 90% to 10%.

(13) Voltage retention rate The ultraviolet light is irradiated with black light made by Eye Graphics Co., Ltd., F40T10/BL (peak wavelength 369 nm), thereby polymerizing the polymerizable compound. The element was charged at 60° C. with a pulse voltage (1 V and 60 microseconds). The decayed voltage was measured with a high-speed voltmeter in a period of 1.67 seconds, and the area A between the voltage curve per unit period and the horizontal axis was obtained. Area B is the area without attenuation. The voltage retention rate is expressed as a percentage of area A relative to area B.

raw material Solmix (registered trademark) A-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (Isopropanol, IPA) (1.1%). )Obtain.

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

Step 1 Place compound (T-1) (100.0 g), p-toluenesulfonic acid monohydrate (PTSA (p-toluene sulfonic acid)·H ₂ O) (4.25 g), and acetone (300 ml) into After stirring at room temperature for 5 hours in the reactor, triethylamine (3.12 ml) was added dropwise. The reaction mixture 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-2) (130.4 g; 100%).

Step 2 Put compound (T-2) (10.0 g) and dichloromethane (20 ml) into the reactor and cool to 0°C. Tosyl chloride (10.1 g) and pyridine (5.5 ml) were added thereto, heated to 40°C and stirred for 2 days. 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 = 3:1) to obtain compound (T-3) (14.3 g; 76%).

Step 3 The compound (T-3) (48.1 g), sodium iodide (54.9 g), and 2-butanone (300 ml) were placed in a reactor, and heated and stirred at 70°C for 4 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl hexanoate. The obtained organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=3:1) to obtain compound (T-4) (38.9 g; 93%).

Step 4 Put sodium hydride (32.6 g) and DMF (1000 ml) into the reactor and cool to 0°C. A DMF solution of compound (T-5) (159.3 g) was added dropwise and stirred for 1 hour. After that, compound (T-4) (101.0 g) was added dropwise, heated to 110°C and stirred for 4 days. The reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure. Water (500 ml), potassium carbonate (98.2 g) and polyoxymethylene (42.7 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 the aqueous layer was extracted with ethyl hexanoate. The obtained organic layer was washed with water and 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 = 8:1) to obtain compound (T-6) (11.4 g; 12%).

Step 5 The compound (T-6) (12.1 g), tetrabutylammonium bromide (TBAB) (1.5 g), water (114.7 ml), and THF (3.82 ml) were put into the reactor and cooled to 0°C. Lithium hydroxide monohydrate (3.95 g) was added thereto, and the mixture was heated and stirred at 50°C for 7 hours. The reaction mixture was poured into water, the water layer was washed with toluene, and then washed with an aqueous citric acid solution to adjust the pH to 4. The obtained aqueous layer was extracted with ethyl hexanoate. The obtained organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to obtain compound (T-7) (10.5 g; 98%).

Step 6 Compound (T-7) (3.9 g), compound (T-8) (5.0 g) synthesized by a known method, N,N-dicyclohexylcarbodiimide (DCC) (3.8 g), Dichloromethane (50 ml) was placed in the reactor and cooled to 0°C. N,N-Dimethylaminopyridine (DMAP) (0.75 g) was added thereto and stirred at room temperature for 12 hours. After filtering the reaction mixture with suction, the filtrate was poured into water, and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=7:1) to obtain compound (T-9) (6.1 g; 81%).

Step 7 Put compound (T-9) (0.5 g), THF (7.5 ml), methanol (7.5 ml), and pyridinium p-toluene sulfonate (PPTS) (0.04 g) into the reactor , Stir at room temperature 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 over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate = 2:1) to obtain compound (1-2-6) (0.3 g; 71% ).

The NMR analysis value of the obtained compound (1-2-6) is as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.48 (s, 1H), 6.12 (s, 1H), 5.75 (s, 1H), 5.60 (s, 1H), 4.26-4.14 (m, 4H ), 3.55-3.51 (m, 2H), 3.41-3.37 (m, 2H), 3.33-3.31 (m, 2H), 2.49 (s, 1H), 2.13-2.08 (m, 1H), 1.97 (s, 3H ), 1.77-1.71 (m, 8H), 1.47-1.12 (m, 17H), 1.04-0.84 (m, 16H).

