TWI775916B - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal composition and an AM device including the composition, the liquid crystal composition fully satisfies high upper limit temperature, low minimum temperature, low viscosity, appropriate optical anisotropy, and positive or negative dielectric anisotropy At least one of the properties, such as large, or at least two of these properties have an appropriate balance. A liquid crystal composition containing a specific ultraviolet absorber as a first additive, a specific compound having a small viscosity or a high upper limit temperature as a first component, and a second component having a large positive dielectric An anisotropic specific compound, a specific compound having a large negative dielectric anisotropy as a third component, or a specific compound having a polymerizable group as a second additive.

Description

Liquid crystal composition and liquid crystal display element

The present invention relates to a liquid crystal composition, a liquid crystal display element containing the composition, and the like. It also relates to a liquid crystal composition with positive or negative dielectric anisotropy, and an active matrix (AM) device containing the composition and having modes such as TN, OCB, IPS, VA, FFS, and FPA. It also relates to a polymer-stabilized alignment type liquid crystal display element.

In liquid crystal display elements, the classification based on the operation mode of 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. Component-based driving methods are classified into passive matrix (PM) and active matrix (AM). PM is classified into static, multiplex, etc., AM is classified into thin film transistor (TFT), metal insulator metal (MIM), and the like. TFTs are classified into amorphous silicon and polycrystal silicon. The latter are classified into high temperature type and low temperature type according to the manufacturing steps. The light source is classified into a reflective type using natural light, a transmissive type using a backlight, and a transflective type using both natural light and backlight.

The liquid crystal display element contains a liquid crystal composition having a nematic phase. The composition has suitable properties. By improving the properties of the composition, an AM device having good properties can be obtained. The associations among these properties are summarized in Table 1 below. The properties of the composition will be further described based on a commercially available AM device. The temperature range of the nematic phase correlates to the temperature range over which the element can be used. The preferable upper limit temperature of the nematic phase is about 70°C or higher, and the preferable lower limit temperature of the nematic phase is about -10°C or less. The viscosity of the composition correlates with the response time of the component. In order to display a moving image with the device, it is preferable to have a short response time. The ideal is a response time of less than 1 millisecond. Therefore, the viscosity of the composition is preferably small. Furthermore, it is preferable that the viscosity at low temperature is small.

[Table 1]

The optical anisotropy of the composition correlates with the contrast of the element. Depending on the mode of the element, a large optical anisotropy or a small optical anisotropy, that is, an appropriate optical anisotropy, is required. The product (Δn×d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the element is designed to maximize the contrast ratio. An appropriate value of the product depends on the type of operation mode. In elements of a mode such as TN, a suitable value is about 0.45 μm. In this case, a composition having a large optical anisotropy is preferable for an element with a small cell gap. The large dielectric anisotropy of the composition contributes to the low threshold voltage, small power consumption and large contrast ratio of the device. Therefore, a large dielectric anisotropy is preferred. Especially in the FFS mode, due to the oblique electric field, the arrangement of some liquid crystal molecules is not parallel to the panel substrate. Therefore, in order to suppress the upward tilt of these liquid crystal molecules, the dielectric constant in the short axis direction of the liquid crystal molecules is preferably (ε⊥) is large. By suppressing the upward inclination of the liquid crystal molecules, the transmittance of the element having the FFS mode can be improved, thereby contributing to a large contrast ratio. The large specific resistance of the composition contributes to the large voltage holding ratio and the large contrast ratio of the element. Therefore, in the initial stage, a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable. And it is preferable that it is a composition which has 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 being used for a long time. The stability of the composition to ultraviolet rays and heat is related to the life of the liquid crystal display element. When the stability of these is high, the life of the element is long. Such characteristics are preferable for AM elements used for liquid crystal monitors, liquid crystal televisions, and the like.

A composition having positive dielectric anisotropy is used in an AM element having a TN mode. A composition having negative dielectric anisotropy is used in an AM element having a VA mode. A composition having positive or negative dielectric anisotropy is used in an AM element having an IPS mode or an FFS mode. In a polymer sustained alignment (PSA) type AM device, a composition having positive or negative dielectric anisotropy is used.

