TW202006124A - Compound, liquid crystal composition and liquid crystal display element - Google Patents

Abstract

The present invention provides a compound having high chemical stability, high ability to align liquid crystal molecules horizontally, high alignment in a wide range of addition concentration, proper reactivity, and high solubility in liquid crystal compositions, etc. At least one characteristic. The present invention provides a compound of the following formula (1). In formula (1), a and b are independently 0, 1, or 2, and 0≦a+b≦3, and ring A ¹ , ring A ² , ring A ^3, and ring A ^{4 are} independently, for example, 1,4- Cyclohexyl, Z ¹ , Z ² , Z ³ , Z ⁴ and Z ^{5 are} independently single bonds or alkyl groups with carbon number 1 to 10, etc. Sp ¹ and Sp ^{2 are} independently single bonds or carbon number 1 to An alkylene group such as 10, and P ¹ and P ^{2 are} independently specific polymerizable groups.

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. Further, in detail, it relates to a polymerizable polar compound having an excellent light absorption structure in one molecule, a liquid crystal composition containing the compound and having a positive or negative dielectric anisotropy, and a liquid crystal containing the composition Display element.

In the liquid crystal display element, the classification based on the operation mode of the liquid crystal molecules is phase change (PC), twisted nematic (TN), super twisted nematic (STN), electronically controlled birefringence ( electrically controlled birefringence (ECB), optically compensated bend (OCB), in-plane switching (IPS), vertical alignment (VA), fringe field switching (FFS), Field-induced photo-reactive alignment (FPA) and other modes. The component-based driving methods are classified into passive matrix (PM) and active matrix (AM). PM is classified as static, multiplex, etc., AM is classified as thin film transistor (TFT), metal-insulator-metal (MIM), etc. TFTs are 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. The classification based on the light source is 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 display element contains a liquid crystal composition having a nematic phase. This composition has appropriate characteristics. By improving the characteristics of the composition, an AM device having good characteristics can be obtained. The correlation between the two characteristics is summarized in Table 1 below. The characteristics of the composition will be further described based on a commercially available AM device. The temperature range of the nematic phase is related to the temperature range in which the device 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 dynamic images with the device, 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 small. More preferably, the viscosity is low at low temperatures.

1）可縮短於液晶顯示元件中注入組成物的時間[Table 1]

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

The 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 the TN mode element, the 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 anisotropy in the composition contributes to the low threshold voltage, small power consumption, and large contrast in the device. Therefore, it is preferably a large positive or negative dielectric anisotropy. The large specific resistance in the composition contributes to a large voltage retention rate and a large contrast in the device. Therefore, it is preferable to have a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase in the initial stage. It is preferable to have 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 an AM element having a TN mode, a composition having positive dielectric anisotropy is used. In an AM element having a VA mode, a composition having negative dielectric anisotropy is used. In an AM element having an IPS mode or an FFS mode, a composition having positive or negative dielectric anisotropy is used. A polymer sustained alignment (PSA) type AM device uses a composition having positive or negative dielectric anisotropy. 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. Then, while applying a voltage between the substrates of the element, the composition was irradiated with ultraviolet rays. The polymerizable compound is polymerized to form a polymer network structure in the composition. In this composition, 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. An element having a mode such as TN, ECB, OCB, IPS, VA, FFS, or FPA can expect such an effect of a polymer.

The report has the following methods: instead of an alignment film such as polyimide, a low-molecular compound with a cinnamate group or a polyvinyl cinnamate, a low-molecular compound with a chalcone structure, and an azo A low molecular compound or dendritic polymer of benzene structure controls the alignment of the liquid crystal (Patent Literature 1, Patent Literature 2, or Patent Literature 3). In the methods of Patent Document 1, Patent Document 2, or Patent Document 3, first, the low-molecular compound or polymer is dissolved as an additive in the liquid crystal composition. Next, a thin film containing the low-molecular compound or polymer is formed on the substrate by phase-separating the additive. Finally, the substrate is irradiated with linear polarized light at a temperature higher than the upper limit temperature of the liquid crystal composition. When a low-molecular compound or polymer undergoes dimerization or isomerization by the linear polarized light, its molecules are arranged in a certain direction. In this method, by selecting the type of low-molecular compound or polymer, a device with a horizontal alignment mode such as IPS or FFS and a device with a vertical alignment mode such as VA can be manufactured. In this method, it is important that the low-molecular compound or polymer easily dissolves at a temperature higher than the upper limit temperature of the liquid crystal composition, and when the temperature is returned to room temperature, the compound easily separates from the liquid crystal composition. However, it is difficult to ensure the compatibility of the low-molecular compound or polymer with the liquid crystal composition.

So far, regarding a liquid crystal display element without an alignment film, as a compound that can align liquid crystal molecules horizontally, Patent Document 2 describes a compound (S-1) (paragraph 0034 of the specification) [Patent 2], Patent Document 3 The compound (S-2) (the compound [14] of P176 in the specification) etc. are described. However, these compounds require high-energy light irradiation in order to align liquid crystal molecules at a sufficient alignment level, and there is an increase in manufacturing time caused by long-time light irradiation or damage to the liquid crystal caused by it Concerns, and thus expect to be improved.

[現有技術文獻] [專利文獻]

[Prior Art Literature] [Patent Literature]

[Patent Literature 1] International Publication No. 2015/146369 [Patent Literature 2] International Publication No. 2017/057162 [Patent Literature 3] International Publication No. 2017/102068

[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 horizontally, high alignment in a wide range of addition concentration, proper reactivity, and high composition in liquid crystal At least one characteristic of the solubility in the substance, and it is expected that the voltage retention rate when used in a liquid crystal display element is large. 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, positive or negative dielectric anisotropy At least one of characteristics such as large anisotropy, large specific resistance, high stability to ultraviolet rays, high stability to heat, and large elastic constant. The third subject is to provide a liquid crystal display device including the composition, and when the composition is irradiated with ultraviolet rays to form a film of a polar compound in the device, the film has an appropriate hardness and low penetration of contact components Performance, high weather resistance, and at least one characteristic of an appropriate volume resistance value, and the liquid crystal display element has a wide temperature range of available elements, a short response time, a high voltage retention rate, a low threshold voltage, At least one characteristic of large contrast and long life. [Means to solve the problem]

（式中的記號的說明將於後敘述） [發明的效果]The inventors of the present invention found that the compound represented by the following formula (1) can solve the above-mentioned problems, and completed the invention.

(The description of the symbols in the formula will be described later) [Effect of the invention]

The first advantage of the present invention is to provide a compound with high chemical stability, high ability to align liquid crystal molecules horizontally, high alignment in a wide range of addition concentration, proper reactivity and high composition in liquid crystal At least one of the solubility in the substance, and it is expected that the voltage retention rate when used in a liquid crystal display element is large. 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, low viscosity, appropriate optical anisotropy, positive or negative dielectric anisotropy At least one of characteristics such as large anisotropy, large specific resistance, high stability to ultraviolet rays, high stability to heat, and large elastic constant. The third advantage is to provide a liquid crystal display element including the composition, which is formed by irradiating ultraviolet rays to the composition to form a film of a polar compound in the element, the film having an appropriate hardness and low penetration of contact components Performance, high weather resistance, and at least one characteristic of an appropriate volume resistance value, and the liquid crystal display element has a wide temperature range of available elements, a short response time, a high voltage retention rate, a low threshold voltage, At least one characteristic of large contrast and long life. By using the liquid crystal composition containing the compound of the present invention, the alignment film formation step is not required, and thus a liquid crystal display element with reduced manufacturing cost can be obtained.

How to use the terms in this specification is as follows. Sometimes the terms "liquid crystal composition" and "liquid crystal display element" are simply referred to as "composition" and "element", respectively. "Liquid crystal display element" is a general term for liquid crystal display panel and liquid crystal display module. "Liquid crystal compound" is a compound having a nematic phase and a smectic phase equivalent liquid crystal phase, and although not having a liquid crystal phase, for the purpose of adjusting the characteristics of the temperature range, viscosity, and dielectric anisotropy of the nematic phase The general term for compounds mixed into the composition. This compound 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. "Polar compounds" help liquid crystal molecules to align by polar groups interacting with the substrate surface.

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

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 B ¹ , C ¹ , and F surrounded by hexagons correspond to rings B ¹ , C ¹ , and F, respectively. The hexagon represents a condensed ring such as a six-membered ring such as a cyclohexane ring or a benzene ring, or a naphthalene ring. A diagonal line that crosses the hexagon indicates that any hydrogen on the ring may be substituted with -Sp ¹ -P ¹ or the like. Subscripts such as e indicate the number of substituted groups. When the subscript is 0, there is no such substitution.

The symbol of the terminal group R ¹¹ is used in various component compounds. In these compounds, the two groups represented by any two R ¹¹ may be the same or different. For example, compound R (2) ¹¹ is ethyl, R compound (3) ¹¹ is ethyl. In some cases, R ¹¹ of compound (2) is ethyl and R ¹¹ of compound (3) is propyl. This rule also applies to other symbols such as terminal groups, rings, and bonding groups. In formula (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. This rule also applies to any two rings D ¹ when i is greater than 2. This rule also applies to other marks such as rings and bonding bases.

The expression "at least one "A"" means that the number of "A" is arbitrary. The expression "at least one'A' can be replaced by'B'", when the number of'A' is one, the position of'A' is arbitrary, and when the number of'A' is more than two, The positions of these'A's can be selected without restriction. The rule also applies to the expression "at least one'A' is replaced by'B'". The expression "at least one A may be substituted by B, C, or D" means including at least one A substituted by B, at least one A substituted by C, and at least one A substituted by D, and then including multiple A In the case of substitution by at least two of B, C, and D. 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, alkoxyalkyl Group, alkoxyalkenyl group, alkenyloxyalkyl group. Furthermore, the situation where two consecutive -CH ₂ -are replaced by -O- to become -OO- is not good. -CH alkyl group, a methyl moiety (-CH ₂ -H) of ₂ - substituted -O- -OH case also becomes poor.

Halogen means fluorine, chlorine, bromine or iodine. The preferred halogen is fluorine or chlorine. A particularly preferred halogen is fluorine. The alkyl group is linear or branched and does not include cyclic alkyl groups. 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 stereo 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 asymmetric divalent groups such as tetrahydropyran-2,5-diyl that are generated by removing two hydrogens from the ring.

The present invention includes the following items.

式（1）中， a及b獨立地為0、1或2，且0≦a+b≦3， 環A¹ 、環A² 、環A³ 及環A⁴ 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、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、吡啶-2,5-二基、芴-2,7-二基、菲-2,7-二基、蒽-2,6-二基、全氫環戊并[a]菲-3,17-二基、2,3,4,7,8,9,10,11,12,13,14,15,16,17-十四氫環戊并[a]菲-3,17-二基、（A-1）所表示的基或（A-2）所表示的基，該些環中，至少一個氫可經氟、氯、碳數1至12的烷基、碳數2至12的烯基、碳數1至11的烷氧基、碳數2至11的烯氧基、-Sp¹ -P¹ 或-Sp² -P² 取代，該些基中，至少一個氫可經氟或氯取代，於a為2時，兩個環A¹ 可不同，於b為2時，兩個環A⁴ 可不同，（A-2）中，c為2、3或4。其中，環A¹ 、環A² 、環A³ 或環A⁴ 中的至少一個為萘-2,6-二基、菲-2,7-二基、（A-1）所表示的基或（A-2）所表示的基；

Z¹ 、Z² 、Z³ 、Z⁴ 及Z⁵ 獨立地為單鍵或碳數1至10的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-、-OCO-或-OCOO-取代，至少一個-(CH₂ )₂ -可經-CH=CH-或-C≡C-取代，該些基中，至少一個氫可經鹵素取代。其中，Z² 、Z³ 或Z⁴ 中的至少一個為-COO-、-OCO-、-CH=CHCOO-、-OCOCH=CH-、-CH=CH-、-CH=CHCO-或-COCH=CH-，於a為2時，兩個Z¹ 可不同，於b為2時，兩個Z⁵ 可不同； Sp¹ 及Sp² 獨立地為單鍵或碳數1至10的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-、-OCO-或-OCOO-取代，至少一個-(CH₂ )₂ -可經-CH=CH-或-C≡C-取代，該些基中，至少一個氫可經鹵素取代，於在結構內存在多個Sp¹ 或Sp² 的情況下，分別可不同； P¹ 及P² 獨立地為式（1b）～式（1h）的任一者所表示的基，於在結構內存在多個P¹ 或P² 的情況下，分別可不同；

式（1b）～式（1h）中， M¹ 、M² 、M³ 及M⁴ 獨立地為氫、鹵素、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； R² 為氫、鹵素、碳數1至5的烷基，該烷基中，至少一個氫可經鹵素取代，至少一個-CH₂ -可經-O-取代； R³ 、R⁴ 、R⁵ 、R⁶ 及R⁷ 獨立地為氫或碳數1至15的烷基，該烷基中，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，該些基中，至少一個氫可經鹵素取代。[1] A compound represented by formula (1).

In formula (1), a and b are independently 0, 1 or 2, and 0≦a+b≦3, ring A ¹ , ring A ² , ring A ³ and ring A ^{4 are} independently 1,4-stretched Cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, decalin-2,6-diyl, 1,2,3,4-tetra Hydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2, 5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl, 2 ,3,4,7,8,9,10,11,12,13,14,15,16,17-tetrahydrocyclopenta[a]phenanthrene-3,17-diyl, (A-1) The group represented by or the group represented by (A-2), in these rings, at least one hydrogen may be fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and carbon 1 Alkoxy groups to 11, alkoxy groups having 2 to 11 carbons, -Sp ¹ -P ¹ or -Sp ² -P ^{2 are} substituted, in these groups, at least one hydrogen may be substituted by fluorine or chlorine, and a is At 2, the two rings A ¹ may be different. When b is 2, the two rings A ⁴ may be different. In (A-2), c is 2, 3 or 4. Wherein, at least one of ring A ¹ , ring A ² , ring A ³ or ring A ⁴ is naphthalene-2,6-diyl, phenanthrene-2,7-diyl, or the group represented by (A-1) or (A-2) represents the base;

Z ¹ , Z ² , Z ³ , Z ⁴ and Z ^{5 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. In this alkylene group, 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-, in these groups, at least one hydrogen may be substituted by halogen replace. Wherein, at least one of Z ² , Z ³ or Z ⁴ is -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO- or -COCH= CH-, when a is 2, the two Z ^1s may be different, and when b is 2, the two Z ^5s may be different; Sp ¹ and Sp ^{2 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, In the alkylene group, at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, -OCO- or -OCOO-, and at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH -Or -C≡C- substitution, in these groups, at least one hydrogen may be substituted by halogen, in the case where there are multiple Sp ¹ or Sp ² in the structure, they may be different; P ¹ and P ^{2 are} independently The basis represented by any one of formula (1b) to formula (1h) may be different when there are multiple P ¹ or P ² in the structure;

In the formula (1b) to the formula (1h), M ¹ , M ² , M ³ and M ^{4 are} independently hydrogen, halogen, an alkyl group having 1 to 5 carbons or at least one hydrogen substituted with halogen and having 1 to 5 carbons R ² is hydrogen, halogen, C 1-5 alkyl group, in this alkyl group, at least one hydrogen may be substituted by halogen, at least one -CH ₂ -may be substituted by -O-; R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are} independently hydrogen or an alkyl group having 1 to 15 carbon atoms, in which 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-, in these groups, at least one hydrogen may be substituted by halogen.

Z¹ 、Z² 、Z³ 、Z⁴ 及Z⁵ 獨立地為單鍵、-(CH₂ )₂ -、-C≡C-、-COO-、-OCO-、-CF₂ O-、-OCF₂ -、-CH₂ O-、-OCH₂ -、-CF=CF-、-CH=CHCOO-、-OCOCH=CH-、-CH=CH-、-CH=CHCO-或-COCH=CH-，其中，Z² 、Z³ 或Z⁴ 中的至少一個為-COO-、-OCO-、-CH=CHCOO-、-OCOCH=CH-、-CH=CH-、-CH=CHCO-或-COCH=CH-，於a為2時，兩個Z¹ 可不同，兩個Z⁵ 可不同； Sp¹ 及Sp² 獨立地為單鍵或碳數1至10的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-COO-或-OCO-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，於在結構內存在多個Sp¹ 或Sp² 的情況下，分別可不同； P¹ 及P² 獨立地為式（1b）～式（1h）的任一者所表示的基，於在結構內存在多個P¹ 或P² 的情況下，分別可不同；

式（1b）～式（1h）中， M¹ 、M² 、M³ 及M⁴ 獨立地為氫、鹵素、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； R² 為氫、鹵素、碳數1至5的烷基，該烷基中，至少一個氫可經鹵素取代，至少一個-CH₂ -可經-O-取代； R³ 、R⁴ 、R⁵ 、R⁶ 及R⁷ 獨立地為氫或碳數1至15的烷基，該烷基中，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，該些基中，至少一個氫可經鹵素取代。[2] The compound according to [1], wherein in formula (1), a and b are independently 0, 1 or 2, and 0≦a+b≦2; ring A ¹ , ring A ² , ring A ³ and Ring A ^{4 are} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6 -Diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, Pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta [a]phenanthrene-3,17-diyl, 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetrahydrocyclopenta[a]phenanthrene -3,17-diyl, the group represented by (A-1) or the group represented by (A-2), in these rings, at least one hydrogen can be substituted by fluorine, chlorine, or an alkyl group having 1 to 12 carbon atoms , An alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, an alkenoxy group having 2 to 11 carbon atoms, -Sp ¹ -P ¹ or -Sp ² -P ² substitution, in these groups, At least one hydrogen can be substituted by fluorine or chlorine. When a is 2, the two rings A ¹ can be different. When b is 2, the two rings A ⁴ can be different. In (A-2), c is 2, 3. Or 4. Wherein, at least one of ring A ¹ , ring A ² , ring A ³ or ring A ⁴ is naphthalene-2,6-diyl, phenanthrene-2,7-diyl, or the group represented by (A-1) or (A-2) represents the base;

Z ¹ , Z ² , Z ³ , Z ⁴ and Z ^{5 are} independently single bonds, -(CH ₂ ) ₂ -, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -CF=CF-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO- or -COCH=CH-, Wherein, at least one of Z ² , Z ³ or Z ⁴ is -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO- or -COCH= CH-, when a is 2, the two Z ¹ may be different, the two Z ⁵ may be different; Sp ¹ and Sp ^{2 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in the alkylene group, At least one -CH ₂ -may be substituted by -O-, -COO- or -OCO-, 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 substitution, which may be different when there are multiple Sp ¹ or Sp ² in the structure; P ¹ and P ^{2 are} independently a group represented by any one of formula (1b) to formula (1h), In the case of multiple P ¹ or P ² in the structure, they can be different;

In the formula (1b) to the formula (1h), M ¹ , M ² , M ³ and M ^{4 are} independently hydrogen, halogen, an alkyl group having 1 to 5 carbons or at least one hydrogen substituted with halogen and having 1 to 5 carbons R ² is hydrogen, halogen, C 1-5 alkyl group, in this alkyl group, at least one hydrogen may be substituted by halogen, at least one -CH ₂ -may be substituted by -O-; R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are} independently hydrogen or an alkyl group having 1 to 15 carbon atoms, in which 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-, in these groups, at least one hydrogen may be substituted by halogen.