Transition temperature: C 50.7 C 52.16 I, Polymerization starting temperature: 206.8℃

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

¹ H-NMR (ppm; CDCl ₃ ): 6.25 (S, 1H), 6.10 (s, 1H), 5.66 (S, 1H), 5.58-5.57 (m, 1H), 4.22-4.10 (m, 4H), 3.80-3.75 (m, 2H), 3.67-3.62 (m, 2H), 2.55-2.52 (m, 2H), 2.37 (d, J=7.4 Hz, 2H), 2.10-2.05 (m, 1H), 1.94 ( s, 3H), 1.90-1.86 (m, 1H), 1.75-1.67 (m, 8H), 1.48-1.37 (m, 2H), 1.32-0.79 (m, 25H).

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

The proportion of each component of the mother liquid crystal (i) is expressed in% by weight.

A sample in which the compound (1-2-6) or the comparative compound (S-1) was added to the mother liquid crystal (i) at a ratio of 3% to 0.5% by weight. After the sample was allowed to stand at 25°C and -20°C for 7 days, it was visually observed, and the case where the nematic phase was maintained was indicated as ○, and the case where crystals or smectic phase precipitated was indicated as ×.

Table 2. Compatibility

Comparing the solubility, the compound (1-2-6) maintains the nematic phase at both 25°C and -20°C even if 3% by weight is added to the mother liquid crystal (i). Compared to this, the compound ( S-1) When 3 wt% is added, crystals are precipitated at -20°C. These compounds are similar in that they have the same ring structure and are bonded with multiple polymerizable groups, but their compatibility is greatly different. The reason for this is that the introduction of ethyl compound (1-2-6) improves the affinity of the liquid crystal composition compared with the comparative compound (S-1). Therefore, the compound of the present application can be said to be an excellent compound having large compatibility.

The compound shown below can be synthesized by referring to the method described in the synthesis example or the item "2. Synthesis of Compound (1)".

2. Examples of the composition The compounds in the examples are represented by symbols based on the definition in Table 3 below. In Table 3, the stereo configuration related to 1,4-cyclohexyl is the trans configuration. The number in parentheses after the symbol corresponds to the compound number. The symbol (-) refers to other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition. Finally, the characteristic values of the liquid crystal composition are summarized. The characteristic is measured according to the method described above, and the measured value is directly recorded (without extrapolation).

NI=95.6℃；η=17.9 mPa·s；Δn=0.107；Δε=5.1.[Use Example 1] 1-BB-3 (2-8) 6% 1-BB-5 (2-8) 7% 2-BTB-1 (2-10) 3% 3-HHB-1 (3-1 ) 7% 3-HHB-3 (3-1) 12% 3-HHB-O1 (3-1) 6% 3-HHB-F (6-1) 4% 2-HHB(F)-F (6- 2) 8% 3-HHB(F)-F (6-2) 8% 5-HHB(F)-F (6-2) 7% 3-HHB(F,F)-F (6-3) 5 % 3-HHEB-F (6-10) 4% 5-HHEB-F (6-10) 4% 2-HB-C (8-1) 6% 3-HB-C (8-1) 13% 1% by weight of the ratio The following compound (1-2-6) was added to the composition.

NI=95.6℃; η=17.9 mPa·s; Δn=0.107; Δε=5.1.

NI=70.6℃；η=20.8 mPa·s；Δn=0.115；Δε=6.0.[Use Example 2] 3-HH-4 (2-1) 11% 5-HB-O2 (2-5) 4% 7-HB-1 (2-5) 2% 5-HBB(F)B-2 (4-5) 5% 5-HBB(F)B-3 (4-5) 5% 3-HB-CL (5-2) 13% 3-HHB(F,F)-F (6-3) 3% 3-HBB(F,F)-F (6-24) 24% 4-HBB(F,F)-F (6-24) 16% 5-HBB(F,F)-F (6-24 ) 17% The following compound (1-2-8) was added to the composition at a ratio of 3% by weight.

NI=70.6℃; η=20.8 mPa·s; Δn=0.115; Δε=6.0.

NI=85.1℃；η=25.3 mPa·s；Δn=0.111；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) 8% 3-HHB(F)-F (6-2) 12% 5-HHB(F)-F (6-2) 10% 2-HBB-F (6-22) ) 4% 3-HBB-F (6-22) 2% 5-HBB-F (6-22) 4% 2-HBB(F)-F (6-23) 9% 3-HBB(F)-F (6-23) 10% 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 (1-2-2) was added to the composition at a ratio of 5% by weight.

NI=85.1℃; η=25.3 mPa·s; Δn=0.111; Δε=5.7.

NI=114.4℃；η=18.7 mPa·s；Δn=0.091；Δε=3.7.[Use Example 4] 2-HH-3 (2-1) 8% 3-HH-4 (2-1) 8% 1O1-HBBH-5 (4-1) 4% 5-HB-CL (5-2 ) 15% 3-HHB-F (6-1) 4% 3-HHB-CL (6-1) 3% 4-HHB-CL (6-1) 4% 3-HHB(F)-F (6- 2) 10% 4-HHB(F)-F (6-2) 9% 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 (1-3-12) was added to the composition at a ratio of 3.5% by weight.

NI=114.4℃; η=18.7 mPa·s; Δn=0.091; Δε=3.7.

NI=106.7℃；η=32.6 mPa·s；Δn=0.123；Δε=8.3.[Use Example 5] V-HBB-2 (3-4) 10% 1O1-HBBH-4 (4-1) 3% 1O1-HBBH-5 (4-1) 5% 3-HHB(F,F)- F (6-3) 9% 3-H2HB(F,F)-F (6-15) 10% 4-H2HB(F,F)-F (6-15) 6% 5-H2HB(F,F) -F (6-15) 8% 3-HBB(F,F)-F (6-24) 10% 5-HBB(F,F)-F (6-24) 21% 3-H2BB(F,F )-F (6-27) 10% 5-HHBB(F,F)-F (7-6) 4% 3-HH2BB(F,F)-F (7-15) 2% 5-HHEBB-F ( 7-17) 2% The following compound (1-5-13) was added to the composition at a ratio of 5% by weight.

NI=106.7℃; η=32.6 mPa·s; Δn=0.123; Δε=8.3.

NI=86.0℃；η=14.6 mPa·s；Δn=0.092；Δε=4.3.[Use Example 6] 5-HBBH-3 (4-1) 3% 3-HB(F)BH-3 (4-2) 3% 5-HB-F (5-2) 12% 6-HB-F (5-2) 9% 7-HB-F (5-2) 7% 2-HHB-OCF3 (6-1) 7% 3-HHB-OCF3 (6-1) 4% 4-HHB-OCF3 (6 -1) 7% 5-HHB-OCF3 (6-1) 8% 3-HHB(F,F)-OCF2H (6-3) 6% 3-HHB(F,F)-OCF3 (6-3) 3 % 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) 5% 5-HBB(F)-F (6-23) 1 5% The following compound (1-5-17) was added to the composition at a ratio of 4% by weight.

NI=86.0℃; η=14.6 mPa·s; Δn=0.092; Δε=4.3.

NI=77.1℃；η=22.4 mPa·s；Δn=0.108；Δε=8.5.[Use Example 7] 2-HH-5 (2-1) 2% 3-HH-4 (2-1) 7% 5-B(F)BB-2 (3-8) 4% 5-HB-CL (5-2) 11% 3-HHB(F,F)-F (6-3) 8% 3-HHEB(F,F)-F (6-12) 5% 4-HHEB(F,F)- F (6-12) 8% 5-HHEB(F,F)-F (6-12) 3% 3-HBB(F,F)-F (6-24) 20% 5-HBB(F,F) -F (6-24) 15% 2-HBEB(F,F)-F (6-39) 3% 3-HBEB(F,F)-F (6-39) 3% 5-HBEB(F,F )-F (6-39) 5% 3-HHBB(F,F)-F (7-6) 6% Add the following compound (1-5-25) to the composition at a ratio of 2% by weight .

NI=77.1℃; η=22.4 mPa·s; Δn=0.108; Δε=8.5.

NI=72.8℃；η=25.0 mPa·s；Δn=0.098；Δε=8.2.[Use Example 8] V2-HHB-1 (3-1) 4% 3-HB-CL (5-2) 3% 5-HB-CL (5-2) 7% 3-HHB-OCF3 (6-1 ) 5% 5-HHB(F)-F (6-2) 7% V-HHB(F)-F (6-2) 4% 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 (1-2-6) was added to the composition at a ratio of 0.5% by weight.

NI=72.8℃; η=25.0 mPa·s; Δn=0.098; Δε=8.2.

NI=71.9℃；η=14.1 mPa·s；Δn=0.075；Δε=2.9.[Use Example 9] 3-HH-4 (2-1) 5% 3-HH-5 (2-1) 10% 3-HB-O2 (2-5) 15% 3-HHB-1 (3-1 ) 5% 3-HHB-O1 (3-1) 8% 5-HB-CL (5-2) 17% 7-HB(F,F)-F (5-4) 3% 2-HHB(F) -F (6-2) 8% 3-HHB(F)-F (6-2) 8% 5-HHB(F)-F (6-2) 5% 3-HHB(F,F)-F ( 6-3) 6% 3-H2HB(F,F)-F (6-15) 5% 4-H2HB(F,F)-F (6-15) 5% 0.7% by weight in the composition The following compound (1-2-8) was added to the product.