式（1-1）至式（1-3）中， 環A¹ 、環A² 、環A³ 及環A⁴ 獨立地為1,4-伸環己基、1,4-伸苯基、萘-2,6-二基、嘧啶-2,5-二基、吡啶-2,5-二基、芴-2,7-二基、菲-2,7-二基、蒽-2,6-二基、（A-1）所表示的基或（A-2）所表示的基，該些環中，至少一個氫可經氟、氯、碳數1至12的烷基、碳數2至12的烯基、碳數1至11的烷氧基、碳數2至11的烯氧基、-Sp¹ -P¹ 或-Sp² -P² 取代，該些基中，至少一個氫可經氟或氯取代，於a為2時，兩個環A¹ 可不同，於b為2時，兩個環A⁴ 可不同，（A-2）中，c為2、3或4。其中，環A¹ 、環A² 、環A³ 或環A⁴ 中的至少一個為萘-2,6-二基、菲-2,7-二基、（A-1）所表示的基或（A-2）所表示的基；

Z² 、Z³ 及Z⁴ 獨立地為單鍵、-(CH₂ )₂ -、-C≡C-、-COO-、-OCO-、-CF₂ O-、-OCF₂ -、-CH₂ O-、-OCH₂ -、-CF=CF-、-CH=CHCOO-、-OCOCH=CH-、-CH=CH-、-CH=CHCO-或-COCH=CH-，其中，Z² 、Z³ 及Z⁴ 中的至少一個為-COO-、-OCO-、-CH=CHCOO-、-OCOCH=CH-、-CH=CH-、-CH=CHCO-或-COCH=CH-； Sp¹ 及Sp² 獨立地為單鍵或碳數1至10的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-COO-、-OCOO-或-OCO-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，於在結構內存在多個Sp¹ 或Sp² 的情況下，分別可不同； P¹ 及P² 獨立地為式（1b）～式（1h）的任一者所表示的基，於在結構內存在多個P¹ 或P² 的情況下，分別可不同；

式（1b）～式（1h）中， M¹ 、M² 、M³ 及M⁴ 獨立地為氫、鹵素、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； R² 為氫、鹵素、碳數1至5的烷基，該烷基中，至少一個氫可經鹵素取代，至少一個-CH₂ -可經-O-取代； R³ 、R⁴ 、R⁵ 、R⁶ 及R⁷ 獨立地為氫或碳數1至15的烷基，該烷基中，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，該些基中，至少一個氫可經鹵素取代。[3] The compound according to [1] or [2], which is represented by any one of formula (1-1) to formula (1-3).

In formula (1-1) to formula (1-3), ring A ¹ , ring A ² , ring A ³ and ring A ^{4 are} independently 1,4-cyclohexyl, 1,4-phenylene, naphthalene -2,6-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6- Diyl, the group represented by (A-1) or the group represented by (A-2), in these rings, at least one hydrogen may be through fluorine, chlorine, alkyl having 1 to 12 carbons, and carbon having 2 to 12 alkenyl groups, C 1-11 alkoxy groups, C 2-11 alkenyl groups, -Sp ¹ -P ¹ or -Sp ² -P ² substitution, in these groups, at least one hydrogen can be Fluorine or chlorine substitution. When a is 2, the two rings A ¹ may be different. When b is 2, the two rings A ⁴ may be different. In (A-2), c is 2, 3 or 4. Wherein, at least one of ring A ¹ , ring A ² , ring A ³ or ring A ⁴ is naphthalene-2,6-diyl, phenanthrene-2,7-diyl, or the group represented by (A-1) or (A-2) represents the base;

Z ² , Z ³ and Z ^{4 are} independently a single bond, -(CH ₂ ) ₂ -, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -CF=CF-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO- or -COCH=CH-, where Z ² , Z At least one of ³ and Z ⁴ is -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO- or -COCH=CH-; Sp ¹ and Sp ^{2 is} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be substituted with -O-, -COO-, -OCOO-, or -OCO-, 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, in the case where there are multiple Sp ¹ or Sp ² in the structure, respectively Different; P ¹ and P ^{2 are} independently the basis represented by any one of formula (1b) to formula (1h), and may be different when there are multiple P ¹ or P ² in the structure;

In the formula (1b) to the formula (1h), M ¹ , M ² , M ³ and M ^{4 are} independently hydrogen, halogen, an alkyl group having 1 to 5 carbons or at least one hydrogen substituted with halogen and having 1 to 5 carbons R ² is hydrogen, halogen, C 1-5 alkyl group, in this alkyl group, at least one hydrogen may be substituted by halogen, at least one -CH ₂ -may be substituted by -O-; R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are} independently hydrogen or an alkyl group having 1 to 15 carbon atoms, in which 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-, in these groups, at least one hydrogen may be substituted by halogen.

Z² 、Z³ 及Z⁴ 獨立地為單鍵、-(CH₂ )₂ -、-C≡C-、-COO-、-OCO-、-CH=CHCOO-、-OCOCH=CH-、-CH=CH-、-CH=CHCO-或-COCH=CH-，其中，Z² 、Z³ 及Z⁴ 中的至少一個為-COO-、-OCO-、-CH=CHCOO-、-OCOCH=CH-、-CH=CH-、-CH=CHCO-或-COCH=CH-； Sp¹ 及Sp² 獨立地為單鍵或碳數1至10的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-COO-、-OCOO-或-OCO-取代，至少一個-(CH₂ )₂ -可經-CH=CH-取代，於在結構內存在多個Sp¹ 或Sp² 的情況下，分別可不同； P¹ 及P² 獨立地為式（1b）、式（1c）、式（1d）或式（1e）的任一者所表示的基，於在結構內存在多個P¹ 或P² 的情況下，分別可不同；

式（1b）～式（1e）中， M¹ 、M² 、M³ 及M⁴ 獨立地為氫、鹵素、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； R² 為氫、鹵素或碳數1至5的烷基，該烷基中，至少一個氫可經鹵素取代，至少一個-CH₂ -可經-O-取代； R³ 、R⁴ 、R⁵ 及R⁶ 獨立地為氫或碳數1至15的烷基，該烷基中，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，該些基中，至少一個氫可經鹵素取代。[4] The compound according to [3], wherein in formula (1-1), formula (1-2) and formula (1-3), ring A ¹ , ring A ² , ring A ³ and ring A ⁴ Independently 1,4-cyclohexyl, 1,4-phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, (A-1 ) Or the group represented by (A-2), in these rings, at least one hydrogen may be fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and carbon number. An alkoxy group of 1 to 11, an alkoxy group of 2 to 11 carbons, -Sp ¹ -P ¹ or -Sp ² -P ^{2 are} substituted, and (A-2), c is 2, 3 or 4. Wherein, at least one of ring A ¹ , ring A ² , ring A ³ or ring A ⁴ is naphthalene-2,6-diyl, phenanthrene-2,7-diyl, or the group represented by (A-1) or (A-2) represents the base;

Z ² , Z ³ and Z ^{4 are} independently a single bond, -(CH ₂ ) ₂ -, -C≡C-, -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH =CH-, -CH=CHCO- or -COCH=CH-, wherein at least one of Z ² , Z ³ and Z ⁴ is -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH- , -CH=CH-, -CH=CHCO- or -COCH=CH-; Sp ¹ and Sp ^{2 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -Can be substituted by -O-, -COO-, -OCOO- or -OCO-, at least one -(CH ₂ ) ₂ -Can be substituted by -CH=CH-, there are multiple Sp ¹ or Sp in the structure ^In the case of ² , they can be different; P ¹ and P ^{2 are} independently the basis represented by any one of formula (1b), formula (1c), formula (1d), or formula (1e), which exists in the structure In the case of multiple P ¹ or P ² , they can be different;

In the formula (1b) to the formula (1e), M ¹ , M ² , M ³ and M ^{4 are} independently hydrogen, halogen, an alkyl group having 1 to 5 carbon atoms or at least one hydrogen substituted with halogen and having 1 to 5 carbon atoms R ² is hydrogen, halogen or C 1-5 alkyl group, in this alkyl group, at least one hydrogen may be substituted by halogen, at least one -CH ₂ -may be substituted by -O-; R ³ , R ^4. R ⁵ and R ^{6 are} independently hydrogen or an alkyl group having 1 to 15 carbon atoms. In this alkyl group, 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-, in these groups, at least one hydrogen may be substituted by halogen.

Z² 、Z³ 及Z⁴ 獨立地為單鍵、-(CH₂ )₂ -、-C≡C-、-COO-、-OCO-、-CH=CHCOO-、-OCOCH=CH-、-CH=CH-、-CH=CHCO-或-COCH=CH-，其中，Z² 、Z³ 及Z⁴ 中的至少一個為-COO-、-OCO-、-CH=CHCOO-、-OCOCH=CH-、-CH=CH-、-CH=CHCO-或-COCH=CH-； Sp¹ 及Sp² 獨立地為單鍵或碳數1至10的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-COO-、-OCOO-或-OCO-取代，至少一個-(CH₂ )₂ -可經-CH=CH-取代，於在結構內存在多個Sp¹ 或Sp² 的情況下，分別可不同； P¹ 及P² 獨立地為式（1b-1）、式（1b-2）、式（1b-3）、式（1b-4）、式（1b-5）、式（1c-1）、式（1d-1）、式（1d-2）或式（1e-1）所表示的基。

[5] The compound according to [3], wherein in formula (1-1), formula (1-2) and formula (1-3), ring A ¹ , ring A ² , ring A ³ and ring A ⁴ Independently 1,4-cyclohexyl, 1,4-phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, (A-1 ) Or the group represented by (A-2), in these rings, at least one hydrogen may be substituted by fluorine, chlorine, methyl or ethyl. In (A-2), c is 2, 3 or 4. Wherein, at least one of ring A ¹ , ring A ² , ring A ³ or ring A ⁴ is naphthalene-2,6-diyl, phenanthrene-2,7-diyl, or the group represented by (A-1) or (A-2) represents the base;

Z ² , Z ³ and Z ^{4 are} independently a single bond, -(CH ₂ ) ₂ -, -C≡C-, -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH =CH-, -CH=CHCO- or -COCH=CH-, wherein at least one of Z ² , Z ³ and Z ⁴ is -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH- , -CH=CH-, -CH=CHCO- or -COCH=CH-; Sp ¹ and Sp ^{2 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -Can be substituted by -O-, -COO-, -OCOO- or -OCO-, at least one -(CH ₂ ) ₂ -Can be substituted by -CH=CH-, there are multiple Sp ¹ or Sp in the structure ^In the case of ² , they can be different; P ¹ and P ^{2 are} independently formula (1b-1), formula (1b-2), formula (1b-3), formula (1b-4), formula (1b-5 ), formula (1c-1), formula (1d-1), formula (1d-2) or formula (1e-1).

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

P¹ 及P² 獨立地為式（1b-1）、式（1b-2）、式（1b-3）、式（1b-4）、式（1b-5）、式（1c-1）、式（1d-1）、式（1d-2）或式（1e-1）所表示的基； Sp¹ 及Sp² 獨立地為單鍵或碳數1至10的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-COO-、-OCOO-或-OCO-取代，至少一個-(CH₂ )₂ -可經-CH=CH-取代； Y為（MES-1-01）至（MES-1-10）的任一式所表示的基，該些基中，至少一個氫可經氟、氯、甲基或乙基取代。

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

P ¹ and P ^{2 are} independently formula (1b-1), formula (1b-2), formula (1b-3), formula (1b-4), formula (1b-5), formula (1c-1), The group represented by formula (1d-1), formula (1d-2) or formula (1e-1); Sp ¹ and Sp ^{2 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, the alkylene group Among them, at least one -CH ₂ -may be substituted by -O-, -COO-, -OCOO- or -OCO-, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH-; Y is (MES- 1-01) to a group represented by any formula of (MES-1-10), in which at least one hydrogen may be substituted with fluorine, chlorine, methyl or ethyl.

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

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

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，該烷基及烯基中，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、-CH₂ CH₂ -、-CH=CH-、-C≡C-或-COO-。[10] The liquid crystal composition according to [9], which further 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 the alkyl groups and alkenyl groups is -CH ₂ -May be substituted by -O-, at least one hydrogen may be substituted by fluorine; Ring B ¹ , Ring B ² , Ring B ³ 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 bonds, -CH ₂ CH ₂ -, -CH=CH-, -C≡C- or -COO-.

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，該烷基及烯基中，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、至少一個氫可經氟取代的1,4-伸苯基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基或嘧啶-2,5-二基； Z¹⁴ 、Z¹⁵ 及Z¹⁶ 獨立地為單鍵、-CH₂ CH₂ -、-CH=CH-、-C≡C-、-COO-、-CF₂ O-、-OCF₂ -、-CH₂ O-、-CF=CF-、-CH=CF-或-(CH₂ )₄ -； L¹¹ 及L¹² 獨立地為氫或氟。[11] The liquid crystal composition according to [9] or [10], which further 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. Among the alkyl groups and alkenyl groups, at least one -CH ₂ -may be passed through -O -Substitution, at least one hydrogen may be substituted by fluorine; X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ or -OCF ₂ CHFCF ₃ ; Ring C ¹ , Ring C ² and Ring C ^{3 are} independently 1,4-cyclohexyl, 1,4-phenylene, tetrahydropyran-2,5-diyl where at least one hydrogen can be substituted with fluorine , 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; Z ¹⁴ , Z ¹⁵ and Z ^{16 are} independently single bonds, -CH ₂ CH ₂ -, -CH=CH -, -C≡C-, -COO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -CF=CF-, -CH=CF- or -(CH ₂ ) ₄ -; L ¹¹ and L ^{12 are} independently hydrogen or fluorine.

式（8）中， R¹⁴ 為碳數1至10的烷基或碳數2至10的烯基，該烷基及烯基中，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、至少一個氫可經氟取代的1,4-伸苯基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基或嘧啶-2,5-二基； Z¹⁷ 為單鍵、-CH₂ CH₂ -、-C≡C-、-COO-、-CF₂ O-、-OCF₂ -或-CH₂ O-； L¹³ 及L¹⁴ 獨立地為氫或氟； i為1、2、3或4。[12] The liquid crystal composition according to any one of [9] to [11], which further contains at least one compound of the compound represented by formula (8).

In formula (8), R ¹⁴ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. In the alkyl group and the alkenyl group, at least one -CH ₂ -may be substituted with -O-, and at least one Hydrogen can be substituted by fluorine; X ¹² is -C≡N or -C≡CC≡N; Ring D ¹ is 1,4-cyclohexyl, at least one hydrogen can be substituted by fluorine, 1,4-phenylene, tetra Hydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; Z ¹⁷ is a single bond, -CH ₂ CH ₂ -, -C ≡C-, -COO-, -CF ₂ O-, -OCF ₂ -, or -CH ₂ O-; L ¹³ and L ^{14 are} independently hydrogen or fluorine; i is 1, 2, 3, or 4.

式（9）至式（15）中， R¹⁵ 及R¹⁶ 獨立地為碳數1至10的烷基或碳數2至10的烯基，該烷基及烯基中，至少一個-CH₂ -可經-O-取代，至少一個氫可經氟取代； R¹⁷ 為氫、氟、碳數1至10的烷基或碳數2至10的烯基，該烷基及烯基中，至少一個-CH₂ -可經-O-取代，至少一個氫可經氟取代； 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、至少一個氫可經氟取代的1,4-伸苯基、四氫吡喃-2,5-二基或十氫萘-2,6-二基； 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、-CH₂ CH₂ -、-COO-、-CH₂ O-、-OCF₂ -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。[13] The liquid crystal composition according to any one of [9] to [12], which further contains at least one compound selected from the group of compounds represented by formula (9) to formula (15).

In formula (9) to formula (15), R ¹⁵ and R ^{16 are} independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and at least one -CH ₂ in the alkyl group and alkenyl group -May be substituted with -O-, at least one hydrogen may be substituted with fluorine; R ¹⁷ is hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. One -CH ₂ -may be substituted with -O- and at least one hydrogen may be substituted with fluorine; ring E ¹ , ring E ² , ring E ³ and ring E ^{4 are} independently 1,4-cyclohexyl, 1,4- Cyclohexenyl, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6-diyl substituted by fluorine for at least one hydrogen; Ring E ⁵ and ring E ^{6 is} 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 a single bond, -CH ₂ CH ₂ -, -COO-, -CH ₂ O-, -OCF ₂ -or -OCF ₂ CH ₂ CH ₂ -; L ¹⁵ and L ^{16 are} independently fluorine or chlorine; S ¹¹ is hydrogen or methyl; X is -CHF- or -CF ₂ -; j, k, m, n, p, q, r, and s are independently It is 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（16）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，該些環中，至少一個氫可經鹵素、碳數1至12的烷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、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，該些環中，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，該伸烷基中，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，該些基中，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-5）所表示的基的群組中的聚合性基；

M¹¹ 、M¹² 及M¹³ 獨立地為氫、氟、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； Sp¹¹ 、Sp¹² 及Sp¹³ 獨立地為單鍵或碳數1至10的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-COO-、-OCO-或-OCOO-取代，至少一個-CH₂ CH₂ -可經-CH=CH-或-C≡C-取代，該些基中，至少一個氫可經氟或氯取代； 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2以上。[14] The liquid crystal composition according to any one of [9] to [13], which contains at least one polymerizable compound of the compound represented by formula (16).

In formula (16), ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan Alkan-2-yl, pyrimidin-2-yl or pyrid-2-yl, in these rings, at least one hydrogen may be substituted by halogen, an alkyl group having 1 to 12 carbons or at least one hydrogen substituted by halogen 12 alkyl substitution; 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, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl Group, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in these rings, at least one hydrogen can be halogen, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons Or at least one hydrogen is substituted with a halogen-substituted alkyl group having 1 to 12 carbon atoms; Z ²² and Z ^{23 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -Can be substituted by -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 )-substitution, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; P ¹¹ , P ¹² and P ^{13 are} independently selected from the formula (P-1) to a polymerizable group in the group represented by formula (P-5);

M ¹¹ , M ¹² and M ^{13 are} independently hydrogen, fluorine, C 1-5 alkyl, or at least one hydrogen substituted with fluorine or chlorine, C 1-5 alkyl; Sp ¹¹ , Sp ¹² and Sp ^{13 is} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be substituted with -O-, -COO-, -OCO- or -OCOO-, at least one -CH ₂ CH ₂ -may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; u is 0, 1 or 2; f, g and h are independent The ground is 0, 1, 2, 3, or 4, and the sum of f, g, and h is 2 or more.

式（16-1）至式（16-27）中， P¹¹ 、P¹² 及P¹³ 獨立地為選自式（P-1）至式（P-3）所表示的基的群組中的聚合性基，此處，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；

Sp¹¹ 、Sp¹² 及Sp¹³ 獨立地為單鍵或碳數1至10的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-COO-、-OCO-或-OCOO-取代，至少一個-CH₂ CH₂ -可經-CH=CH-或-C≡C-取代，該些基中，至少一個氫可經氟或氯取代。[15] The liquid crystal composition according to any one of [9] to [14], which contains at least one selected from the group of compounds represented by formula (16-1) to formula (16-27) Polymerizable compound.