NI=71.9℃; η=14.1 mPa·s; Δn=0.075; Δε=2.9.

NI=87.1℃；η=21.7 mPa·s；Δn=0.071；Δε=5.9.[Use Example 10] 3-HH-4 (2-1) 12% 3-HH-5 (2-1) 7% 3-HHB-1 (3-1) 13% 5-HB-CL (5-2 ) 3% 7-HB(F)-F (5-3) 7% 2-HHB(F,F)-F (6-3) 2% 3-HHB(F,F)-F (6-3) 7% 3-HHEB-F (6-10) 8% 5-HHEB-F (6-10) 8% 3-HHEB(F,F)-F (6-12) 5% 4-HHEB(F,F )-F (6-12) 10% 3-GHB(F,F)-F (6-109) 6% 4-GHB(F,F)-F (6-109) 5% 5-GHB(F, F)-F (6-109) 7% The following compound (1-2-2) was added to the composition at a ratio of 0.3% by weight.

NI=87.1℃; η=21.7 mPa·s; Δn=0.071; Δε=5.9.

NI=80.8℃；η=10.8 mPa·s；Δn=0.130；Δε=6.6.[Use Example 11] 3-HH-VFF (2-1) 8% 5-HH-VFF (2-1) 22% 2-BTB-1 (2-10) 10% 3-HHB-1 (3-1 ) 4% VFF-HHB-1 (3-1) 10% VFF2-HHB-1 (3-1) 9% 3-H2BTB-2 (3-17) 5% 3-H2BTB-3 (3-17) 5 % 3-H2BTB-4 (3-17) 3% 3-HB-C (8-1) 18% 1V2-BEB(F,F)-C (8-15) 6% 0.2% by weight to all The following compound (1-3-12) is added to the composition.

NI=80.8℃; η=10.8 mPa·s; Δn=0.130; Δε=6.6.

NI=78.0℃；η=12.1 mPa·s；Δn=0.097；Δε=5.5.[Use Example 12] 3-HH-V (2-1) 30% 3-HH-V1 (2-1) 5% 5-HH-V (2-1) 10% 3-HHB-1 (3-1 ) 5% V-HHB-1 (3-1) 4% 2-BB(F)B-3 (3-6) 5% 3-HHEH-5 (3-13) 3% 1V2-BB-F (5 -1) 3% 3-BB(F,F)XB(F,F)-F (6-97) 8% 3-BB(2F,3F)XB(F,F)-F (6-114) 5 % 3-HHBB(F,F)-F (7-6) 2% 3-HBBXB(F,F)-F (7-32) 4% 5-HB(F)B(F,F)XB(F ,F)-F (7-41) 5% 3-BB(F)B(F,F)XB(F,F)-F (7-47) 4% 4-BB(F)B(F,F )XB(F,F)-F (7-47) 4% 5-BB(F)B(F,F)XB(F,F)-F (7-47) 3% at 1.5 weight % The following compound (1-5-13) is added to the composition.

NI=78.0℃; η=12.1 mPa·s; Δn=0.097; Δε=5.5.

NI=81.5℃；η=13.3 mPa·s；Δn=0.106；Δε=7.3.[Use Example 13] 3-HH-V (2-1) 25% 3-HH-V1 (2-1) 10% V-HH-V1 (2-1) 9% 3-HHB-1 (3-1 ) 4% V-HHB-1 (3-1) 5% 1-BB(F)B-2V (3-6) 4% 3-HHEH-5 (3-13) 3% 1V2-BB-F (5 -1) 3% 3-BB(F,F)XB(F,F)-F (6-97) 6% 3-HHXB(F,F)-CF3 (6-100) 2% 3-GB(F ,F)XB(F,F)-F (6-113) 4% 3-GB(F)B(F,F)-F (6-116) 4% 3-HHBB(F,F)-F ( 7-6) 3% 3-BB(F)B(F,F)XB(F,F)-F (7-47) 5% 4-BB(F)B(F,F)XB(F,F )-F (7-47) 5% 5-BB(F)B(F,F)XB(F,F)-F (7-47) 3% 3- GB(F)B(F,F)XB(F,F)-F (7-57) 5% The following compound (1-5-17) was added to the composition at a ratio of 0.5% by weight.

NI=81.5℃; η=13.3 mPa·s; Δn=0.106; Δε=7.3.