In formula (16-1) to formula (16-27), P ¹¹ , P ¹² and P ^{13 are} independently selected from the group of groups represented by formula (P-1) to formula (P-3) A polymerizable group, where M ¹¹ , M ¹² and M ^{13 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with halogen;

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

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

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

The present invention also includes the following items. (A) The liquid crystal composition further contains a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antifoaming agent and the like At least two additives. (B) A polymerizable composition prepared by adding a polymerizable compound different from the compound (1) or the compound (16) to the liquid crystal composition. (C) A polymerizable composition prepared by adding compound (1) and compound (16) to the liquid crystal composition. (D) A liquid crystal composite prepared by polymerizing a polymerizable composition. (E) A polymer-stable alignment type element containing the liquid crystal composite. (F) A polymer-stabilized alignment element made by using a polymerizable composition by adding compound (1) and compound (16) to the liquid crystal composition And a polymerizable compound different from compound (1) or compound (16). The form 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) according to an embodiment of the present invention is characterized by a polar compound having a mesogen portion including at least one excellent light absorption structure and a polymerizable group. The compound (1) has high light absorption characteristics and the characteristics of absorbing light in a relatively long wavelength region due to the phenanthrene, naphthalene, tolane and other structures in the molecule. In contrast, sufficient characteristics are exhibited by short-time or low-energy light irradiation.

One of the uses of the compound (1) is an additive for a liquid crystal composition used in a liquid crystal display element. The compound (1) is added for the purpose of horizontally controlling the alignment of liquid crystal molecules. Such additives are preferably chemically stable under the condition of being sealed in the element, have high solubility in the liquid crystal composition, and have a large voltage retention rate when used in a liquid crystal display element. Compound (1) largely satisfies this characteristic.

The preferred examples of the compound (1) will be described. Preferred examples of R ¹ , Z ¹ to Z ⁵ , A ¹ to A ⁴ , Sp ¹ , Sp ² , P ¹ , P ² , a, and b in the compound (1) are also applicable to the subordinate formula of the compound (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.

Ring A ¹ , ring A ² , ring A ³ and ring A ^{4 are} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6- Diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-diyl Oxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2, 6-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl, 2,3,4,7,8,9,10,11,12,13,14,15,16,17- Tetrahydrocyclopenta[a]phenanthrene-3,17-diyl, the group represented by (A-1) or the group represented by (A-2), in these rings, at least one hydrogen can be Chlorine, C1-C12 alkyl, C2-C12 alkenyl, C1-C11 alkoxy, C2-C11 alkenoxy, -Sp ¹ -P ¹ or -Sp ² -P ² substitution, in these groups, at least one hydrogen may be substituted by fluorine or chlorine, when a is 2, the two rings A ¹ may be different, when b is 2, the two rings A ⁴ may be different, (A -2), c is 2, 3 or 4. Wherein, at least one of ring A ¹ , ring A ² , ring A ³ or ring A ⁴ is naphthalene-2,6-diyl, phenanthrene-2,7-diyl, or the group represented by (A-1) or (A-2) represents the base;

Preferred ring A ¹ , ring A ² , ring A ³ and ring A ^{4 are} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene and naphthalene-2 ,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1, 3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl, 2, 3,4,7,8,9,10,11,12,13,14,15,16,17-tetrahydrocyclopenta[a]phenanthrene-3,17-diyl, (A-1) The group represented by or the group represented by (A-2), preferably c is 1 or 2, in these rings, at least one hydrogen can be through fluorine, chlorine, alkyl having 1 to 12 carbons, carbon having 2 to 12 is an alkenyl group, an alkoxy group having 1 to 11 carbon atoms or an alkenoxy group having 2 to 11 carbon atoms. In these groups, at least one hydrogen may be substituted with fluorine or chlorine. Particularly preferred are 1,4-cyclohexyl, 1,4-phenylene, perhydrocyclopenta[a]phenanthrene-3,17-diyl or 2,3,4,7,8,9,10, 11,12,13,14,15,16,17-tetrahydrocyclopenta[a]phenanthrene-3,17-diyl, in these rings, at least one hydrogen can be fluorine or carbon number 1 to 5 Alkyl substitution. Particularly preferred are 1,4-cyclohexyl, 1,4-phenylene or perhydrocyclopenta[a]phenanthrene-3,17-diyl. In these rings, at least one hydrogen can be substituted by fluorine, methyl Or ethyl substitution.

Z ¹ , Z ² , Z ³ , Z ⁴ and Z ^{5 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. In this alkylene group, 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-, in these groups, at least one hydrogen may be substituted by halogen replace. Wherein, at least one of Z ² , Z ³ or Z ⁴ is -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO-, -COCH= In either of CH-, when a is 2, two Z ^1s may be different, and two Z ^5s may be different. Preferred Z ¹ , Z ² , Z ³ , Z ⁴ and Z ^{5 are} independently single bonds, -(CH ₂ ) ₂ -, -CH=CH-, -C≡C-, -COO-, -OCO- , -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -or -CF=CF-. Particularly preferred is a single bond, -(CH ₂ ) ₂ -or -CH=CH-. Tejia is a single key.

Sp ¹ and Sp ^{2 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. In this alkylene group, at least one -CH ₂ -may be passed through -O-, -CO-, -COO-, -OCO- Or -OCOO- substitution, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by halogen. Preferably, Sp ¹ and Sp ^{2 are} independently a single bond, an alkylene group having 1 to 6 carbon atoms, a -CH ₂ -alkylene group having 1 to 6 carbon atoms substituted with -O-, or -OCOO-. Particularly preferred is an alkylene group having 1 to 6 carbon atoms or -OCOO-.

P ¹ and P ^{2 are} independently a group represented by any one of formula (1b) to formula (1h).

Preferably, P ¹ and P ^{2 are} independently a group represented by any of (1b), (1c), (1d), and (1e).

Preferred M ¹ , M ² , M ³ and M ^{4 are} independently hydrogen, fluorine, methyl, ethyl or trifluoromethyl. Particularly preferred is hydrogen.

R ² is hydrogen, halogen or an alkyl group having 1 to 5 carbon atoms. In this alkyl group, at least one hydrogen may be substituted with halogen, and at least one -CH ₂ -may be substituted with -O-.

Preferred R ² is hydrogen, fluorine, methyl, ethyl, methoxymethyl or trifluoromethyl. Particularly preferred is hydrogen.

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

Preferably, R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are} independently hydrogen, a linear alkyl group having 1 to 10 carbon atoms, a linear alkenyl group having 2 to 10 carbon atoms, and a carbon number 1 to 1 A linear alkoxy group of 10 or a cyclic alkyl group having 3 to 6 carbon atoms. Particularly preferred are hydrogen, a linear alkyl group having 2 to 6 carbon atoms, a linear alkenyl group having 2 to 6 carbon atoms, a linear alkoxy group having 1 to 5 carbon atoms, or a cyclic ring having 4 to 6 carbon atoms. alkyl.

式（1b）～式（1h）中，M¹ 及M² 獨立地為氫、鹵素、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。Particularly preferred bases are formula (1b-1), formula (1b-2), formula (1b-3), formula (1b-4), formula (1b-5), formula (1c-1), and formula (1d -1), the group represented by formula (1d-2) or formula (1e-1).

In the formula (1b) to the formula (1h), M ¹ and M ^{2 are} independently hydrogen, halogen, 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 halogen.

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

式（1-1）至式（1-3）中， 環A¹ 、環A² 、環A³ 及環A⁴ 獨立地為1,4-伸環己基、1,4-伸苯基、萘-2,6-二基、嘧啶-2,5-二基、吡啶-2,5-二基、芴-2,7-二基、菲-2,7-二基、蒽-2,6-二基、（A-1）所表示的基或（A-2）所表示的基，該些環中，至少一個氫可經氟、氯、碳數1至12的烷基、碳數2至12的烯基、碳數1至11的烷氧基、碳數2至11的烯氧基、-Sp¹ -P¹ 或-Sp² -P² 取代，該些基中，至少一個氫可經氟或氯取代，於a為2時，兩個環A¹ 可不同，於b為2時，兩個環A⁴ 可不同，（A-2）中，c為2、3或4。其中，環A¹ 、環A² 、環A³ 或環A⁴ 中的至少一個為萘-2,6-二基、菲-2,7-二基、（A-1）所表示的基或（A-2）所表示的基；

該些環中，至少一個氫可經氟、氯、碳數1至12的烷基、碳數2至12的烯基、碳數1至11的烷氧基、碳數2至11的烯氧基、-Sp¹ -P¹ 或-Sp² -P² 取代，該些基中，至少一個氫可經氟或氯取代； Z² 、Z³ 及Z⁴ 獨立地為單鍵、-(CH₂ )₂ -、-C≡C-、-COO-、-OCO-、-CF₂ O-、-OCF₂ -、-CH₂ O-、-OCH₂ -、-CF=CF-、-CH=CHCOO-、-OCOCH=CH-、-CH=CH-、-CH=CHCO-或-COCH=CH-，其中，Z² 、Z³ 及Z⁴ 中的至少一個為-COO-、-OCO-、-CH=CHCOO-、-OCOCH=CH-、-CH=CH-、-CH=CHCO-或-COCH=CH-； Sp¹ 及Sp² 獨立地為單鍵或碳數1至10的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-COO-、-OCOO-或-OCO-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，於在結構內存在多個Sp¹ 或Sp² 的情況下，分別可不同； P¹ 及P² 獨立地為式（1b）～式（1h）的任一者所表示的基，於在結構內存在多個P¹ 或P² 的情況下，分別可不同；

式（1b）～式（1h）中， M¹ 、M² 、M³ 及M⁴ 獨立地為氫、鹵素、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； R² 為氫、鹵素、碳數1至5的烷基，該烷基中，至少一個氫可經鹵素取代，至少一個-CH₂ -可經-O-取代； R³ 、R⁴ 、R⁵ 、R⁶ 及R⁷ 獨立地為氫或碳數1至15的烷基，該烷基中，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，該些基中，至少一個氫可經鹵素取代。Preferred examples of the compound (1) are formula (1-1) to formula (1-3).

In formula (1-1) to formula (1-3), ring A ¹ , ring A ² , ring A ³ and ring A ^{4 are} independently 1,4-cyclohexyl, 1,4-phenylene, naphthalene -2,6-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6- Diyl, the group represented by (A-1) or the group represented by (A-2), in these rings, at least one hydrogen may be through fluorine, chlorine, alkyl having 1 to 12 carbons, and carbon having 2 to 12 alkenyl groups, C 1-11 alkoxy groups, C 2-11 alkenyl groups, -Sp ¹ -P ¹ or -Sp ² -P ² substitution, in these groups, at least one hydrogen can be Fluorine or chlorine substitution. When a is 2, the two rings A ¹ may be different. When b is 2, the two rings A ⁴ may be different. In (A-2), c is 2, 3 or 4. Wherein, at least one of ring A ¹ , ring A ² , ring A ³ or ring A ⁴ is naphthalene-2,6-diyl, phenanthrene-2,7-diyl, or the group represented by (A-1) or (A-2) represents the base;

In these rings, at least one hydrogen can be substituted by fluorine, chlorine, C 1-12 alkyl, C 2-12 alkenyl, C 1-11 alkoxy, C 2-11 alkenoxy Group, -Sp ¹ -P ¹ or -Sp ² -P ² , in these groups, at least one hydrogen may be substituted by fluorine or chlorine; Z ² , Z ³ and Z ^{4 are} independently a single bond, -(CH ₂ ) ₂ -, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -CF=CF-, -CH=CHCOO -, -OCOCH=CH-, -CH=CH-, -CH=CHCO- or -COCH=CH-, wherein at least one of Z ² , Z ³ and Z ⁴ is -COO-, -OCO-,- CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO- or -COCH=CH-; Sp ¹ and Sp ^{2 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, In the alkylene group, at least one -CH ₂ -may be substituted with -O-, -COO-, -OCOO- or -OCO-, and at least one -(CH ₂ ) ₂ -may be substituted with -CH=CH-, the In these groups, at least one hydrogen may be replaced by fluorine or chlorine, and may be different when there are multiple Sp ¹ or Sp ² in the structure; P ¹ and P ^{2 are} independently formula (1b) to formula (1h ) The basis represented by any one of them may be different if there are multiple P ¹ or P ² in the structure;

In the formula (1b) to the formula (1h), M ¹ , M ² , M ³ and M ^{4 are} independently hydrogen, halogen, an alkyl group having 1 to 5 carbons or at least one hydrogen substituted with halogen and having 1 to 5 carbons R ² is hydrogen, halogen, C 1-5 alkyl group, in this alkyl group, at least one hydrogen may be substituted by halogen, at least one -CH ₂ -may be substituted by -O-; R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are} independently hydrogen or an alkyl group having 1 to 15 carbon atoms, in which 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-, in these groups, at least one hydrogen may be substituted by halogen.

Among the compounds represented by formula (1-1), formula (1-2) or formula (1-3), any of Z ² , Z ³ or Z ⁴ is preferably -COO- or -OCO-. In addition, among the compounds represented by formula (1-1), formula (1-2) or formula (1-3), any of Z ² , Z ³ or Z ⁴ is preferably -CH=CHCOO-,- OCOCH=CH-, -CH=CH-, -CH=CHCO- or -COCH=CH-.

P¹ 及P² 獨立地為式（1b-1）、式（1b-2）、式（1b-3）、式（1b-4）、式（1b-5）、式（1c-1）、式（1d-1）、式（1d-2）或式（1e-1）所表示的基； Sp¹ 及Sp² 獨立地為單鍵或碳數1至10的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-COO-、-OCOO-或-OCO-取代，至少一個-(CH₂ )₂ -可經-CH=CH-取代；

Y為（MES-1-01）至（MES-1-10）的任一式所表示的基，該些基中，至少一個氫可經氟、氯、甲基或乙基取代。

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

P ¹ and P ^{2 are} independently formula (1b-1), formula (1b-2), formula (1b-3), formula (1b-4), formula (1b-5), formula (1c-1), The group represented by formula (1d-1), formula (1d-2) or formula (1e-1); Sp ¹ and Sp ^{2 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, the alkylene group Among them, at least one -CH ₂ -may be substituted by -O-, -COO-, -OCOO- or -OCO-, and at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH-;

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

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

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

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

Preferably, P ¹¹ , P ¹² and P ¹³ are polymerizable groups selected from the group represented by formula (P-1) to formula (P-5). Particularly preferred P ¹¹ , P ¹² and P ¹³ are radical (P-1), radical (P-2) or radical (P-3). A particularly preferred group (P-1) is -OCO-CH=CH ₂ or -OCO-C(CH ₃ )=CH ₂ . The wavy line from base (P-1) to base (P-5) indicates the location where the bonding is performed.

In the group (P-1) to the group (P-5), M ¹¹ , M ¹² and M ^{13 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons or at least one hydrogen substituted with halogen and a carbon number 1 to 5 alkyl. In order to improve the reactivity, M ¹¹ , M ¹² and M ¹³ are preferably hydrogen or methyl. Particularly preferred M ¹¹ is methyl, and particularly preferred M ¹² and M ¹³ are hydrogen.

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

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

Ring F and Ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, Pyrimidin-2-yl or pyridin-2-yl, in these rings, at least one hydrogen may be substituted by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or at least one hydrogen substituted by halogen Alkyl substitution with 1 to 12 carbons.

Preferred ring F and ring I are phenyl. 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, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl or pyridine-2,5-diyl, in these rings, at least one hydrogen may be halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or at least one hydrogen passing through halogen Substituted alkyl groups with 1 to 12 carbon atoms. Particularly preferred ring G is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ²² and Z ^{23 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. In this alkylene group, 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, in these groups, at least one hydrogen may be substituted by fluorine or chlorine.

Preferably, Z ²² and Z ²³ are single bonds, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, or -OCO-. Particularly preferred Z ²² and Z ²³ are single bonds.

u is 0, 1, or 2.

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

2. Synthesis of Compound (1) The synthesis method of 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 are "Organic Syntheses" (John Wiley & Sons, Inc), "Organic Reactions" (John Wiley & Sons Publishing Company) (John Wiley & Sons, Inc)), "Comprehensive Organic Synthesis" (Pergamon Press), "New Experimental Chemistry Lecture" (Maruzen) and other methods to synthesize .

2-1. Formation of the bonding group Z ¹ , the bonding group Z ² , the bonding group Z ³ , the bonding group Z ⁴ and the bonding group Z ⁵ Examples of the method of generating the bonding group in the compound (1) are as follows The process is described. 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 (1J) correspond to compound (1) or an intermediate of compound (1).

(I) Single key generation The compound (1A) is synthesized by reacting the arylboronic acid (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 then in the presence of dichlorobis(triphenylphosphine) palladium catalyst Reacts with compound (22).

(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 phenol (25) derived from the compound (21) in 1,3-dicyclohexylcarbodiimide (DCC) and 4-dimethylamino Dehydration in the presence of 4-dimethylamino pyridine (DMAP) to synthesize -COO- compound (1B). Compounds with -OCO- are also synthesized using this method.

(III) Formation of -CF ₂ O- and -OCF ₂ -Compound (26) is obtained by sulfurizing Compound (1B) with Lawesson's reagent. Compound (1C) with -CF ₂ O- was synthesized by fluorinating compound (26) with hydrogen fluoride pyridine complex and N-bromosuccinimide (NBS). Refer to M. Kuroboshi et al. "Chem. Lett." 1992 No. 827. Compound (1C) can also be synthesized by fluorinating compound (26) with (diethylamino) sulphur trifluoride (DAST). Refer to WH Bunnelle et al. "Journal of Organic Chemistry (J. Org. Chem.)" 1990, No. 55, p. 768. Compounds with -OCF ₂ -are also 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 phosphorus ylide, and the phosphorus ylide is reacted with 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) -CH ₂ CH ₂ -is generated in the presence of a palladium-carbon catalyst, and the compound (1D) is hydrogenated to synthesize the compound (1E).

(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 with -OCH ₂ -are also 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).

(VIV) Generation of -CH=CHCO- and -COCH=CH- Compound (1I) is synthesized by subjecting compound (40) and compound (27) to an aldol condensation reaction in the presence of NaOH.

(X) Generation of -CH=CHCOO- and -OCOCH=CH- Compound (1J) was synthesized by dehydrating cinnamic acid (41) and compound (25) in the presence of 1,3-dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine (DMAP).

2-2. Formation of Ring A ¹ , Ring A ² , Ring A ³ and Ring A ⁴ About 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, 2- Fluorine-1,4-phenylene, 2-methyl-1,4-phenylene, 2-ethyl-1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2 ,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-di , Pyrimidine-2,5-diyl, pyridine-2,5-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl, 2,3,4,7,8,9,10 ,11,12,13,14,15,16,17-tetrahydrocyclopenta[a]phenanthrene-3,17-diyl and other rings, starting materials are commercially available, or synthetic methods are widely known. The group represented by (A-1) and the group represented by (A-2) can be synthesized by referring to the generation of -C≡C-.

2-3. Or a linking group linking group Sp ¹ and Sp ^{2. 1} polymerizable group or polymerizable group P P ^{P. 1} to generate a polymerizable group or a polymerizable group P ² of the preferred embodiment ² of Bing Xixi group (1b) , Maleimide (1c), itaconic acid ester (1d), vinyl ester (1e), oxetanyl (1g) or vinyloxy (1h).

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

(1) Synthesis of compounds with single bonds Sp ¹ or Sp ² are compounds with single bonds. In this scheme, MSG ¹ is a monovalent organic group having at least one ring. Compound (1S) to compound (1Z) correspond to compound (1). When the polymerizable group is an acrylate derivative, it is synthesized by esterification of corresponding acrylic acid and HO-MSG ¹ . Vinyloxy is synthesized by the etherification of HO-MSG ¹ with vinyl bromide. The oxetanyl group is synthesized by oxidation of the terminal double bond. Maleimide diimide group is synthesized by the reaction of amine group with maleic anhydride. Itaconic acid ester is synthesized by esterification of the corresponding itaconic acid and HO-MSG ¹ . Vinyl esters are synthesized by transesterification of vinyl acetate with HOOC-MSG ¹ .

The synthesis method of the compound in which the linking group Sp ¹ or the linking group Sp ² is a single bond has been described above. The method of generating other linking groups can be synthesized by referring to the synthesis method of the bonding group Z ¹ , the bonding group Z ² , the bonding group Z ³ , the bonding group Z ⁴ and the bonding group Z ⁵ .

2-4. Synthesis Examples Examples of methods for synthesizing compound (1) are as follows. Among these compounds, MES is a mesogen group having at least one ring. The definitions of P ¹ , M ¹ , M ² , Sp ¹ and Sp ² are the same as described above. The compound (51A) and the compound (51B) are commercially available or can be synthesized using a mesogen (MES) having an appropriate ring structure as a starting material and according to a general organic synthesis method. In the case of synthesizing a compound in which MES and Sp ¹ are connected by an ether bond, the compound (53A) can be obtained by etherifying the compound (51A) using a compound (52) and a base such as potassium hydroxide. ). In addition, in the case of synthesizing a compound in which MES and Sp ¹ are connected by a single bond, a cross-coupling reaction can be carried out by using compound (51B) as a starting material and using compound (52), a metal catalyst such as palladium and a base, Thus, compound (53B) is obtained. Compound (53A) or Compound (53B) is sometimes derived as compound (54A) or compound that makes trimethylsilyl (TMS), Tetrahydropyranyl (THP) and other protective groups function as needed (54B). Thereafter, compound (53A), compound (53B), compound (54A), or compound (54B) is reetherified in the presence of a base such as compound (55) and potassium hydroxide to obtain compound (57A) ) Or compound (57B). At this time, in the case where the protecting group functions in the previous stage, the protecting group is removed by a deprotection reaction.

P² 為式（1b-3）所表示的基的化合物（1A）可由化合物（57），利用以下方法來合成。由化合物（57），於化合物（58）、DCC及DMAP的存在下進行酯化反應，藉此可衍生為化合物（1A）。

Compound (1A) where P ² is a group represented by formula (1b-3) can be synthesized from compound (57) by the following method. From compound (57), an esterification reaction is carried out in the presence of compound (58), DCC, and DMAP, thereby derivatizing compound (1A).

3. Liquid crystal composition The liquid crystal composition of the embodiment of the present invention contains the compound (1) as the component A. The compound (1) can contribute to the control of the alignment of liquid crystal molecules by non-covalent bonding with the substrate of the device. The composition preferably contains the compound (1) as the component A, and further contains a liquid crystal compound selected from the components B, C, D and E shown below. Component B is compound (2) to compound (4). Component C is compound (5) to compound (7). Component D is compound (8). Component E is compound (9) to compound (16). This composition may contain other liquid crystal compounds different from the compound (2) to the compound (16). When preparing the composition, it is preferable to select component B, component C, component D, and component E in consideration of the magnitude of positive or negative dielectric anisotropy and the like. A properly selected composition has a high upper limit temperature, a low lower limit temperature, a small viscosity, an appropriate optical anisotropy (ie, a large optical anisotropy or a small optical anisotropy), a large positive or Negative dielectric anisotropy, large specific resistance, stability to heat or ultraviolet rays, and appropriate elastic constants (ie, large elastic constants or small elastic constants).

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

Component B is a compound in which both terminal groups are alkyl or the like. 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 the compound of component B, 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 alkyl group or alkenyl group, at least one -CH ₂ -may be passed through -O -Substitution, at least one hydrogen may be substituted by fluorine.

Since the absolute value of dielectric anisotropy is small, component B is a compound close to neutral. 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 optical anisotropy.

As the content of component B is increased, the dielectric 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 is preferably more. In the case of preparing a composition for modes such as IPS and VA, based on the weight of the liquid crystal composition, the content of component B is preferably 30% by weight or more, and particularly preferably 40% by weight or more.

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

The dielectric anisotropy of the component C is positive, and its stability to heat, light, etc. is very excellent. Therefore, it can be used for the preparation of a composition for modes such as IPS, FFS, and OCB. Based on the weight of the liquid crystal composition, the content of component C is suitably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, and particularly preferably in the range of 40% by weight to 95% by weight. When component C is added to a composition with negative dielectric anisotropy, the content of component C is preferably 30% by weight or less based on the 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) whose right terminal group is -C≡N or -C≡CC≡N. Preferred examples of component D include compound (8-1) to compound (8-64). In the compound of component D, R ¹⁴ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. In this alkyl group and alkenyl group, at least one -CH ₂ -may be substituted with -O-, and at least one Hydrogen can be substituted by fluorine; 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 can be mainly used for the preparation of a composition for TN and other modes. By adding this component D, the dielectric anisotropy of the composition can be increased. Component D brings the effects of expanding the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. Component D is also useful for adjusting the voltage-transmittance curve of the device.

In the case of preparing a composition for TN and other modes, based on the weight of the liquid crystal composition, the content of component D 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, Particularly preferred is the range of 40% by weight to 95% by weight. When component D is added to a composition with negative dielectric anisotropy, the content of component D is preferably 30% by weight or less based on the 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 (9) to compound (16). These compounds have a phenylene group substituted by two halogens in a lateral position like 2,3-difluoro-1,4-phenylene group.

Preferred examples of component E include compound (9-1) to compound (9-8), compound (10-1) to compound (10-17), compound (11-1), compound (12-1) to Compound (12-3), Compound (13-1) to Compound (13-11), Compound (14-1) to Compound (14-3), Compound (15-1) to Compound (15-3) and Compound (16-1) to compound (16-3). In the compound of component E, R ¹⁵ and R ^{16 are} independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Among the alkyl groups and alkenyl groups, at least one -CH ₂ -may be passed through -O -Substitution, at least one hydrogen may be substituted by fluorine; R ¹⁷ is hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and at least one -CH _2- May be substituted by -O-, at least one hydrogen may be substituted by fluorine.

The dielectric anisotropy of component E is negative and large. Component E can be used for the preparation of IPS, VA, PSA and other modes of the composition. As the content of component E is increased, the dielectric anisotropy of the composition becomes negative and increases, 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 is preferably 40% by weight or more based on the weight of the liquid crystal composition.

In component E, compound (9) is a bicyclic compound, so it is mainly effective in reducing viscosity, adjusting optical anisotropy, or increasing dielectric anisotropy. Compound (10) and compound (11) are tricyclic compounds, and therefore have the effects of raising the maximum temperature, increasing optical anisotropy, or increasing dielectric anisotropy. Compounds (12) to (16) have the effect of increasing dielectric anisotropy.

In the case of preparing a composition for modes such as IPS, VA, and PSA, based on the weight of the liquid crystal composition, the content of component E is preferably 40% by weight or more, and particularly preferably 50% 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 based on the weight of the liquid crystal composition. By adding component E, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the 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: the upper limit temperature is high, the lower limit temperature is low, the viscosity is low, and the optical anisotropy is appropriate , Positive or negative dielectric anisotropy, large specific resistance, high stability to ultraviolet light, high stability to heat, large elastic constant, etc. If necessary, a liquid crystal compound different from component B, component C, component D, and component E may be added.

The liquid crystal composition is prepared by a well-known method. For example, the component compounds are mixed and then dissolved by heating. Additives may be added to this composition depending on the application. Examples of additives are polymerizable compounds other than formula (1) and formula (16), polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, defoamers Agent. 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. The polymerizable compound is compounded with the compound (1) by irradiating ultraviolet rays while a voltage is applied between the electrodes, thereby generating a polymer in the liquid crystal composition. At this time, the compound (1) is fixed in a state where the polar group interacts with the glass (or metal oxide) substrate surface in a non-covalent bonding manner. With this, the ability to control the alignment of the liquid crystal molecules is further improved, and at the same time, the compound (1) does not leak into the liquid crystal composition. In addition, an appropriate pretilt angle is also obtained on the surface of the glass (or metal oxide) substrate, so a liquid crystal display element with a reduced response time and a large voltage retention rate can be obtained.

Preferred examples of the polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane) and vinyl ketone. Particularly preferred examples are compounds having at least one acryloyloxy group and compounds having at least one methacryloyloxy group. Particularly preferred examples also include compounds having both acryloxy and methacryloxy.

Particularly preferred examples of the polymerizable compound are compound (M-1) to compound (M-17). In compound (M-1) to compound (M-17), R ²⁵ to R ^{31 are} independently hydrogen or methyl; s, v, and x are independently 0 or 1; t and u are independently 1 to 10. Integer; L ²¹ to L ^{26 are} independently hydrogen or fluorine, and L ²⁷ and L ^{28 are} independently hydrogen, fluorine or methyl.

The polymerizable compound can be rapidly polymerized by adding a polymerization initiator. By optimizing the reaction temperature, the amount of remaining polymerizable compound can be reduced. Examples of photo-radical polymerization initiators are TPO, 1173, and 4265 in the Darocure series of BASF, 184, 369, 500, 651, 784 in the Irgacure series, 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 the compound (1) having an ester bond group, a cinnamate bond, a chalcone skeleton or a stilbene skeleton is mixed into the composition, the compound (1) as the component A has the characteristics of the composition The main effects are as follows. The compound (1) is arranged in a certain direction at the molecular level when Fries rearrangement, photodimerization, or double bond cis-trans isomerization is generated by polarized light. Therefore, a thin film prepared from a polar compound aligns liquid crystal molecules in the same manner as an alignment film such as polyimide.

In the case of a compound (1) having an aromatic ester and a polymerizable group, the aromatic ester site undergoes photolysis by irradiation with ultraviolet light, thereby forming free radicals and generating photo-Frisian rearrangement. In the optical Fries rearrangement, when the polarization direction of polarized ultraviolet light is the same as the long axis direction of the aromatic ester portion, photolysis of the aromatic ester portion occurs. After photolysis, re-bonding is performed and hydroxyl groups are generated in the molecule by tautomerization. It is considered that the interaction of the substrate interface occurs due to the hydroxyl group, so that the polar compound has anisotropy and is easily adsorbed on the substrate interface side. In addition, since it has a polymerizable group, the compound (1) that reacts in the direction of polarized light by polymerization is fixed without losing its directivity. This property can be used to prepare thin films capable of aligning liquid crystal molecules. In order to prepare the film, the ultraviolet rays irradiated are suitably linearly polarized light. First, the compound (1) as a polar compound is added to the liquid crystal composition in a range of 0.1% by weight to 10% by weight, and the composition is heated to dissolve the polar compound. This composition was injected into an element having no alignment film. Then, while heating the element, linearly polarized light is irradiated, thereby polarizing Frisian rearrangement and polymerization of the polar compound. The polar compounds rearranged by the photo-Fris are arranged in a certain direction, and the thin film formed after polymerization has a function as a liquid crystal alignment film.

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

The optically active compound brings about the effect of preventing reverse twisting by inducing a helical 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. Preferred examples of the optically active compound include the following compound (Op-1) to compound (Op-18). 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.

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

In order to maintain a large voltage retention rate, a light stabilizer such as an amine having steric hindrance is preferred. Preferred examples of light stabilizers include the following compounds (AO-5) and compounds (AO-6); TINUVIN 144, TINUVIN 765 and TINUVIN 770DF ( Trade name: BASF (BASF) company). In order to maintain a large voltage retention rate, a heat stabilizer is also effective. A preferred example is IRGAFOS 168 (trade name: BASF). To prevent foaming, defoamers are effective. 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 groups. In compound (AO-2) and compound (AO-5), R ⁴² is an alkyl group having 1 to 20 carbon atoms. In compound (AO-5), R ⁴³ is hydrogen, methyl or O ^· (oxygen radical), ring G is 1,4-cyclohexyl or 1,4-phenylene, z is 1, 2 or 3 .

4. Liquid crystal display element The liquid crystal composition can be used in a liquid crystal display device having operating modes such as PC, TN, STN, OCB, and PSA and driven in an active matrix manner. The composition can also be 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 can also be used for nematic curvilinear aligned phase (NCAP) devices produced by microencapsulating nematic liquid crystals, and polymer dispersed liquid crystal display devices produced by forming three-dimensional network polymers in liquid crystals (Polymer dispersed liquid crystal display, PDLCD), and polymer network liquid crystal display (PNLCD). When the addition amount of the polymerizable compound is about 10% by weight or less based on the weight of the liquid crystal composition, a PSA mode liquid crystal display element can be produced. Based on the weight of the liquid crystal composition, the preferred ratio of the polymerizable compound is in the range of about 0.1% by weight to about 2% by weight. Based on the weight of the liquid crystal composition, a particularly preferred ratio is in the range of about 0.2% by weight to about 1.0% by weight. PSA mode components can be driven by active matrix, passive matrix and other driving methods. This type of device can also be applied to any type of reflection type, transmission type, and semi-transmission type. By increasing the amount of the polymerizable compound added, a polymer dispersed mode element can also be produced.

In a polymer-stable alignment type element, the polymer contained in the composition aligns liquid crystal molecules. The compound (1), which is a polar compound, assists in aligning liquid crystal molecules. That is, the compound (1) 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 of the substrates has an electrode layer. The liquid crystal compound is mixed to prepare a liquid crystal composition. A polymerizable compound and a compound (1) as a polar compound are added to this composition. Add additives as needed. The composition is injected into the device. The element is irradiated with light. 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.

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

In this procedure, the compound (1) as a polar compound interacts with the surface of the substrate, so it tends to exist on the substrate. This compound (1) aligns the liquid crystal molecules by the irradiation of polarized ultraviolet rays, and at the same time, the polymerizable compound is polymerized by the ultraviolet rays, thereby generating a polymer that maintains the alignment. Due to the effect of the polymer, the alignment of liquid crystal molecules is more stabilized, so the response time of the device is shortened. The afterimage of the image is a malfunction of the liquid crystal molecules, so the afterimage is also improved by the effect of the polymer. In particular, the compound (1) according to the embodiment of the present invention is a polymerizable polar compound, so the liquid crystal molecules are aligned and copolymerized with other polymerizable compounds. By this, the polar compound does not leak into the liquid crystal composition, so a liquid crystal display element with a large voltage retention rate can be obtained. [Example]

The present invention will be further described in detail by examples (including synthesis examples and use examples of devices). The invention is not limited by these embodiments. The present invention includes a mixture of the composition of Use Example 1 and the composition of Use Example 2. The present invention also includes a mixture prepared by mixing at least two of the compositions of the use examples. 1. Examples of compound (1)

Compound (1) was synthesized by the procedure shown in Example 1 and the like. As long as there is no special description, the reaction is carried out under a nitrogen atmosphere. 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, quin refers to quintet, sex refers to hexatet, and m refers to multiplex Peak, br refers to broad peak.

Gas chromatography analysis: For 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.

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 diameter 5 μm) manufactured by Vermec (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 recording meter, C-R7A plus manufactured by Shimadzu Corporation was used.

UV-Vis spectroscopic analysis: For the measurement, PharmaSpec UV-1700 manufactured by Shimadzu Corporation was 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. 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 (Mettler's FP-52 hot stage) equipped with a melting point measuring device of a polarizing microscope. While heating the sample at a rate of 3°C/min, the phase state and its change were observed with a polarizing microscope to determine the type of phase.

(2) Transition temperature (℃) For the measurement, the scanning calorimeter Diamond DSC system manufactured by Perkin Elmer or the high-sensitivity differential scanning calorimeter X-DSC7000 manufactured by SSI Nanotechnology is 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, the symbol of T _NI is used. When the sample is a mixture of the compound (1) and the compounds such as component B, component C, and component D, the symbol of NI is used.

(4) lower limit temperature (T _C; ℃) nematic phase A sample having a nematic phase at 0 ℃, -10 ℃, -20 ℃ , a freezer of -30 ℃ and -40 ℃ for 10 days To 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 Keiki 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 by 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 by the following formula. (Specific resistance) = {(voltage) × (capacitance of the container)}/{(DC current) × (dielectric constant of vacuum)}.

For samples with a positive dielectric anisotropy and samples with a negative dielectric anisotropy, the measurement method of the characteristics may be different. The method of measuring the dielectric anisotropy is described in the items (8a) to (12a). When the dielectric 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 anisotropy: the measurement is based on the method described in "Molecular Crystals and Liquid Crystals" by M. Imai et al. (Vol. 259, 37 (1995)) . 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 page 40 of the paper by 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 element whose rotational viscosity was measured.

(8b) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s) Negative dielectric anisotropy: The measurement is based on the method described in "Molecular Crystals and Liquid Crystals" by M. Imai et al. (Vol. 259, 37 (1995)). 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 page 40 of the paper by M. Imai et al., the value of rotational viscosity was obtained. The dielectric anisotropy necessary for this calculation is a value measured using the terms of dielectric anisotropy described below.

(9a) Dielectric anisotropy (Δε; measured at 25°C) Positive dielectric anisotropy: A sample was placed in a TN device with a gap (cell gap) of 9 μm between two glass substrates and a twist angle of 80 degrees. A sine wave (10 V, 1 kHz) was applied to the 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 by the formula Δε=ε∥-ε⊥.

(9b) Dielectric anisotropy (Δε; measured at 25°C) Negative dielectric anisotropy: The value of dielectric anisotropy is calculated by the formula Δε=ε∥-ε⊥. The dielectric 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 obtained alignment film was subjected to rubbing treatment. 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 anisotropy: An HPR 4284A LCR meter manufactured by Yokogawa-Hewlett Packard Co., Ltd. was used for the measurement. 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 capacitance (C) and the applied voltage (V), using the formula (2.99) The values of K ₁₁ and K ₃₃ are obtained. Then, 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 anisotropy: The EC-1 type elastic constant measured by TOYO Technica Co., Ltd. was used for the measurement Device. 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 Industrial Daily) to fit the values of the electrostatic capacitance (C) and the applied voltage (V), and obtain the elastic constant from the formula (2.100) Value.

(11a) Threshold voltage (Vth; measured at 25°C; V) Positive dielectric anisotropy: LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is 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 a voltage when the transmittance becomes 90%.

(11b) Threshold voltage (Vth; measured at 25°C; V) Negative dielectric anisotropy: LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is 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 a voltage when the transmittance becomes 10%.