NI=81.9℃；η=13.5 mPa·s；Δn=0.092；Δε=5.8.[Use Example 14] 3-HH-V (2-1) 30% 3-HH-V1 (2-1) 10% 3-HHB-1 (3-1) 5% V-HHB-1 (3-1 ) 3% 3-HBB-2 (3-4) 6% V2-BB(F)B-1 (3-6) 5% 3-HHEH-3 (3-13) 3% 3-HHEH-5 (3 -13) 3% 1V2-BB-F (5-1) 3% 3-BB(F,F)XB(F,F)-F (6-97) 4% 3-GB(F,F)XB( F,F)-F (6-113) 3% 3-HHBB(F,F)-F (7-6) 3% 3-HBB(F,F)XB(F,F)-F (7-38 ) 3% 3-BB(F)B(F,F)XB(F)-F (7-46) 4% 4-BB(F)B(F,F)XB(F,F)-F (7 -47) 2% 5-BB(F)B(F,F)XB(F,F)-F (7-47) 3% 3-GB(F)B(F,F)XB(F,F)-F (7-57) 3% 4-GB(F)B(F,F)XB(F,F)-F (7- 57) 5% 5-GB(F)B(F,F)XB(F,F)-F (7-57) 2% Add the following compound to the composition in the proportion of 4% by weight (1- 5-25).

NI=81.9℃; η=13.5 mPa·s; Δn=0.092; Δε=5.8.

NI=84.6℃；η=19.3 mPa·s；Δn=0.102；Δε=5.6.[Use Example 15] 3-HH-V (2-1) 30% 3-HH-V1 (2-1) 8% 3-HHB-1 (3-1) 4% V-HHB-1 (3-1 ) 5% V2-BB(F)B-1 (3-6) 4% 3-HHEH-5 (3-13) 4% 3-HHEBH-3 (4-6) 3% 1V2-BB-F (5 -1) 4% 3-BB(F)B(F,F)-F (6-69) 5% 3-BB(F,F)XB(F,F)-F (6-97) 3% 3 -HHBB(F,F)-F (7-6) 3% 5-HB(F)B(F,F)XB(F,F)-F (7-41) 4% 3-BB(F,F )XB(F)B(F,F)-F (7-56) 5% 4-BB(F)B(F,F)XB(F,F)-F (7-47) 3% 5-BB (F)B(F,F)XB(F,F)-F (7-47) 4% 2-dhBB(F,F)XB(F,F)-F (7-50) 3% 3-dhBB (F,F )XB(F,F)-F (7-50) 2% 3-GBB(F)B(F,F)-F (7-55) 2% 4-GBB(F)B(F,F)- F (7-55) 4% The following compound (1-2-6) was added to the composition at a ratio of 3% by weight.

NI=84.6℃; η=19.3 mPa·s; Δn=0.102; Δε=5.6.

NI=83.5℃；η=16.6 mPa·s；Δn=0.098；Δε=6.2. [產業上之可利用性][Use Example 16] 3-HH-V (2-1) 25% 3-HH-V1 (2-1) 10% 3-HHB-1 (3-1) 5% V-HHB-1 (3-1 ) 7% V2-BB(F)B-1 (3-6) 5% 3-HHEH-5 (3-13) 3% 1V2-BB-F (5-1) 5% 3-BB(F)B (F,F)-CF3 (6-69) 3% 3-BB(F,F)XB(F,F)-F (6-97) 5% 3-HHXB(F,F)-F (6- 100) 5% 3-GB(F,F)XB(F,F)-F (6-113) 3% 3-GB(F)B(F)-F (6-115) 3% 3-HHBB( F,F)-F (7-6) 2% 5-HB(F)B(F,F)XB(F,F)-F (7-41) 5% 3-GB(F)B(F, F)XB(F,F)-F (7-57) 3% 3-GBB(F,F)XB(F,F)-F (7-58) 4% 4-GBB (F,F)XB(F,F)-F (7-58) 2% 5-GBB(F,F)XB(F,F)-F (7-58) 2% 3-GB(F)B (F) B(F)-F (7-59) 3% The following compound (1-2-8) was added to the composition at a ratio of 1% by weight.

NI=83.5℃; η=16.6 mPa·s; Δn=0.098; Δε=6.2. [Industry availability]

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

no

no

Claims (16)

A compound, represented by formula (1),

In formula (1), R ¹ is hydrogen or an alkyl group having 1 to 15 carbon atoms. In R ¹ , at least one -CH ₂ -may be substituted with -O- or -S-, and at least one -(CH ₂ ) ₂ -May be substituted with -CH=CH- or -C≡C-, at least one hydrogen may be substituted with fluorine or chlorine; Ring A ¹ and Ring A ^{2 are} independently 1,2-cyclopropyl, 1,3- Cyclobutyl, 1,3-cyclopentyl, 1,4-cyclohexyl, 1,4-cycloheptyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene -2,6-diyl, decalin-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in the ring A ¹ and ring A ² , at least one hydrogen can pass Fluorine, chlorine, C 1-10 alkyl, C 2-10 alkenyl, C 1-9 alkoxy, or C 2-9 alkenoxy, at least one hydrogen can be substituted by fluorine Or chlorine substitution; a is 0, 1, 2, 3, or 4; Z ^{1 is} independently a single bond or an alkylene group having 1 to 6 carbon atoms, and in Z ¹ , at least one -CH ₂ -may be passed through- O-, -CO-, -COO-, -OCO-, or -OCOO-, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH- or -C≡C-, at least one hydrogen may be substituted by Fluorine or chlorine substitution; Sp ⁰ , Sp ² , Sp ³ , and Sp ^{4 are} independently a single bond or an alkylene group having 1 to 15 carbon atoms, and among the Sp ⁰ , Sp ² , Sp ³ , and Sp ⁴ , at least One -CH ₂ -may be substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH- or -C≡C -Substitution, at least one hydrogen may be substituted by fluorine or chlorine; M ¹ and M ^{2 are} independently hydrogen, fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen having a carbon number 1 substituted by fluorine or chlorine to 5 alkyl; R ² is an alkyl group having 1 to 10 carbon atoms, said R ^2, at least one -CH ₂ - may be substituted by -O- or -S-, the at least one - (CH _{2) 2} - May be substituted by -CH=CH- or -C≡C-, at least one hydrogen may be substituted by fluorine or chlorine; X ^{1 is} independently -OH, -NH ₂ , -OR ⁴ , -N(R ⁴ ) ₂ ,- COOH, -SH, or -Si(R ⁴ ) ₃ ; -OR ⁴ , -N(R ⁴ ) ₂ , and -Si(R ⁴ ) ₃ , R ⁴ is hydrogen or an alkyl group having 1 to 10 carbon atoms, In R ⁴ , at least one -CH ₂ -may be substituted by -O-, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH-, and in these groups, at least one hydrogen may be substituted by fluorine or chlorine Substitution; in ring A ² or Sp ⁰ , at least one hydrogen is substituted with a group represented by formula (1-a);

In the formula (1-a), Sp ⁵ is a single bond or an alkylene group having 1 to 10 carbon atoms. In the Sp ⁵ , at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH- or -C≡C-, at least one hydrogen may be substituted by fluorine or chlorine; M ³ , and M ⁴ Independently hydrogen, fluorine, chlorine, C 1-5 alkyl, or at least one hydrogen substituted with fluorine or chlorine, C 1-5 alkyl; R ³ is C 1-10 alkyl, so In R ³ , at least one -CH ₂ -may be substituted by -O- or -S-, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH- or -C≡C-, and at least one hydrogen may Replaced by fluorine or chlorine. The compound as described in item 1 of the patent application, wherein in formula (1), Z ^{1 is} independently a single bond, -(CH ₂ ) ₂ -, -(CH ₂ ) ₄ -, -CH=CH-,- C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, or -CF=CF-; Ring A ¹ and Ring A ^{2 are} independent 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1 ,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in ring A ¹ and ring A ² , at least one hydrogen can be fluorinated , Chlorine, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenoxy having 2 to 9 carbons, at least one hydrogen may be substituted by fluorine or Chlorine substitution; in ring A ² or Sp ⁰ , at least one hydrogen is substituted by formula (1-a). The compound described in item 1 of the patent application scope is represented by any one of formula (1-1) to formula (1-8),

In formula (1-1) to formula (1-8), R ¹ is an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, or 2 carbon atoms ~14 alkenyloxy group, at least one hydrogen in R ¹ may be substituted with fluorine; Ring A ¹ to Ring A ^{5 are} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1 ,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl, the ring A ¹ to In ring A ⁵ , at least one hydrogen can be substituted by fluorine, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyl having 2 to 9 carbons Substitution, at least one hydrogen may be substituted by fluorine; b to e are independently 0, 1, 2, 3, or 4, the total of these is 1, 2, 3, or 4; Z ¹ to Z ^{4 are} independently mono Bond, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, or -CF=CF-; Sp ⁰ to Sp ^{8 are} independently a single bond or an alkylene group having 1 to 7 carbon atoms, and among the Sp ⁰ to Sp ⁸ , at least one -CH ₂ -may be passed through -O- , -COO-, or -OCO-, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH-, at least one hydrogen may be substituted by fluorine; M ¹ to M ^{10 are} independently hydrogen, fluorine, carbon An alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine; R ² to R ^{6 are} independently an alkyl group having 1 to 10 carbon atoms, and R ² to R ⁶ , At least one -CH ₂ -may be substituted with -O-; X ^{1 is} independently -OH, -NH ₂ , or -SH. The compound described in item 1 of the patent application scope is represented by any one of formula (1-9) to formula (1-16),