(12a) Response time (τ; measured at 25°C; ms) Positive dielectric anisotropy: LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is 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: LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is 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, while applying a voltage of 5.6 V, 23.5 mW/cm ² of ultraviolet light was irradiated 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 the time required for the transmission rate to change from 90% to 10% (fall time; fall time; milliseconds).

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

[Synthesis Example 1] Synthesis of compound (No. 81)

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

Step 2 Put compound (T-3) (1.55 g), compound (T-4) (1.69 g), DMAP (0.12 g) and dichloromethane (100 ml) into the reactor and cool to 0°C. DCC (1.14 g) was added thereto, returned to room temperature and stirred for 12 hours. After oven-dissolving the insoluble matter, the reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, the residue was purified by silica gel chromatography (volume ratio, ethyl acetate:toluene=1:4), and reprecipitated with heptane to obtain compound (No. 81 ) (2.34 g; 80%). Furthermore, the compound (T-4) is a known substance, and those with ordinary knowledge in the technical field can easily obtain a synthesis method.

The NMR analysis value of the obtained compound (No. 81) is as follows. ¹ H-NMR: chemical shift δ (ppm; CDCl ₃ ): 8.61 (d, 1H), 8.55 (d, 2H), 8.21 (d, 2H), 7.70 (d, 1H), 7.68 (s, 1H), 7.67 (s, 1H), 7.48 (dd, 1H), 7.31 (dd, 1H), 7.27 (d, 1H), 6.98 (d, 2H), 6.43 (dd, 1H), 6.42 (dd, 1H), 6.18 (dd, 1H), 6.13 (dd, 1H), 5.85 (dd, 1H), 5.84 (dd, 1H), 4.60 (t, 2H), 4.37 (t, 2H), 4.18 (t, 2H), 4.04 ( t, 2H), 1.84 (quint, 2H), 1.72 (quint, 2H), 1.55 (quint, 2H), 1.46 (quint, 2H).

The physical properties of Compound (No. 81) are as follows. Transition temperature (℃): C 82.5 I Polymerization temperature (℃): 136.49

第1步驟 將4-碘苯酚（30.0 g）、三甲基矽烷基乙炔（16.1 g）、碘化銅（1.3 g）、Pd(PPh₃ )₂ Cl₂ （1.91 g）、四氫呋喃（Tetrahydrofuran，THF）（200 ml）及三乙基胺（200 ml）採集至容器中，並於氮氣環境下攪拌一晚。於其中添加THF（200 ml）、MeOH（200 ml）及KF（15.8 g），並於空氣環境下攪拌一晚。將反應混合物注入至水中，利用甲苯進行萃取，並利用水進行清洗，然後利用無水硫酸鎂進行乾燥，並進行減壓濃縮而獲得淡茶色固體。將該固體製成溶液，利用矽膠管柱層析法（容積比，乙酸乙酯：甲苯=1：4）進行純化而獲得化合物（T-5）（12.7 g；80%）。[Synthesis Example 2] Synthesis of compound (No. 165)

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

In the next two steps, the compound (T-5) can be used instead of the compound (T-1) and the compound (T-6 can be used instead of the compound (T-2) in the first and second steps of Synthesis Example 1. ), and perform the same operation to synthesize. In addition, the compound (T-6) is a known substance, and those with ordinary knowledge in the technical field can easily obtain a synthesis method.

The NMR analysis value of the obtained compound (No. 165) is as follows. ¹ H-NMR: chemical shift δ (ppm; CDCl ₃ ): 8.13 (d, 2H), 7.57 (d, 2H), 7.46 (d, 2H), 7.19 (d, 2H), 6.97 (d, 2H), 6.85 (d, 2H), 6.42 (dd, 1H), 6.41 (dd, 1H), 6.13 (dd, 1H), 6.11 (dd, 1H), 5.84 (dd, 1H), 5.82 (dd, 1H), 4.24 (t, 2H), 4.18 (t, 2H), 4.05 (t, 2H), 4.01 (t, 2H), 1.91 (t, 2H), 1.90 (t, 2H), 1.84 (quint, 2H), 1.73 ( quint, 2H), 1.57 (quint, 2H), 1.48 (quint, 2H).

The physical properties of Compound (No. 165) are as follows. Transition temperature (℃): C 80.0 I Polymerization temperature (℃): 230.8

[Synthesis Example 3] Synthesis of compound (No. 148)

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

Step 2 In the second step of Synthesis Example 1, instead of the compound (T-3), the compound (T-7) was used and the same operation was performed, thereby synthesizing the compound (No. 148).

The NMR analysis value of the obtained compound (No. 148) is as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 8.12 (d, 2H), 7.58 (d, 2H), 7.55 (d, 2H), 7.20 (d, 2H), 7.14 (d, 2H), 6.96 (d, 2H), 6.62 (dd, 1H), 6.41 (dd, 1H), 6.31 (dd, 1H), 6.13 (dd, 1H), 6.04 (dd, 1H), 5.82 (dd, 1H), 4.18 (t, 2H), 4.05 (t, 2H), 1.84 (quint, 2H), 1.73 (quint, 2H), 1.53 (quint, 2H), 1.48 (quint, 2H).

The physical properties of compound (No. 148) are as follows. Transition temperature (℃): C 113.8 I Polymerization temperature (℃): 259.1

第1步驟 將4-碘-2-甲基苯酚（6 g）、1,4-二乙炔基苯（1.53 g）、碘化銅（0.12 g）、Pd(PPh₃ )₂ Cl₂ （0.90 g）、THF（50 ml）及三乙基胺（50 ml）採集至容器中，並於氮氣環境下攪拌一晚。將反應混合物注入至水中，利用甲苯進行萃取，並利用水進行清洗，然後利用無水硫酸鎂進行乾燥，並進行減壓濃縮而獲得淡茶色固體。將該固體製成溶液，利用矽膠管柱層析法（容積比，乙酸乙酯：甲苯=1：3）進行純化，將所獲得者溶解於MeOH（100 ml）、THF（100 ml）的混合溶液中。於其中添加KF（7.7 g），並於室溫下攪拌一晚。對所獲得者進行濃縮，利用矽膠管柱層析法（容積比，乙酸乙酯：甲苯=1：4）進行純化而獲得化合物（T-8）（2.95 g；68%）。[Synthesis Example 4] Synthesis of compound (No. 221)

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

The next two steps can be synthesized by using Compound (T-8) instead of Compound (T-1) in Steps 1 and 2 of Synthesis Example 1, and performing the same operation.

The NMR analysis value of the obtained compound (No. 221) is as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 8.15 (d, 2H), 7.48 (s, 4H), 7.45 (s, 1H), 7.42 (d, 1H), 7.35 (d, 1H), 7.34 (s, 1H), 7.13 (d, 1H), 6.98 (d, 2H), 6.78 (d, 1H), 6.45 (dd, 1H), 6.40 (dd, 1H), 6.17 (dd, 1H), 6.13 (dd, 1H), 5.87 (dd, 1H), 5.82 (dd, 1H), 4.55 (t, 2H), 4.24 (t, 2H), 4.18 (t, 2H), 4.05 (t, 2H), 1.85 ( quint, 2H), 1.73 (quint, 2H), 1.54 (quint, 2H), 1.47 (quint, 2H).

The physical properties of Compound (No. 221) are as follows. Transition temperature (℃): C 77.22 N 95.28 I Polymerization temperature (℃): 198.8

合成例1中，代替化合物（T-1）而使用化合物（T-10），代替化合物（T-4）而使用化合物（T-9），並進行相同的操作，藉此合成化合物（No.16）。再者，化合物（T-9）及化合物（T-10）為已知物質，若為本技術領域具通常知識者，則可容易獲得合成法。[Synthesis Example 5] Synthesis of compound (No. 16)

In Synthesis Example 1, the compound (T-10) was used instead of the compound (T-1), and the compound (T-9) was used instead of the compound (T-4), and the same operation was performed, thereby synthesizing the compound (No. 16). Furthermore, the compound (T-9) and the compound (T-10) are known substances, and those with ordinary knowledge in the technical field can easily obtain a synthesis method.

The NMR analysis value of the obtained compound (No. 16) is as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 8.73 (s, 1H), 8.18 (dd, 1H), 7.90 (d, 1H), 7.82 (d, 1H), 7.53 (d, 2H), 7.46 (s, 1H), 7.43 (dd, 1H), 7.23 (dd, 1H), 7.22 (d, 1H), 7.19 (s, 1H), 7.00 (d, 2H), 6.46 (dd, 1H), 6.41 (dd, 1H), 6.19 (dd, 1H), 6.13 (dd, 1H), 5.87 (dd, 1H), 5.82 (dd, 1H), 4.55 (t, 2H), 4.27 (t, 2H), 4.19 ( t, 2H), 4.13 (t, 2H), 1.90 (quint, 2H), 1.75 (quint, 2H), 1.58 (quint, 2H), 1.50 (quint, 2H).

The physical properties of Compound (No. 16) are as follows. Transition temperature (℃): C 96.8 N 154.3 I Polymerization temperature (℃): 176.8

[Synthesis Example 6] Synthesis of compound (No. 158)

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

Step 2 The compound (T-12) (35.0 g), trimethylsilylacetylene (15.6 g), copper iodide (2.5 g), Pd(PPh ₃ ) ₂ Cl ₂ (4.67 g) and triethyl Amine (200 ml) was collected into the container and stirred overnight. The reaction mixture was poured into water, extracted with toluene, washed with water, then dried with anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a light brown solid. This solid was made into a solution and purified by silica gel column chromatography (volume ratio, ethyl acetate:toluene=1:4), and the obtained was dissolved in a mixture of methanol (100 ml) and THF (100 ml) In solution. KF (7.7 g) was added thereto and stirred at room temperature overnight. The obtained person was concentrated and purified by silica gel column chromatography (volume ratio, ethyl acetate:toluene=1:4) to obtain compound (T-13) (17.9 g; 83%). Step 3 Put compound (T-13) (32.5 g), acrylic acid (20.0 g), DMAP (2.7 g) and dichloromethane (500 ml) into the reactor, and cool to 0°C. DCC (48.1 g) was added thereto, returned to room temperature and stirred for 12 hours. After oven-classifying the insoluble matter, the reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene) to obtain compound (T-14) (45 g; 93%). Step 4: Compound (T-14) (24.0 g), trimethylsilylacetylene (54.5 g), copper iodide (2.11 g), Pd(PPh ₃ ) ₂ Cl ₂ (3.89 g), THF (200 ml) and triethylamine (200 ml) were collected into a container and stirred overnight under oxygen. The reaction mixture was poured into water, extracted with toluene, washed with water, then dried with anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a light brown solid. This solid was made into a solution and purified by silica gel column chromatography (volume ratio, ethyl acetate:toluene=1:4), and the obtained was dissolved in a mixture of methanol (100 ml) and THF (100 ml) In solution. KF (7.7 g) was added thereto and stirred at room temperature overnight. The obtained person was concentrated and purified by silica gel column chromatography (volume ratio, ethyl acetate:toluene=1:4) to obtain compound (T-15) (12.6 g; 66%). Step 5 Put 4-iodo-2-methylphenol (50.0 g), compound (T-16) (65.5 g), DMAP (5.2 g) and dichloromethane (1000 ml) into the reactor, and Cool to 0°C. DCC (46.2 g) was added thereto, returned to room temperature and stirred for 12 hours. After oven-classifying the insoluble matter, the reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, ethyl acetate:toluene=1:9) to obtain compound (T-17) (86 g; 79%). Step 6: Compound (T-17) (4.9 g), compound (T-15) (2.2 g), copper iodide (0.05 g), Pd(PPh ₃ ) ₂ Cl ₂ (0.18 g), THF (200 ml) and triethylamine (200 ml) were collected into a container and stirred overnight. The reaction mixture was poured into water, extracted with toluene, washed with water, then dried with anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a light brown solid. This solid was made into a solution and purified by silica gel column chromatography (volume ratio, ethyl acetate:toluene=1:9) to obtain compound (No. 158) (21 g; 64.5%).

The NMR analysis value of the obtained compound (No. 158) is as follows. ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 8.13 (d, 2H), 7.49 (d, 2H), 7.44 (s, 1H), 7.40 (d, 1H), 7.11 (d, 1H), 6.98 (d, 2H), 6.88 (d, 2H), 6.43 (dd, 2H), 6.15 (dd, 2H), 5.85 (dd, 2H), 4.52 (t, 2H), 4.23 (t, 2H), 4.18 (t, 2H), 4.05 (t, 2H), 2.21 (s, 3H), 1.84 (quint, 2H), 1.73 (quint, 2H), 1.55 (quint, 2H), 1.47 (quint, 2H).

The physical properties of Compound (No. 158) are as follows. Transition temperature (℃): C 77.9 N 82.5 I Polymerization temperature (℃): 231.86

The following compound (No. 1) to compound (No. 224) can be synthesized according to the synthesis method described in Synthesis Examples.

2. Use Examples of Elements The compounds in the use examples are indicated by symbols based on the definition in Table 2 below. In Table 2, 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.

1. Raw materials Into a device without an alignment film, a composition added with a polar compound is injected. After irradiating linearly polarized light, the alignment of the liquid crystal molecules in the device was confirmed. First, the raw materials will be described. The raw material is suitably selected from the group consisting of a composition (M1) to a composition (M41), and a polar compound such as a compound (No. 1) to a compound (No. 224). The composition is as follows.

[Composition (M1)] 3-HB(2F,3F)-O2 (9-1) 10% 5-HB(2F,3F)-O2 (9-1) 7% 2-BB(2F,3F)-O2 (9-3) 7% 3-BB(2F,3F)-O2 (9-3) 7% 3-B(2F,3F)B(2F,3F)-O2 (9-7) 3% 2-HHB(2F,3F)-O2 (10-1) 5% 3-HHB(2F,3F)-O2 (10-1) 10% 2-HBB(2F,3F)-O2 (10-7) 8% 3-HBB(2F,3F)-O2 (10-7) 10% 2-HH-3 (2-1) 14% 3-HB-O1 (2-5) 5% 3-HHB-1 (3-1) 3% 3-HHB-O1 (3-1) 3% 3-HHB-3 (3-1) 4% 2-BB(F)B-3 (3-6) 4% NI=73.2℃; Tc<-20℃; Δn=0.113; Δε=-4.0; Vth=2.18 V; η=22.6 mPa·s.

[Composition (M2)] 3-HB(2F,3F)-O4 (9-1) 6% 3-H2B(2F,3F)-O2 (9-4) 8% 3-H1OB(2F,3F)-O2 (9-5) 4% 3-BB(2F,3F)-O2 (9-3) 7% 2-HHB(2F,3F)-O2 (10-1) 7% 3-HHB(2F,3F)-O2 (10-1) 7% 3-HH2B(2F,3F)-O2 (10-4) 7% 5-HH2B(2F,3F)-O2 (10-4) 4% 2-HBB(2F,3F)-O2 (10-7) 5% 3-HBB(2F,3F)-O2 (10-7) 5% 4-HBB(2F,3F)-O2 (10-7) 6% 2-HH-3 (2-1) 12% 1-BB-5 (2-8) 12% 3-HHB-1 (3-1) 4% 3-HHB-O1 (3-1) 3% 3-HBB-2 (3-4) 3% NI=82.8℃; Tc<-30℃; Δn=0.118; Δε=-4.4; Vth=2.13 V; η=22.5 mPa·s.

[Composition (M3)] 3-HB(2F,3F)-O2 (9-1) 7% 5-HB(2F,3F)-O2 (9-1) 7% 3-BB(2F,3F)-O2 (9-3) 8% 3-HHB(2F,3F)-O2 (10-1) 5% 5-HHB(2F,3F)-O2 (10-1) 4% 3-HH1OB(2F,3F)-O2 (10-5) 4% 2-BB(2F,3F)B-3 (11-1) 5% 2-HBB(2F,3F)-O2 (10-7) 3% 3-HBB(2F,3F)-O2 (10-7) 8% 4-HBB(2F,3F)-O2 (10-7) 5% 5-HBB(2F,3F)-O2 (10-7) 8% 3-HH-V (2-1) 27% 3-HH-V1 (2-1) 6% V-HHB-1 (3-1) 3% NI=78.1℃; Tc<-30℃; Δn=0.107; Δε=-3.2; Vth=2.02 V; η=15.9 mPa·s.

[Composition (M4)] 3-HB(2F,3F)-O2 (9-1) 10% 5-HB(2F,3F)-O2 (9-1) 10% 3-H2B(2F,3F)-O2 (9-4) 8% 5-H2B(2F,3F)-O2 (9-4) 8% 2-HBB(2F,3F)-O2 (10-7) 6% 3-HBB(2F,3F)-O2 (10-7) 8% 4-HBB(2F,3F)-O2 (10-7) 7% 5-HBB(2F,3F)-O2 (10-7) 7% 3-HDhB(2F,3F)-O2 (10-3) 5% 3-HH-4 (2-1) 14% V-HHB-1 (3-1) 10% 3-HBB-2 (3-4) 7% NI=88.5℃; Tc<-30℃; Δn=0.108; Δε=-3.8; Vth=2.25 V; η=24.6 mPa·s; VHR-1=99.1%; VHR-2=98.2%; VHR-3= 97.8%.

[Composition (M5)] 3-HB(2F,3F)-O2 (9-1) 7% 3-HB(2F,3F)-O4 (9-1) 8% 3-H2B(2F,3F)-O2 (9-4) 8% 3-BB(2F,3F)-O2 (9-3) 10% 2-HHB(2F,3F)-O2 (10-1) 4% 3-HHB(2F,3F)-O2 (10-1) 7% 3-HHB(2F,3F)-1 (10-1) 6% 2-HBB(2F,3F)-O2 (10-7) 6% 3-HBB(2F,3F)-O2 (10-7) 6% 4-HBB(2F,3F)-O2 (10-7) 5% 5-HBB(2F,3F)-O2 (10-7) 4% 3-HEB(2F,3F)B(2F,3F)-O2 (16-1) 3% 3-H1OCro(7F,8F)-5 (13-2) 3% 3-HDhB(2F,3F)-O2 (10-3) 5% 3-HH-O1 (2-1) 5% 1-BB-5 (2-8) 4% V-HHB-1 (3-1) 4% 5-HB(F)BH-3 (4-2) 5% NI=81.1℃; Tc<-30℃; Δn=0.119; Δε=-4.5; Vth=1.69 V; η=31.4 mPa·s.

[Composition (M6)] 3-HB(2F,3F)-O4 (9-1) 15% 3-HBB(2F,3F)-O2 (10-7) 8% 4-HBB(2F,3F)-O2 (10-7) 5% 5-HBB(2F,3F)-O2 (10-7) 7% 3-dhBB(2F,3F)-O2 (10-9) 5% 3-chB(2F,3F)-O2 (16-2) 7% 2-HchB(2F,3F)-O2 (16-3) 8% 5-HH-V (2-1) 18% 7-HB-1 (2-5) 5% V-HHB-1 (3-1) 7% V2-HHB-1 (3-1) 7% 3-HBB(F)B-3 (4-5) 8% NI=98.8℃; Tc<-30℃; Δn=0.111; Δε=-3.2; Vth=2.47 V; η=23.9 mPa·s.