In formula (1-9) to formula (1-16), R ¹ is a C 1-10 alkyl group, a C 2-10 alkenyl group, or a C 1-9 alkoxy group; Ring A ¹ To Ring A ^{5 is} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5 -Diyl, or 1,3-dioxane-2,5-diyl, in the ring A ¹ to ring A ⁵ , at least one hydrogen can be through fluorine, alkyl group with carbon number 1 to 5, carbon number 2 Alkenyl to 5 or alkoxy substituted with 1 to 4 carbons; b to e are independently 0, 1, 2, 3, or 4, the total of these is 1, 2, 3, or 4; Z ¹ to Z ^{4 are} independently a single bond, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C-, -CH ₂ O-, or -OCH ₂ -; Sp ⁰ to Sp ^{8 are} independently A single bond or an alkylene group having 1 to 5 carbon atoms. In Sp ⁰ to Sp ⁸ , at least one -CH ₂ -may be substituted with -O-, and at least one -(CH ₂ ) ₂ -may be substituted with -CH=CH -Substitution; M ¹ to M ^{10 are} independently hydrogen, fluorine, C 1-5 alkyl, or at least one hydrogen substituted with fluorine, C 1-5 alkyl; R ² is C 1-3 Alkyl; R ³ to R ^{6 are} independently C 1-10 alkyl or C 1-9 alkoxy. The compound described in item 1 of the patent application range is represented by any one of formula (1-17) to formula (1-53),

In formula (1-17) to formula (1-53), R ¹ is a C 1-10 alkyl group, a C 2-10 alkenyl group, or a C 1-9 alkoxy group; Z ¹ to Z ^{3 is} independently a single bond or -(CH ₂ ) ₂ -; Sp ⁰ , Sp ¹ , Sp ² , Sp ⁵ , Sp ⁶ , and Sp ^{7 are} independently a single bond or an alkylene group having 1 to 5 carbon atoms, Of the Sp ⁰ , Sp ¹ , Sp ² , Sp ⁵ , Sp ⁶ , and Sp ⁷ , at least one -CH ₂ -may be substituted with -O-; Y ¹ to Y ^{11 are} independently hydrogen, fluorine, and carbon number 1 Alkyl group up to 5, alkenyl group having 2 to 5 carbons, or alkoxy group having 1 to 4 carbons; R ² is alkyl group having 1 to 10 carbons, or alkoxy group having 1 to 9 carbons; R ³ , R ⁴ and R ^{5 are} independently C 1-3 alkyl groups; M ¹ and M ^{2 are} independently hydrogen, fluorine, C 1-5 alkyl groups, or at least one hydrogen-substituted carbon Number 1 to 5 alkyl. The compound described in item 1 of the patent application range is represented by any one of formula (1-54) to formula (1-88),

In formula (1-54) to formula (1-88), R ¹ is an alkyl group having 1 to 10 carbon atoms; Z ¹ and Z ^{2 are} independently a single bond or -(CH ₂ ) ₂ -; Y ¹ to Y ^{11 is} independently hydrogen, fluorine, methyl, or ethyl; Sp ⁰ , Sp ¹ , Sp ² , Sp ⁵ , Sp ⁶ , and Sp ^{7 are} independently single bonds or alkylene groups having 1 to 5 carbon atoms, so In Sp ⁰ , Sp ¹ , Sp ² , Sp ⁵ , Sp ⁶ , and Sp ⁷ , at least one -CH ₂ -may be substituted with -O-; R ² is an alkyl group having 1 to 10 carbon atoms; M ¹ and M ^{2 is} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine. A liquid crystal composition containing at least one compound as described in item 1 of the patent application scope. The liquid crystal composition as described in item 7 of the patent application scope contains at least one compound selected from the group of compounds represented by formula (2) to formula (4),

In formula (2) to formula (4), R ¹¹ and R ^{12 are} independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and at least one of -CH in the R ¹¹ and R ¹² ₂ -may be substituted with -O-, at least one hydrogen may be substituted with fluorine; ring B ¹ , ring B ² , ring B ³ , and ring B ^{4 are} independently 1,4-cyclohexyl, 1,4-phenylene Group, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, or pyrimidine-2,5-diyl; Z ¹¹ , Z ¹² , and Z ^{13 are} independently It is a single bond, -COO-, -CH ₂ CH ₂ -, -CH=CH-, or -C≡C-. The liquid crystal composition according to item 7 of the patent application scope contains at least one compound selected from the group of compounds represented by formula (5) to formula (7),

In formula (5) to formula (7), R ¹³ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in R ¹³ , at least one -CH ₂ -may be substituted with -O- , At least one hydrogen may be substituted with 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-cyclohexyl, 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 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 7 of the patent application scope 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. In R ¹⁴ , at least one -CH ₂ -may be substituted with -O-, and at least one hydrogen may Substituted by fluorine; X ¹² is -C≡N or -C≡CC≡N; Ring D ¹ is 1,4-cyclohexyl, 1,4-phenylene, tetrahydropyran-2,5-diyl , 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or 1,4-phenylene with at least one hydrogen substituted by fluorine; Z 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 as described in item 7 of the patent application scope 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 the R ¹⁵ , R ¹⁶ , and In R ¹⁷ , at least one -CH ₂ -may be substituted with -O-, in these groups, at least one hydrogen may be substituted with fluorine, and R ¹⁷ may also be hydrogen or fluorine; ring E ¹ , ring E ² , ring E ³ , and ring E ^{4 is} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, tetrahydropyran-2,5-diyl, decahydronaphthalene -2,6-diyl, or 1,4-phenylene with at least one hydrogen substituted with fluorine; ring E ⁵ and ring E ^{6 are} independently 1,4-cyclohexyl, 1,4-cyclohexene Group, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl; Z ¹⁸ , Z ¹⁹ , Z ²⁰ , and Z ^{21 are} independently single Bond, -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ OCH ₂ CH ₂ -, or- OCF ₂ CH ₂ CH ₂ -; L ¹⁵ and L ^{16 are} independently fluorine or chlorine; S ¹¹ is hydrogen or methyl; X is -CHF- or -CF ₂ -; j, k, m, n, p, q , R, and s are independently 0 or 1, the sum of k, m, n, and p is 1 or 2, the sum of q, r, and s is 0, 1, 2, or 3, and t is 1, 2 , Or 3. The liquid crystal composition according to item 7 of the patent application scope 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-dioxan Alkyl-2-yl, pyrimidin-2-yl, or pyrid-2-yl, in ring F and ring I, at least one hydrogen can be halogen, alkyl having 1 to 12 carbons, and having 1 to 12 carbons Alkoxy, or at least one hydrogen is substituted with halogen substituted alkyl having 1 to 12 carbons; ring G is 1,4-cyclohexyl, 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, said ring G In which, at least one hydrogen may be substituted with halogen, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or at least one hydrogen is substituted with a halogen and a C 1-12 alkyl group; Z ²² and Z ^{23 is} independently a single bond or an alkylene group having 1 to 10 carbon atoms. In Z ²² and Z ²³ , at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, or -OCO- Substitution, at least one -CH ₂ CH ₂ -can be replaced by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )-, or -C(CH ₃ )=C(CH ₃ )-Substitution, 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 single bonds or carbon numbers 1 to 10 Alkylene, at least one of -CH ₂ -in Sp ¹¹ , Sp ¹² , and Sp ¹³ may be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -May be substituted by -CH=CH- or -C≡C-, 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 as described in item 12 of the patent application range, wherein in formula (20), P ¹¹ , P ¹² , and P ^{13 are} independently selected from formula (P-1) to formula (P-5) The 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 carbons, or a carbon number in which at least one hydrogen is substituted with halogen 1 to 5 alkyl groups. The liquid crystal composition according to item 12 of the patent application scope, 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. Among Sp ¹¹ , Sp ¹² , and Sp ¹³ , at least one -CH ₂ -may be passed through -O-, -COO-, -OCO-, or -OCOO-, at least one -CH ₂ CH ₂ -may be substituted by -CH=CH- or -C≡C-, at least one hydrogen may 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 with halogen 1 to 5 alkyl groups. The liquid crystal composition according to item 7 of the patent application scope contains a polymerizable compound different from the compound represented by formula (1) or formula (20), a polymerization initiator, a polymerization inhibitor, an optically active compound, At least one of the group of antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, pigments, and defoamers. A liquid crystal display element comprising a group selected from the group consisting of a liquid crystal composition as described in item 7 of the patent application scope and a liquid crystal composition as described in item 7 of the patent application scope as polymerized At least one.