[Composition (M7)] 3-H2B(2F,3F)-O2 (9-4) 18% 5-H2B(2F,3F)-O2 (9-4) 17% 3-HHB(2F,3Cl)-O2 (10-12) 5% 3-HBB(2F,3Cl)-O2 (10-13) 8% 5-HBB(2F,3Cl)-O2 (10-13) 7% 3-HDhB(2F,3F)-O2 (10-3) 5% 3-HH-V (2-1) 11% 3-HH-VFF (2-1) 7% F3-HH-V (2-1) 10% 3-HHEH-3 (3-13) 4% 3-HB(F)HH-2 (4-7) 4% 3-HHEBH-3 (4-6) 4% NI=77.5℃; Tc<-30℃; Δn=0.084; Δε=-2.6; Vth=2.43 V; η=22.8 mPa·s.

[Composition (M8)] 3-HB(2F,3F)-O2 (9-1) 8% 3-H2B(2F,3F)-O2 (9-4) 10% 3-BB(2F,3F)-O2 (9-3) 10% 2O-BB(2F,3F)-O2 (9-3) 3% 2-HHB(2F,3F)-O2 (10-1) 4% 3-HHB(2F,3F)-O2 (10-1) 7% 2-HHB(2F,3F)-1 (10-1) 5% 2-BB(2F,3F)B-3 (11-1) 6% 2-BB(2F,3F)B-4 (11-1) 6% 2-HBB(2F,3F)-O2 (10-7) 4% 3-HBB(2F,3F)-O2 (10-7) 7% 3-HH1OCro(7F,8F)-5 (13-6) 4% 3-HDhB(2F,3F)-O2 (10-3) 6% 3-dhBB(2F,3F)-O2 (10-9) 4% 3-HH-V (2-1) 11% 1-BB-5 (2-8) 5% NI=70.6℃; Tc<-20℃; Δn=0.129; Δε=-4.3; Vth=1.69 V; η=27.0 mPa·s.

[Composition (M9)] 3-HB(2F,3F)-O4 (9-1) 14% 3-H1OB(2F,3F)-O2 (9-5) 3% 3-BB(2F,3F)-O2 (9-3) 10% 2-HHB(2F,3F)-O2 (10-1) 7% 3-HHB(2F,3F)-O2 (10-1) 7% 3-HH1OB(2F,3F)-O2 (10-5) 6% 2-HBB(2F,3F)-O2 (10-7) 4% 3-HBB(2F,3F)-O2 (10-7) 6% 4-HBB(2F,3F)-O2 (10-7) 4% 3-HH-V (2-1) 14% 1-BB-3 (2-8) 3% 3-HHB-1 (3-1) 4% 3-HHB-O1 (3-1) 4% V-HBB-2 (3-4) 4% 1-BB(F)B-2V (3-6) 6% 5-HBBH-1O1 (4-1) 4% NI=93.0℃; Tc<-30℃; Δn=0.123; Δε=-4.0; Vth=2.27 V; η=29.6 mPa·s.

[Composition (M10)] 3-HB(2F,3F)-O4 (9-1) 6% 3-H2B(2F,3F)-O2 (9-4) 8% 3-H1OB(2F,3F)-O2 (9-5) 5% 3-BB(2F,3F)-O2 (9-3) 10% 2-HHB(2F,3F)-O2 (10-1) 7% 3-HHB(2F,3F)-O2 (10-1) 7% 5-HHB(2F,3F)-O2 (10-1) 7% 2-HBB(2F,3F)-O2 (10-7) 4% 3-HBB(2F,3F)-O2 (10-7) 7% 5-HBB(2F,3F)-O2 (10-7) 6% 3-HH-V (2-1) 11% 1-BB-3 (2-8) 6% 3-HHB-1 (3-1) 4% 3-HHB-O1 (3-1) 4% 3-HBB-2 (3-4) 4% 3-B(F)BB-2 (3-8) 4% NI=87.6℃; Tc<-30℃; Δn=0.126; Δε=-4.5; Vth=2.21 V; η=25.3 mPa·s.

[Composition (M11)] 3-HB(2F,3F)-O4 (9-1) 6% 3-H2B(2F,3F)-O2 (9-4) 8% 3-H1OB(2F,3F)-O2 (9-5) 4% 3-BB(2F,3F)-O2 (9-3) 7% 2-HHB(2F,3F)-O2 (10-1) 6% 3-HHB(2F,3F)-O2 (10-1) 10% 5-HHB(2F,3F)-O2 (10-1) 8% 2-HBB(2F,3F)-O2 (10-7) 5% 3-HBB(2F,3F)-O2 (10-7) 7% 5-HBB(2F,3F)-O2 (10-7) 5% 2-HH-3 (2-1) 12% 1-BB-3 (2-8) 6% 3-HHB-1 (3-1) 3% 3-HHB-O1 (3-1) 4% 3-HBB-2 (3-4) 6% 3-B(F)BB-2 (3-8) 3% NI=93.0℃; Tc<-20℃; Δn=0.124; Δε=-4.5; Vth=2.22 V; η=25.0 mPa·s.

[Composition (M12)] 3-HB(2F,3F)-O2 (9-1) 7% 5-HB(2F,3F)-O2 (9-1) 7% 3-BB(2F,3F)-O2 (9-3) 8% 3-HHB(2F,3F)-O2 (10-1) 4% 5-HHB(2F,3F)-O2 (10-1) 5% 3-HH1OB(2F,3F)-O2 (10-5) 5% 2-BB(2F,3F)B-3 (11-1) 4% 2-HBB(2F,3F)-O2 (10-7) 3% 3-HBB(2F,3F)-O2 (10-7) 8% 4-HBB(2F,3F)-O2 (10-7) 5% 5-HBB(2F,3F)-O2 (10-7) 8% 3-HH-V (2-1) 33% V-HHB-1 (3-1) 3% NI=76.4℃; Tc<-30℃; Δn=0.104; Δε=-3.2; Vth=2.06 V; η=15.6 mPa·s.

[Composition (M13)] 2-H1OB(2F,3F)-O2 (9-5) 6% 3-H1OB(2F,3F)-O2 (9-5) 4% 3-BB(2F,3F)-O2 (9-3) 3% 2-HH1OB(2F,3F)-O2 (10-5) 14% 2-HBB(2F,3F)-O2 (10-7) 7% 3-HBB(2F,3F)-O2 (10-7) 11% 5-HBB(2F,3F)-O2 (10-7) 9% 2-HH-3 (2-1) 5% 3-HH-VFF (2-1) 30% 1-BB-3 (2-8) 5% 3-HHB-1 (3-1) 3% 3-HBB-2 (3-4) 3% NI=78.3℃; Tc<-20℃; Δn=0.103; Δε=-3.2; Vth=2.17 V; η=17.7 mPa·s.

[Composition (M14)] 3-HB(2F,3F)-O2 (9-1) 5% 5-HB(2F,3F)-O2 (9-1) 7% 3-BB(2F,3F)-O2 (9-3) 8% 3-HHB(2F,3F)-O2 (10-1) 5% 5-HHB(2F,3F)-O2 (10-1) 4% 3-HH1OB(2F,3F)-O2 (10-5) 5% 2-BB(2F,3F)B-3 (11-1) 4% 2-HBB(2F,3F)-O2 (10-7) 3% 3-HBB(2F,3F)-O2 (10-7) 9% 4-HBB(2F,3F)-O2 (10-7) 4% 5-HBB(2F,3F)-O2 (10-7) 8% 3-HH-V (2-1) 27% 3-HH-V1 (2-1) 6% V-HHB-1 (3-1) 5% NI=81.2℃; Tc<-20℃; Δn=0.107; Δε=-3.2; Vth=2.11 V; η=15.5 mPa·s.

[Composition (M15)] 3-H2B(2F,3F)-O2 (9-4) 7% 3-HHB(2F,3F)-O2 (10-1) 8% 3-HH1OB(2F,3F)-O2 (10-5) 5% 2-BB(2F,3F)B-3 (11-1) 7% 2-BB(2F,3F)B-4 (11-1) 7% 3-HDhB(2F,3F)-O2 (10-3) 3% 5-HDhB(2F,3F)-O2 (10-3) 4% 2-HchB(2F,3F)-O2 (16-3) 8% 4-HH-V (2-1) 15% 3-HH-V1 (2-1) 6% 1-HH-2V1 (2-1) 6% 3-HH-2V1 (2-1) 4% V2-BB-1 (2-8) 5% 1V2-BB-1 (2-8) 5% 3-HHB-1 (3-1) 6% 3-HB(F)BH-3 (4-2) 4% NI=88.7℃; Tc<-30℃; Δn=0.115; Δε=-1.9; Vth=2.82 V; η=17.3 mPa·s.

[Composition (M16)] V2-H2B(2F,3F)-O2 (9-4) 8% V2-H1OB(2F,3F)-O4 (9-5) 4% 3-BB(2F,3F)-O2 (9-3) 7% 2-HHB(2F,3F)-O2 (10-1) 7% 3-HHB(2F,3F)-O2 (10-1) 7% 3-HH2B(2F,3F)-O2 (10-4) 7% 5-HH2B(2F,3F)-O2 (10-4) 4% V-HH2B(2F,3F)-O2 (10-4) 6% V2-HBB(2F,3F)-O2 (10-7) 5% V-HBB(2F,3F)-O2 (10-7) 5% V-HBB(2F,3F)-O4 (10-7) 6% 2-HH-3 (2-1) 12% 1-BB-5 (2-8) 12% 3-HHB-1 (3-1) 4% 3-HHB-O1 (3-1) 3% 3-HBB-2 (3-4) 3% NI=89.9℃; Tc<-20℃; Δn=0.122; Δε=-4.2; Vth=2.16 V; η=23.4 mPa·s.

[Composition (M17)] 3-HB(2F,3F)-O2 (9-1) 3% V-HB(2F,3F)-O2 (9-1) 3% V2-HB(2F,3F)-O2 (9-1) 5% 5-H2B(2F,3F)-O2 (9-4) 5% V2-BB(2F,3F)-O2 (9-3) 3% 1V2-BB(2F,3F)-O2 (9-3) 3% 3-HHB(2F,3F)-O2 (10-1) 6% V-HHB(2F,3F)-O2 (10-1) 6% V-HHB(2F,3F)-O4 (10-1) 5% V2-HHB(2F,3F)-O2 (10-1) 4% V2-BB(2F,3F)B-1 (11-1) 4% V2-HBB(2F,3F)-O2 (10-7) 5% V-HBB(2F,3F)-O2 (10-7) 4% V-HBB(2F,3F)-O4 (10-7) 5% V-HHB(2F,3Cl)-O2 (10-12) 3% 3-HH-V (2-1) 27% 3-HH-V1 (2-1) 6% V-HHB-1 (3-1) 3% NI=77.1℃; Tc<-20℃; Δn=0.101; Δε=-3.0; Vth=2.04 V; η=13.9 mPa·s.

[Composition (M18)] V-HB(2F,3F)-O2 (9-1) 10% V2-HB(2F,3F)-O2 (9-1) 10% 2-H1OB(2F,3F)-O2 (9-5) 3% 3-H1OB(2F,3F)-O2 (9-5) 3% 2O-BB(2F,3F)-O2 (9-3) 3% V2-BB(2F,3F)-O2 (9-3) 8% V2-HHB(2F,3F)-O2 (10-1) 5% 2-HBB(2F,3F)-O2 (10-7) 3% 3-HBB(2F,3F)-O2 (10-7) 3% V-HBB(2F,3F)-O2 (10-7) 6% V-HBB(2F,3F)-O4 (10-7) 8% V-HHB(2F,3Cl)-O2 (10-12) 7% 3-HH-4 (2-1) 14% V-HHB-1 (3-1) 10% 3-HBB-2 (3-4) 7% NI=75.9℃; Tc<-20℃; Δn=0.114; Δε=-3.9; Vth=2.20 V; η=24.7 mPa·s.

[Composition (M19)] 2-H1OB(2F,3F)-O2 (9-5) 7% 3-H1OB(2F,3F)-O2 (9-5) 11% 3-HH1OB(2F,3F)-O2 (10-5) 8% 2-HBB(2F,3F)-O2 (10-7) 3% 3-HBB(2F,3F)-O2 (10-7) 9% 5-HBB(2F,3F)-O2 (10-7) 7% V-HBB(2F,3F)-O2 (10-7) 8% 3-HDhB(2F,3F)-O2 (10-3) 3.5% 2-HH-3 (2-1) 21% 3-HH-4 (2-1) 5% 3-HB-O2 (2-5) 2.5% 1-BB-3 (2-8) 4% 3-HHB-1 (3-1) 1.5% 3-HBB-2 (3-4) 9.5% NI=80.8℃; Tc<-20℃; Δn=0.108; Δε=-3.8; Vth=2.02 V; η=19.8 mPa·s.

[Composition (M20)] 2-H1OB(2F,3F)-O2 (9-5) 5.5% 2-BB(2F,3F)-O2 (9-3) 11% 2-HH1OB(2F,3F)-O2 (10-5) 13% 3-HH1OB(2F,3F)-O2 (10-5) 15.5% 3-HBB(2F,3F)-O2 (10-7) 9% 2-HH-3 (2-1) 25% 3-HH-4 (2-1) 3% 3-HBB-2 (3-4) 14% 5-B(F)BB-2 (3-8) 4% NI=85.3℃; Tc<-20℃; Δn=0.109; Δε=-3.6; Vth=2.06 V; η=20.9 mPa·s.

[Composition (M21)] V-HB(2F,3F)-O2 (9-1) 7% V-2BB(2F,3F)-O2 (9-3) 10% V-HHB(2F,3F)-O1 (10-1) 7% V-HHB(2F,3F)-O2 (10-1) 9% V-2HHB(2F,3F)-O2 (10-1) 8% 3-HH2B(2F,3F)-O2 (10-4) 9% V-HBB(2F,3F)-O2 (10-7) 7% V-HBB(2F,3F)-O4 (10-7) 7% 2-HH-3 (2-1) 9% 3-HH-4 (2-1) 3% 3-HH-V (2-1) 15% 3-HH-V1 (2-1) 6% 1V2-HH-3 (2-1) 3% NI=87.5℃; Tc<-20℃; Δn=0.100; Δε=-3.4; Vth=2.25 V; η=16.6 mPa·s.

[Composition (M22)] 3-HHXB(F,F)-F (6-100) 6% 3-BB(F,F)XB(F,F)-F (6-97) 13% 3-HHBB(F,F)-F (7-6) 4% 4-HHBB(F,F)-F (7-6) 5% 3-HBBXB(F,F)-F (7-32) 3% 3-BB(F)B(F,F)XB(F)-F (7-46) 2% 4-BB(F)B(F,F)XB(F,F)-F (7-47) 8% 5-BB(F)B(F,F)XB(F,F)-F (7-47) 7% 3-HH-V (2-1) 44% V-HHB-1 (3-1) 6% 2-BB(F)B-3 (3-6) 2% NI=79.8℃; Tc<-30℃; Δn=0.106; Δε=8.5; Vth=1.45 V; η=11.6 mPa·s; γ1=60.0 mPa·s.

[Composition (M23)] 5-HXB(F,F)-F (5-13) 3% 3-HHXB(F,F)-F (6-100) 3% 3-HHXB(F,F)-CF3 (6-100) 3% 3-HGB(F,F)-F (6-103) 3% 3-HB(F)B(F,F)-F (6-50) 5% 3-BB(F,F)XB(F,F)-F (6-97) 6% 3-HHBB(F,F)-F (7-6) 6% 5-BB(F)B(F,F)XB(F)B(F,F)-F (-) 2% 3-BB(2F,3F)XB(F,F)-F (6-114) 4% 3-B(2F,3F)BXB(F,F)-F (6-115) 5% 3-HHB(F,F)XB(F,F)-F (7-29) 4% 3-HB-CL (5-2) 3% 3-HHB-OCF3 (6-1) 3% 3-HH-V (2-1) 22% 3-HH-V1 (2-1) 10% 5-HB-O2 (2-5) 5% 3-HHEH-3 (3-13) 3% 3-HBB-2 (3-4) 7% 5-B(F)BB-3 (3-8) 3% NI=71.2℃; Tc<-20℃; Δn=0.099; Δε=6.1; Vth=1.74 V; η=13.2 mPa·s; γ1=59.3 mPa·s.

[Composition (M24)] 5-HXB(F,F)-F (5-13) 6% 3-HHXB(F,F)-F (6-100) 6% V-HB(F)B(F,F)-F (6-50) 5% 3-HHB(F)B(F,F)-F (7-9) 7% 2-BB(F)B(F,F)XB(F)-F (7-47) 3% 3-BB(F)B(F,F)XB(F)-F (7-47) 3% 4-BB(F)B(F,F)XB(F)-F (7-47) 4% 5-HB-CL (5-2) 5% 2-HH-5 (2-1) 8% 3-HH-V (2-1) 10% 3-HH-V1 (2-1) 7% 4-HH-V (2-1) 10% 4-HH-V1 (2-1) 8% 5-HB-O2 (2-5) 7% 4-HHEH-3 (3-13) 3% 1-BB(F)B-2V (3-6) 3% 1O1-HBBH-3 (4-1) 5% NI=78.5℃; Tc<-20℃; Δn=0.095; Δε=3.4; Vth=1.50 V; η=8.4 mPa·s; γ1=54.2 mPa·s.

[Composition (M25)] 3-HHEB(F,F)-F (6-12) 5% 3-HHXB(F,F)-F (6-100) 7% 5-HBEB(F,F)-F (6-39) 5% 3-BB(F,F)XB(F,F)-F (6-97) 10% 2-HHB(F)B(F,F)-F (7-9) 3% 3-HB(2F,3F)BXB(F,F)-F (7-58) 3% 3-BB(2F,3F)BXB(F,F)-F (7-59) 2% 5-HHB(F,F)XB(F,F)-F (7-29) 6% 2-HH-3 (2-1) 8% 3-HH-V (2-1) 20% 3-HH-V1 (2-1) 7% 4-HH-V (2-1) 6% 5-HB-O2 (2-5) 5% V2-B2BB-1 (3) 3% 3-HHEBH-3 (4-6) 5% 3-HHEBH-5 (4-6) 5% NI=90.3℃; Tc<-20℃; Δn=0.089; Δε=5.5; Vth=1.65 V; η=13.6 mPa·s; γ1=60.1 mPa·s.

[Composition (M26)] 3-BB(F,F)XB(F,F)-F (6-97) 12% 3-HHBB(F,F)-F (7-6) 5% 4-HHBB(F,F)-F (7-6) 4% 3-HBBXB(F,F)-F (7-32) 3% 3-BB(F)B(F,F)XB(F)-F (7-46) 3% 3-BB(F)B(F,F)XB(F,F)-F (7-47) 3% 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) 4% 2-HH-3 (2-1) 6% 3-HH-5 (2-1) 6% 3-HH-V (2-1) 25% 3-HH-VFF (2-1) 6% 5-HB-O2 (2-5) 7% V-HHB-1 (3-1) 6% V-HBB-2 (3-4) 5% NI=78.3℃; Tc<-20℃; Δn=0.107; Δε=7.0; Vth=1.55 V; η=11.6 mPa·s; γ1=55.6 mPa·s.

[Composition (M27)] 3-HHXB(F,F)-F (6-100) 3% 3-BBXB(F,F)-F (6-91) 3% 3-BB(F,F)XB(F,F)-F (6-97) 8% 3-HHBB(F,F)-F (7-6) 5% 4-HHBB(F,F)-F (7-6) 4% 3-BB(F)B(F,F)XB(F,F)-F (7-47) 3% 4-BB(F)B(F,F)XB(F,F)-F (7-47) 6% 5-BB(F)B(F,F)XB(F,F)-F (7-47) 5% 3-HH-V (2-1) 30% 3-HH-V1 (2-1) 5% 3-HHB-O1 (3-1) 2% V-HHB-1 (3-1) 5% 2-BB(F)B-3 (3-6) 6% F3-HH-V (2-1) 15% NI=80.4℃; Tc<-20℃; Δn=0.106; Δε=5.8; Vth=1.40 V; η=11.6 mPa·s; γ1=61.0 mPa·s.

[Composition (M28)] 3-HGB(F,F)-F (6-103) 3% 5-GHB(F,F)-F (6-109) 4% 3-GB(F,F)XB(F,F)-F (6-113) 5% 3-BB(F)B(F,F)-CF3 (6-69) 2% 3-HHBB(F,F)-F (7-6) 4% 3-GBB(F)B(F,F)-F (7-55) 2% 2-dhBB(F,F)XB(F,F)-F (7-50) 4% 3-GB(F)B(F,F)XB(F,F)-F (7-57) 3% 3-HGB(F,F)XB(F,F)-F (-) 5% 7-HB(F,F)-F (5-4) 3% 2-HH-3 (2-1) 14% 2-HH-5 (2-1) 4% 3-HH-V (2-1) 26% 1V2-HH-3 (2-1) 5% 1V2-BB-1 (2-8) 3% 2-BB(F)B-3 (3-6) 3% 3-HB(F)HH-2 (4-7) 4% 5-HBB(F)B-2 (4-5) 6% NI=78.4℃; Tc<-20℃; Δn=0.094; Δε=5.6; Vth=1.45 V; η=11.5 mPa·s; γ1=61.7 mPa·s.

[Composition (M29)] 3-HBB(F,F)-F (6-24) 5% 5-HBB(F,F)-F (6-24) 4% 3-BB(F)B(F,F)-F (6-69) 3% 3-BB(F)B(F,F)XB(F,F)-F (7-47) 3% 4-BB(F)B(F,F)XB(F,F)-F (7-47) 5% 3-BB(F,F)XB(F)B(F,F)-F (7-60) 3% 5-BB(F)B(F,F)XB(F)B(F,F)-F (-) 4% 3-HH2BB(F,F)-F (7-15) 3% 4-HH2BB(F,F)-F (7-15) 3% 2-HH-5 (2-1) 8% 3-HH-V (2-1) 25% 3-HH-V1 (2-1) 7% 4-HH-V1 (2-1) 6% 5-HB-O2 (2-5) 5% 7-HB-1 (2-5) 5% VFF-HHB-O1 (3-1) 8% VFF-HHB-1 (3-1) 3% NI=80.0℃; Tc<-20℃; Δn=0.101; Δε=4.6; Vth=1.71 V; η=11.0 mPa·s; γ1=47.2 mPa·s.

[Composition (M30)] 3-HHB(F,F)-F (6-3) 8% 3-GB(F)B(F)-F (6-116) 2% 3-GB(F)B(F,F)-F (6-117) 3% 3-BB(F,F)XB(F,F)-F (6-97) 8% 3-GB(F)B(F,F)XB(F,F)-F (7-57) 6% 5-GB(F)B(F,F)XB(F,F)-F (7-57) 5% 3-HH-V (2-1) 30% 3-HH-V1 (2-1) 10% 1V2-HH-3 (2-1) 8% 3-HH-VFF (2-1) 8% V2-BB-1 (2-8) 2% 5-HB(F)BH-3 (4-2) 5% 5-HBBH-3 (4-1) 5% NI=78.6℃; Tc<-20℃; Δn=0.088; Δε=5.6; Vth=1.85 V; η=13.9 mPa·s; γ1=66.9 mPa·s.

[Composition (M31)] 3-HHEB(F,F)-F (6-12) 4% 5-HHEB(F,F)-F (6-12) 3% 3-HBEB(F,F)-F (6-39) 3% 5-HBEB(F,F)-F (6-39) 3% 3-BB(F)B(F,F)-F (6-69) 3% 3-GB(F)B(F,F)XB(F,F)-F (7-57) 5% 4-GB(F)B(F,F)XB(F,F)-F (7-57) 5% 5-HB-CL (2-5) 5% 3-HHB-OCF3 (3-1) 4% 3-HHB(F,F)XB(F,F)-F (7-29) 5% 5-HHB(F,F)XB(F,F)-F (7-29) 3% 3-HGB(F,F)XB(F,F)-F (-) 5% 2-HH-5 (2-1) 3% 3-HH-5 (2-1) 5% 3-HH-V (2-1) 24% 4-HH-V (2-1) 5% 1V2-HH-3 (2-1) 5% 3-HHEH-3 (3-13) 5% 5-B(F)BB-2 (3-8) 3% 5-B(F)BB-3 (3-8) 2% NI=82.9℃; Tc<-20℃; Δn=0.093; Δε=6.9; Vth=1.50 V; η=16.3 mPa·s; γ1=65.2 mPa·s.

[Composition (M32)] 3-HHXB(F,F)-F (6-100) 9% 3-HBB(F,F)-F (6-24) 3% 3-BB(F)B(F,F)-F (6-69) 4% 3-BB(F)B(F,F)-CF3 (6-69) 4% 3-BB(F,F)XB(F,F)-F (6-97) 5% 3-GBB(F)B(F,F)-F (7-55) 3% 4-GBB(F)B(F,F)-F (7-55) 4% 3-HH-V (2-1) 25% 3-HH-V1 (2-1) 10% 5-HB-O2 (2-5) 10% 7-HB-1 (2-5) 5% V2-BB-1 (2-8) 3% 3-HHB-1 (3-1) 4% 1V-HBB-2 (3-4) 5% 5-HBB(F)B-2 (4-5) 6% NI=79.6℃; Tc<-20℃; Δn=0.111; Δε=4.7; Vth=1.86 V; η=9.7 mPa·s; γ1=49.9 mPa·s.

[Composition (M33)] 3-BB(F,F)XB(F,F)-F (6-97) 14% 5-BB(F)B(F,F)XB(F,F)-F (7-47) 7% 7-HB(F,F)-F (5-4) 6% 2-HH-5 (2-1) 5% 3-HH-V (2-1) 30% 3-HH-V1 (2-1) 3% 3-HH-VFF (2-1) 10% 3-HHB-1 (3-1) 4% 3-HHB-3 (3-1) 5% 3-HHB-O1 (3-1) 3% 1-BB(F)B-2V (3-6) 3% 3-HHEBH-3 (4-6) 3% 3-HHEBH-4 (4-6) 4% 3-HHEBH-5 (4-6) 3% NI=83.0℃; Tc<-20℃; Δn=0.086; Δε=3.8; Vth=1.94 V; η=7.5 mPa·s; γ1=51.5 mPa·s.

[Composition (M34)] 3-HBB(F,F)-F (6-24) 5% 5-HBB(F,F)-F (6-24) 4% 3-BB(F)B(F,F)-F (6-69) 3% 3-BB(F)B(F,F)XB(F,F)-F (7-47) 3% 4-BB(F)B(F,F)XB(F,F)-F (7-47) 5% 3-BB(F,F)XB(F)B(F,F)-F (7-60) 3% 5-BB(F)B(F,F)XB(F)B(F,F)-F (-) 4% 3-HH2BB(F,F)-F (7-15) 3% 4-HH2BB(F,F)-F (7-15) 3% 2-HH-5 (2-1) 8% 3-HH-V (2-1) 28% 4-HH-V1 (2-1) 7% 5-HB-O2 (2-5) 2% 7-HB-1 (2-5) 5% VFF-HHB-O1 (3-1) 8% VFF-HHB-1 (3-1) 3% 2-BB(2F,3F)B-3 (11-1) 4% 3-HBB(2F,3F)-O2 (10-7) 2% NI=81.9℃; Tc<-20℃; Δn=0.109; Δε=4.8; Vth=1.75 V; η=13.3 mPa·s; γ1=57.4 mPa·s.

[Composition (M35)] 3-HHEB(F,F)-F (6-12) 4% 3-HBEB(F,F)-F (6-39) 3% 5-HBEB(F,F)-F (6-39) 3% 3-BB(F)B(F,F)-F (6-69) 3% 3-HBBXB(F,F)-F (7-32) 6% 4-GBB(F,F)XB(F,F)-F (7-62) 2% 5-GBB(F,F)XB(F,F)-F (7-62) 2% 3-GB(F)B(F,F)XB(F,F)-F (7-57) 5% 4-GB(F)B(F,F)XB(F,F)-F (7-57) 5% 5-HHB(F,F)XB(F,F)-F (7-29) 3% 5-HEB(F,F)-F (5-10) 3% 5-HB-CL (5-2) 2% 3-HHB-OCF3 (6-1) 4% 3-HH-5 (2-1) 4% 3-HH-V (2-1) 21% 3-HH-V1 (2-1) 3% 4-HH-V (2-1) 4% 1V2-HH-3 (2-1) 6% 5-B(F)BB-2 (3-8) 3% 5-B(F)BB-3 (3-8) 2% 3-HB(2F,3F)-O2 (9-1) 3% 3-BB(2F,3F)-O2 (9-3) 2% 3-HHB(2F,3F)-O2 (10-1) 4% F3-HH-V (2-1) 3% NI=78.2℃; Tc<-20℃; Δn=0.101; Δε=6.7; Vth=1.45 V; η=17.8 mPa·s; γ1=67.8 mPa·s.

[Composition (M36)] 3-HHB(F,F)-F (6-3) 10% 3-HHXB(F,F)-F (6-100) 2% 3-GHB(F,F)-F (6-109) 5% 3-BB(F)B(F,F)-F (6-69) 6% 3-BB(F,F)XB(F,F)-F (6-97) 14% 4-BB(F)B(F,F)XB(F,F)-F (7-47) 10% 5-BB(F)B(F,F)XB(F,F)-F (7-47) 6% 2-HH-3 (2-1) 5% 3-HH-4 (2-1) 11% 3-HH-O1 (2-1) 5% 5-HB-O2 (2-5) 8% 3-HHB-1 (3-1) 6% 3-HHB-3 (3-1) 6% 3-HHB-O1 (3-1) 6% NI=77.6℃; Tc<-20℃; Δn=0.109; Δε=10.6; Vth=1.34 V; η=22.6 mPa·s; γ1=92.4 mPa·s.

[Composition (M37)] 3-HBB-F (6-22) 3% 3-BB(F,F)XB(F)-OCF3 (6-96) 3% 3-HHB(F)-F (6-2) 3% 3-HGB(F,F)-F (6-103) 3% 5-GHB(F,F)-F (6-109) 3% 3-HBB(F,F)-F (6-24) 4% 3-BB(F,F)XB(F,F)-F (6-97) 5% 3-HHBB(F,F)-F (7-6) 5% 3-HBBXB(F,F)-F (7-32) 5% 3-BBVFFXB(F,F)-F (6-119) 8% 3-HH-V (2-1) 39% 1-HH-V1 (2-1) 3% 1-HH-2V1 (2-1) 4% 3-HHEH-5 (3-13) 3% 1-BB(F)B-2V (3-6) 3% 3-HHEBH-3 (4-6) 3% 5-HBB(F)B-2 (4-5) 3% NI=85.2℃; Tc<-20℃; Δn=0.102; Δε=4.1; γ1=43.0 mPa·s.

[Composition (M38)] 3-HHBB(F)-F (7-5) 3% 2-HHEB(F,F)-F (6-12) 3% 5-BB(F)B(F,F)-F (6-69) 7% 3-HHB(F)B(F,F)-F (7-9) 3% 3-GB(F)B(F,F)XB(F,F)-F (7-57) 3% 3-BB(F,F)XB(F)B(F,F)-F (7-60) 3% 3-HHVFFXB(F,F)-F (6-120) 5% 3-BBVFFXB(F,F)-F (6-119) 5% 3-HBBVFFXB(F,F)-F (7-63) 3% 2-HH-5 (2-1) 5% 3-HH-V (2-1) 20% 5-HH-V (2-1) 12% 3-HH-V1 (2-1) 4% 4-HH-V1 (2-1) 5% 2-HH-2V1 (2-1) 3% 1-BB-3 (2-8) 3% V2-BB(F)B-1 (3-6) 5% V2-B(F)BB-1 (3-8) 5% 3-HB(F)HH-5 (4-7) 3% NI=85.8℃; Tc<-20℃; Δn=0.115; Δε=4.2; γ1=41.4 mPa·s.

[Composition (M39)] 3-BB(F)XB(F)B(F,F)-F (7-60) 5% 3-HGB(F,F)-F (6-103) 3% 5-GHB(F,F)-F (6-109) 4% 3-GB(F,F)XB(F,F)-F (6-113) 5% 3-HHBB(F,F)-F (7-6) 4% 2-dhBB(F,F)XB(F,F)-F (7-50) 4% 3-GB(F)B(F,F)XB(F,F)-F (7-57) 3% 3-HGB(F,F)XB(F,F)-F (7) 5% 7-HB(F,F)-F (5-4) 3% 2-HH-3 (2-1) 14% 2-HH-5 (2-1) 4% 3-HH-V (2-1) 26% 1V2-HH-3 (2-1) 5% 1V2-BB-1 (2-8) 3% 2-BB(F)B-3 (3-6) 3% 3-HB(F)HH-2 (4-7) 4% 5-HBB(F)B-2 (4-5) 5% NI=78.4℃; Tc<-20℃; Δn=0.094; Δε=5.6; Vth=1.45 V; η=11.5 mPa·s; γ1=61.7 mPa·s.

[Composition (M40)] 3-HBB(F,F)-F (6-24) 5% 5-HBB(F,F)-F (6-24) 4% 3-BB(F)B(F,F)XB(F,F)-F (7-47) 3% 4-BB(F)B(F,F)XB(F,F)-F (7-47) 5% 3-BB(F,F)XB(F)B(F,F)-F (7-60) 10% 3-HH2BB(F,F)-F (7-15) 3% 4-HH2BB(F,F)-F (7-15) 3% 2-HH-5 (2-1) 4% 3-HH-V (2-1) 25% 3-HH-V1 (2-1) 10% 4-HH-V1 (2-1) 7% 5-HB-O2 (2-5) 5% 7-HB-1 (2-5) 5% VFF-HHB-O1 (3-1) 8% VFF-HHB-1 (3-1) 3% NI=79.3℃; Tc<-20℃; Δn=0.099; Δε=5.0; Vth=1.64 V; η=10.4 mPa·s; γ1=44.7 mPa·s.

[Composition (M41)] 3-GBXB(F)B(F,F)-F (7) 5% 3-HHB(F,F)-F (6-3) 7% 3-GB(F)B(F)-F (6-116) 2% 3-GB(F)B(F,F)-F (6-117) 3% 3-BB(F,F)XB(F,F)-F (6-97) 7% 3-GB(F)B(F,F)XB(F,F)-F (7-57) 4% 5-GB(F)B(F,F)XB(F,F)-F (7-57) 5% 3-HH-V (2-1) 30% 3-HH-V1 (2-1) 10% 1V2-HH-3 (2-1) 8% 3-HH-VFF (2-1) 8% V2-BB-1 (2-8) 2% 5-HB(F)BH-3 (4-2) 4% 5-HBBH-3 (4-1) 5% NI=79.7℃; Tc<-20℃; Δn=0.091; Δε=5.7; Vth=1.83 V; η=14.9 mPa·s; γ1=69.3 mPa·s.

2. Alignment of liquid crystal molecules Use Example 1 to Use Example 7 (Preparation of samples) 0.1%, 0.3%, 0.5%, 1.0%, 3.0%, 5.0% by weight in the composition (M1) 1. A compound (No. 148) as the first additive was added at a ratio of 10.0% by weight, and a compound (AO-1) with R ⁴⁰ being an n-heptyl group as an antioxidant was added at a ratio of 150 ppm. The mixture was heated and stirred at 100° C. After that, it was returned to room temperature and allowed to stand for one week. As a result, no crystals or the like were precipitated and completely dissolved. (Fabrication of device) This mixture was injected into an IPS device without an alignment film at 90°C (above the upper limit temperature of the nematic phase). While heating the IPS element at 90°C, the element is irradiated with polarized ultraviolet light having a peak at a wavelength of 313 nm, a wavelength of 335 nm, and a wavelength of 365 nm from the normal direction for a certain period of time, thereby performing alignment processing and continuing Irradiate until the alignment becomes good. (Illumination condition of polarized ultraviolet rays) × The illumination intensity at a wavelength of 313 nm is 3 mW/cm ² . UIT-150 and UVD-S313 manufactured by Ushio Motor Co., Ltd. were used for the measurement. ×UHIO250U manufactured by Ushio Electric Co., Ltd. is used as the ultraviolet irradiation lamp. ×The exposure unit uses ML-251A/B manufactured by Ushio Motor Co., Ltd. × Polarized ultraviolet rays are formed using a wire grid polarizing element (ProFlux UVT260A manufactured by Polatechno Co., Ltd.). (Alignment confirmation method) The element is parallel to the polarization axis of linear polarized light, and is provided on a polarizing microscope where the polarizing element and the analyzer are arranged orthogonally, and the element is irradiated with light from below to observe the presence or absence of light leakage. When the light does not pass through the device, the alignment is judged to be "good". When the light transmitted through the element was observed, it was determined that the alignment was "poor" and the irradiation was insufficient. (Evaluation of easiness of alignment) The irradiation time was changed from 1 minute to 60 minutes, and the alignment at each irradiation time was confirmed. The irradiation ends at the time point when the alignment becomes good. The irradiation time until the alignment becomes good is summarized in Table 3 below.

Use Example 8 to Use Example 42 Using the composition (M1), a compound (AO-1) in which R ⁴⁰ is an n-heptyl group as an antioxidant was added at a rate of 150 ppm, and mixed in the ratio shown in Table 3 below. Additives. In addition, the operation was performed in the same manner as in Example 1. The irradiation time was measured by the same method as in Example 1. The results are summarized in Table 3 below.

table 3

In Use Example 1 to Use Example 42, the composition used was changed to M2 to M41, and the same operation was performed. As a result, in either case, the irradiation time did not change significantly.

The first additive from the composition (M1) to the composition (M41), the compound (No. 1) to the compound (No. 224) is appropriately selected, and the same operation is performed. Results: any of , The irradiation time is within 15 minutes.

Comparative Example 1 to Comparative Example 21 The compound (A-1-1-1), the compound (S-1) described in Patent Document 3, and the compound (S-2) described in Patent Document 2 were used as the first additive, Then, it was mixed with the composition (M1) in the ratio shown in Table 4 below, and the irradiation time was evaluated by the same operation as the use example. As a result, compared with the compound of the embodiment of the present invention, in any compound, when the longest irradiation time in the use example was 10 minutes, good alignment could not be obtained, and it was confirmed that the good alignment irradiation time was 30 minutes the above. In addition, the same evaluation was performed using the composition (M2) to the composition (M41), and the results were all the same as the case of using the composition (M1).

Table 4

In the use example, although the type and amount of the composition or the polar compound (1) were changed, there was no dissolution residue or precipitation, and no light leakage of the device was observed during the irradiation within 15 minutes. This result shows that even if there is no alignment film such as polyimide in the device, the alignment is good, and all the liquid crystal molecules are aligned in a certain direction. On the other hand, in the comparative example, if the irradiation is within 30 minutes, light leakage from the device is observed, and the alignment is not good. Therefore, as long as the compound (1) of the embodiment of the present invention is used, it can be used for short-time or low-energy light irradiation, thereby reducing the shortening of the tact time and damage to the mother liquid crystal caused by light irradiation. In addition, as long as the liquid crystal composition of the embodiment of the present invention is used, a temperature range with a wide usable element, a short response time, a high voltage retention rate, a low threshold voltage, a large contrast ratio, and a long A liquid crystal display element having at least one characteristic of life. Furthermore, a liquid crystal display element having a liquid crystal composition having a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a low viscosity, an appropriate optical anisotropy, and a negative dielectric each can be obtained At least one of characteristics such as high anisotropy, high specific resistance, high stability to ultraviolet rays, and high stability to heat is satisfied. [Industry availability]

The liquid crystal composition of the embodiment of the present invention can be used for liquid crystal monitors, liquid crystal televisions, and the like.

no

no

Claims (17)

A compound represented by formula (1);

In formula (1), a and b are independently 0, 1 or 2, and 0≦a+b≦3, ring A ¹ , ring A ² , ring A ³ and ring A ^{4 are} independently 1,4-stretched Cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, decalin-2,6-diyl, 1,2,3,4-tetra Hydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2, 5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl, 2 ,3,4,7,8,9,10,11,12,13,14,15,16,17-tetrahydrocyclopenta[a]phenanthrene-3,17-diyl, formula (A-1 ) Or the group represented by formula (A-2), in these rings, at least one hydrogen may be fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon Alkoxy groups having 1 to 11 carbon atoms, alkoxy groups having 2 to 11 carbon atoms, -Sp ¹ -P ¹ or -Sp ² -P ² , in these groups, at least one hydrogen may be substituted by fluorine or chlorine, When a is 2, the two rings A ¹ may be different. When b is 2, the two rings A ⁴ may be different. In formula (A-2), c is 2, 3, or 4; wherein, ring A ¹ , ring At least one of A ² , ring A ³ or ring A ⁴ is naphthalene-2,6-diyl, phenanthrene-2,7-diyl, the group represented by formula (A-1) or formula (A-2) The base represented;

Z ¹ , Z ² , Z ³ , Z ⁴ and Z ^{5 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be passed through -O-,- CO-, -COO-, -OCO- or -OCOO- substitution, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by Halogen substitution; wherein at least one of Z ² , Z ³ or Z ⁴ is -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO- or -COCH=CH-, when a is 2, the two Z ¹ may be different, when b is 2, the two Z ⁵ may be different; Sp ¹ and Sp ^{2 are} independently a single bond or an extension of carbon number 1 to 10 Alkyl group, in the alkylene group, at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, -OCO- or -OCOO-, and at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH- or -C≡C- substitution, in these groups, at least one hydrogen can be substituted by halogen, in the case where there are multiple Sp ¹ or Sp ² in the structure, they can be different; P ¹ and P ^{2 is} independently the basis represented by any one of formula (1b) to formula (1h), which may be different when there are multiple P ¹ or P ² in the structure;

In the formula (1b) to the formula (1h), M ¹ , M ² , M ³ and M ^{4 are} independently hydrogen, halogen, an alkyl group having 1 to 5 carbons or at least one hydrogen substituted with halogen and having 1 to 5 carbons R ² is hydrogen, halogen, C 1-5 alkyl group, in the alkyl group, at least one hydrogen may be substituted by halogen, at least one -CH ₂ -may be substituted by -O-; R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are} independently hydrogen or an alkyl group having 1 to 15 carbon atoms, in which 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-, in these groups, at least one hydrogen may be substituted by halogen. The compound as described in item 1 of the patent application, wherein in formula (1), a and b are independently 0, 1 or 2, and 0≦a+b≦2; ring A ¹ , ring A ² , ring A ³ and Ring A ^{4 are} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6 -Diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, Pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta [a]phenanthrene-3,17-diyl, 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetrahydrocyclopenta[a]phenanthrene -3,17-diyl, the group represented by the formula (A-1) or the group represented by the formula (A-2), in these rings, at least one hydrogen can be substituted by fluorine, chlorine, carbon number 1 to 12 Alkyl, C2-C12 alkenyl, C1-C11 alkoxy, C2-C11 alkenoxy, -Sp ¹ -P ¹ or -Sp ² -P ² substitution, these groups In at least one hydrogen may be substituted by fluorine or chlorine. When a is 2, the two rings A ¹ may be different. When b is 2, the two rings A ⁴ may be different. In formula (A-2), c is 2, 3 or 4; wherein at least one of ring A ¹ , ring A ² , ring A ³ or ring A ⁴ is naphthalene-2,6-diyl, phenanthrene-2,7-diyl, formula (A- 1) the base represented by or the base represented by formula (A-2);

Z ¹ , Z ² , Z ³ , Z ⁴ and Z ^{5 are} independently single bonds, -(CH ₂ ) ₂ -, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -CF=CF-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO- or -COCH=CH-, Wherein, at least one of Z ² , Z ³ or Z ⁴ is -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO- or -COCH= CH-, when a is 2, two Z ^1s may be different, and two Z ^5s may be different; Sp ¹ and Sp ^{2 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. , At least one -CH ₂ -may be substituted by -O-, -COO- or -OCO-, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH-, and of these groups, at least one hydrogen may be substituted by The fluorine or chlorine substitution may be different when there are multiple Sp ¹ or Sp ² in the structure; P ¹ and P ^{2 are} independently represented by any one of formula (1b) to formula (1h) The basis may be different if there are multiple P ¹ or P ² in the structure;

In the formula (1b) to the formula (1h), M ¹ , M ² , M ³ and M ^{4 are} independently hydrogen, halogen, an alkyl group having 1 to 5 carbons or at least one hydrogen substituted with halogen and having 1 to 5 carbons R ² is hydrogen, halogen, C 1-5 alkyl group, in the alkyl group, at least one hydrogen may be substituted by halogen, at least one -CH ₂ -may be substituted by -O-; R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are} independently hydrogen or an alkyl group having 1 to 15 carbon atoms, in which 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-, in these groups, at least one hydrogen may be substituted by halogen. The compound as described in item 1 or item 2 of the patent application scope, which is represented by any one of formula (1-1) to formula (1-3);

In formula (1-1) to formula (1-3), ring A ¹ , ring A ² , ring A ³ and ring A ^{4 are} independently 1,4-cyclohexyl, 1,4-phenylene, naphthalene -2,6-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6- Diyl, a group represented by formula (A-1) or a group represented by formula (A-2), in these rings, at least one hydrogen can pass through fluorine, chlorine, alkyl having 1 to 12 carbons, and carbon number Alkenyl groups of 2 to 12, alkoxy groups of 1 to 11 carbons, alkenyl groups of 2 to 11 carbons, -Sp ¹ -P ¹ or -Sp ² -P ² substitutions, in these groups, at least one hydrogen It can be substituted by fluorine or chlorine. When a is 2, the two rings A ¹ can be different. When b is 2, the two rings A ⁴ can be different. In formula (A-2), c is 2, 3 or 4 ; Where at least one of ring A ¹ , ring A ² , ring A ³ or ring A ⁴ is represented by naphthalene-2,6-diyl, phenanthrene-2,7-diyl, formula (A-1) Radical or radical represented by formula (A-2);

Z ² , Z ³ and Z ^{4 are} independently a single bond, -(CH ₂ ) ₂ -, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -CF=CF-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO- or -COCH=CH-, where Z ² , Z At least one of ³ and Z ⁴ is -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH=CH-, -CH=CHCO- or -COCH=CH-; Sp ¹ and Sp ^{2 is} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be substituted with -O-, -COO-, -OCOO- or -OCO-, 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, in the case where there are multiple Sp ¹ or Sp ² in the structure, respectively May be different; P ¹ and P ^{2 are} independently the basis represented by any one of formula (1b) to formula (1h), and may be different when there are multiple P ¹ or P ² in the structure;

In the formula (1b) to the formula (1h), M ¹ , M ² , M ³ and M ^{4 are} independently hydrogen, halogen, an alkyl group having 1 to 5 carbons or at least one hydrogen substituted with halogen and having 1 to 5 carbons R ² is hydrogen, halogen, C 1-5 alkyl group, in the alkyl group, at least one hydrogen may be substituted by halogen, at least one -CH ₂ -may be substituted by -O-; R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 are} independently hydrogen or an alkyl group having 1 to 15 carbon atoms, in which 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-, in these groups, at least one hydrogen may be substituted by halogen. The compound as described in item 3 of the patent application scope, wherein in formula (1-1), formula (1-2) and formula (1-3), ring A ¹ , ring A ² , ring A ³ and ring A ⁴ Independently 1,4-cyclohexyl, 1,4-phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, formula (A- 1) The group represented by or the group represented by formula (A-2), in these rings, at least one hydrogen may be through fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, C 1-11 alkoxy, C 2-11 alkoxy, -Sp ¹ -P ¹ or -Sp ² -P ² substitution, in formula (A-2), c is 2, 3 or 4 ; Where at least one of ring A ¹ , ring A ² , ring A ³ or ring A ⁴ is represented by naphthalene-2,6-diyl, phenanthrene-2,7-diyl, formula (A-1) Radical or radical represented by formula (A-2);

Z ² , Z ³ and Z ^{4 are} independently a single bond, -(CH ₂ ) ₂ -, -C≡C-, -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH =CH-, -CH=CHCO- or -COCH=CH-, wherein at least one of Z ² , Z ³ and Z ⁴ is -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH- , -CH=CH-, -CH=CHCO- or -COCH=CH-; Sp ¹ and Sp ^{2 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and of the alkylene groups, at least one- CH ₂ -may be substituted by -O-, -COO-, -OCOO- or -OCO-, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH-, and there are multiple Sp ¹ or In the case of Sp ² , they may be different respectively; P ¹ and P ^{2 are} independently a group represented by any one of formula (1b), formula (1c), formula (1d), or formula (1e). In the case of multiple P ¹ or P ² , the memory can be different;

In the formula (1b) to the formula (1e), M ¹ , M ² , M ³ and M ^{4 are} independently hydrogen, halogen, an alkyl group having 1 to 5 carbon atoms or at least one hydrogen substituted with halogen and having 1 to 5 carbon atoms R ² is hydrogen, halogen or a C 1-5 alkyl group, in the alkyl group, at least one hydrogen may be substituted by halogen, at least one -CH ₂ -may be substituted by -O-; R ³ , R ⁴ , R ⁵ and R ^{6 are} independently hydrogen or an alkyl group having 1 to 15 carbon atoms, in which 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-, in these groups, at least one hydrogen may be substituted by halogen. The compound as described in item 3 of the patent application scope, wherein in formula (1-1), formula (1-2) and formula (1-3), ring A ¹ , ring A ² , ring A ³ and ring A ⁴ Independently 1,4-cyclohexyl, 1,4-phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, formula (A- 1) The group represented by or the group represented by formula (A-2), in these rings, at least one hydrogen may be substituted by fluorine, chlorine, methyl or ethyl, in formula (A-2), c is 2 , 3 or 4; wherein at least one of ring A ¹ , ring A ² , ring A ³ or ring A ⁴ is naphthalene-2,6-diyl, phenanthrene-2,7-diyl, formula (A-1 ) Represented by the group or the group represented by the formula (A-2);

Z ² , Z ³ and Z ^{4 are} independently a single bond, -(CH ₂ ) ₂ -, -C≡C-, -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH-, -CH =CH-, -CH=CHCO- or -COCH=CH-, wherein at least one of Z ² , Z ³ and Z ⁴ is -COO-, -OCO-, -CH=CHCOO-, -OCOCH=CH- , -CH=CH-, -CH=CHCO- or -COCH=CH-; Sp ¹ and Sp ^{2 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and of the alkylene groups, at least one- CH ₂ -may be substituted by -O-, -COO-, -OCOO- or -OCO-, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH-, and there are multiple Sp ¹ or In the case of Sp ² , they can be different respectively; P ¹ and P ^{2 are} independently formula (1b-1), formula (1b-2), formula (1b-3), formula (1b-4), formula (1b- 5), the group represented by formula (1c-1), formula (1d-1), formula (1d-2) or formula (1e-1);

. The compound as described in item 3 of the patent application scope, wherein in the compound represented by formula (1-1), formula (1-2) or formula (1-3), any of Z ² , Z ³ or Z ⁴ One is -COO- or -OCO-. The compound described in item 1 or item 2 of the scope of patent application is represented by formula (1-A);

P ¹ and P ^{2 are} independently formula (1b-1), formula (1b-2), formula (1b-3), formula (1b-4), formula (1b-5), formula (1c-1), The group represented by formula (1d-1), formula (1d-2) or formula (1e-1); Sp ¹ and Sp ^{2 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, the alkylene group In the group, at least one -CH ₂ -may be substituted by -O-, -COO-, -OCOO- or -OCO-, at least one -(CH ₂ ) ₂ -may be substituted by -CH=CH-; Y is the formula ( MES-1-01) to the group represented by any one of formulas (MES-1-10), in which at least one hydrogen may be substituted by fluorine, chlorine, methyl or ethyl;

. The compound as described in item 7 of the patent application, wherein in the compound represented by formula (1-A), Sp ¹ and Sp ^{2 are} independently an alkylene group having 1 to 10 carbon atoms. At least one -CH ₂ -may be substituted with -O-, -COO-, -OCOO-, or -OCO-, and at least one -(CH ₂ ) ₂ -may be substituted with -CH=CH-. A liquid crystal composition containing at least one compound as described in any one of claims 1 to 8. The liquid crystal composition according to item 9 of the patent application scope, which further 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 the alkyl groups and alkenyl groups is -CH 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 , 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 bonds , -CH ₂ CH ₂ -, -CH=CH-, -C≡C- or -COO-. The liquid crystal composition according to item 9 or 10 of the patent application scope, which further 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. Among the alkyl groups and alkenyl groups, at least one -CH ₂ -may be passed through- O-substituted, 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-di Group, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; Z ¹⁴ , Z ¹⁵ and Z ^{16 are} independently a single bond, -CH ₂ CH ₂ -, -CH= CH-, -C≡C-, -COO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -CF=CF-, -CH=CF- or -(CH ₂ ) ₄ -; L ¹¹ and L ^{12 are} independently hydrogen or fluorine. The liquid crystal composition according to item 9 or 10 of the patent application scope, which further contains at least one compound of the compound represented by formula (8);

In formula (8), R ¹⁴ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. In the alkyl group and the alkenyl group, at least one -CH ₂ -may be substituted with -O-, at least One hydrogen may be substituted with fluorine; X ¹² is -C≡N or -C≡CC≡N; Ring D ¹ is 1,4-cyclohexyl, at least one hydrogen may be substituted with fluorine, 1,4-phenylene, Tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; Z ¹⁷ is a single bond, -CH ₂ CH ₂ -,- C≡C-, -COO-, -CF ₂ O-, -OCF ₂ -, or -CH ₂ O-; L ¹³ and L ^{14 are} independently hydrogen or fluorine; i is 1, 2, 3, or 4. The liquid crystal composition according to item 9 or 10 of the patent application scope, which further contains at least one compound selected from the group of compounds represented by formula (9) to formula (15);

In formula (9) to formula (15), R ¹⁵ and R ^{16 are} independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and of the alkyl group and alkenyl group, at least one -CH ₂ -May be substituted with -O-, at least one hydrogen may be substituted with fluorine; R ¹⁷ is hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. , At least one -CH ₂ -may be substituted by -O-, at least one hydrogen may be substituted by fluorine; ring E ¹ , ring E ² , ring E ³ and ring E ^{4 are} independently 1,4-cyclohexyl, 1, 4-cyclohexenyl, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6-diyl which may be substituted with fluorine for at least one hydrogen; ring E ⁵ And ring E ^{6 is} 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 a single bond, -CH ₂ CH ₂ -, -COO-, -CH ₂ O-, -OCF ₂ -or -OCF ₂ CH ₂ CH ₂ -; L ¹⁵ and L ^{16 are} independently fluorine or chlorine; S ¹¹ is hydrogen or methyl; X is -CHF- or -CF ₂ -; j, k, m, n, p, q, r, and s 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 9 or 10 of the patent application scope, which contains at least one polymerizable compound of the compound represented by formula (16);

In formula (16), ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan Alkan-2-yl, pyrimidin-2-yl or pyrid-2-yl, in these rings, at least one hydrogen may be substituted by halogen, an alkyl group having 1 to 12 carbons or at least one hydrogen substituted by halogen 12 alkyl substitution; 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, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl Group, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in these rings, at least one hydrogen can be halogen, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons Or at least one hydrogen is substituted with a halogen-substituted alkyl group having 1 to 12 carbon atoms; Z ²² and Z ^{23 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -May be substituted by -O-, -CO-, -COO- or -OCO-, at least one -CH ₂ CH ₂ -may be substituted by -CH=CH-, -C(CH ₃ )=CH-, -CH= C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ )-substitution, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; P ¹¹ , P ¹² and P ^{13 are} independently selected from The polymerizable group in the group represented by formula (P-1) to formula (P-5);

M ¹¹ , M ¹² and M ^{13 are} independently hydrogen, fluorine, C 1-5 alkyl, or at least one hydrogen substituted with fluorine or chlorine, C 1-5 alkyl; Sp ¹¹ , Sp ¹² and Sp ^{13 is} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be substituted with -O-, -COO-, -OCO- or -OCOO-, at least One -CH ₂ CH ₂ -may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; u is 0, 1 or 2; f, g and h It is independently 0, 1, 2, 3, or 4, and the sum of f, g, and h is 2 or more. The liquid crystal composition according to item 9 or 10 of the patent application scope, which contains at least one polymerizable compound selected from the group of compounds represented by formula (16-1) to formula (16-27);

In formula (16-1) to formula (16-27), P ¹¹ , P ¹² and P ^{13 are} independently selected from the group of groups represented by formula (P-1) to formula (P-3) A polymerizable group, where M ¹¹ , M ¹² and M ^{13 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with halogen;

Sp ¹¹ , Sp ¹² and Sp ^{13 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be passed through -O-, -COO-, -OCO- Or -OCOO- substitution, at least one -CH ₂ CH ₂ -may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine or chlorine. The liquid crystal composition according to item 9 or 10 of the patent application scope, which further contains a polymerizable compound other than formula (1) and formula (16), a polymerization initiator, a polymerization inhibitor, an optically active compound, At least one of an oxidizing agent, an ultraviolet absorber, a light stabilizer, a heat stabilizer, and an antifoaming agent. A liquid crystal display element containing the liquid crystal composition as described in any one of claims 9 to 16.