On the other hand, Patent Document 1 describes compounds that improve the stability of thermosetting compositions and thermoplastic compositions to heat, oxygen, or light. [Prior Art Document] [Patent Document]

[Patent Document 1] International Publication No. 2002/079173

[Problem to be Solved by the Invention] An object of the present invention is to provide a liquid crystal composition having high stability against ultraviolet rays. Another object is to provide a liquid crystal composition, which fully satisfies the requirements of high upper limit temperature of nematic phase, low minimum temperature of nematic phase, low viscosity, suitable optical anisotropy, large dielectric anisotropy, large specific resistance, and high specific resistance for the nematic phase. It is at least one of characteristics such as high thermal stability and poor suppression of afterimages. Yet another object is to provide a liquid crystal composition having an appropriate balance between at least two of these properties. Another object is to provide a compound that can be added to a liquid crystal composition to improve the stability of the liquid crystal composition to ultraviolet rays. Still another object is to provide a liquid crystal display element containing such a composition and having characteristics such as short response time, high voltage holding ratio, low threshold voltage, high contrast ratio, and long life. [Means of Solving Problems]

式（1）中，R¹ 為氫、碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、碳數2至12的烯基氧基、或者至少一個氫經氟或氯取代的碳數1至12的烷基；R² 為碳數1至12的烷基、碳數2至12的烯基、至少一個氫經氟或氯取代的碳數1至12的烷基，該些基中，至少一個-CH₂ -可經-O-、-COO-、或-OCO-取代，或者為式（A-1）所表示的基；環A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，至少一個氫可經氟、氯、碳數1至12的烷基、碳數1至12的烷氧基、或者至少一個氫經氟或氯取代的碳數1至12的烷基取代；a為1或2；b為0、1、2、3、或4；

式（A-1）中，R^a 為氟、氯、碳數1至12的烷基、碳數2至12的烯基、或者至少一個氫經氟或氯取代的碳數1至12的烷基，該些基中，至少一個-CH₂ -可經-O-、-COO-、或-OCO-取代；Z^a 為碳數1至20的亦可分支的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-COO-、或-OCO-取代，至少一個-CH₂ -CH₂ -可經-CH=CH-取代；s為0或1；t為0、1、2、3、4、或5。The present invention relates to a liquid crystal composition containing at least one compound (hereinafter, sometimes described as a compound ( 1)) as the first additive and has a nematic phase.

In formula (1), R ¹ is hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, Or at least one alkyl group with 1 to 12 carbons substituted by fluorine or chlorine; R ² is alkyl with 1 to 12 carbons, alkenyl with 2 to 12 carbons, at least one carbon substituted with fluorine or chlorine The alkyl group of numbers 1 to 12, among these groups, at least one -CH ₂ - may be substituted by -O-, -COO-, or -OCO-, or a group represented by formula (A-1); Ring A 1,4-cyclohexylene, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4 -diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene -2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl Diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen may be fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen C 1-12 alkyl substituted by fluorine or chlorine; a is 1 or 2; b is 0, 1, 2, 3, or 4;

In formula (A-1), R ^a is fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkane having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine group, among these groups, at least one -CH ₂ - can be substituted by -O-, -COO-, or -OCO-; Z ^a is a branched alkylene with 1 to 20 carbon atoms, the alkylene In, at least one -CH ₂ - can be substituted by -O-, -COO-, or -OCO-, and at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH-; s is 0 or 1; t is 0, 1, 2, 3, 4, or 5.

式（1'）中，R¹ 為氫、碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、碳數2至12的烯基氧基、或者至少一個氫經氟或氯取代的碳數1至12的烷基；R² 為碳數1至12的烷基、碳數2至12的烯基、至少一個氫經氟或氯取代的碳數1至12的烷基，該些基中，至少一個-CH₂ -可經-O-、-COO-、或-OCO-取代；環A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，至少一個氫可經氟、氯、碳數1至12的烷基、碳數1至12的烷氧基、或者至少一個氫經氟或氯取代的碳數1至12的烷基取代；a為1或2；b為0、1、2、3、或4。 [發明的效果]In addition, the present invention relates to a compound represented by the following formula (1').

In formula (1'), R ¹ is hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons , or an alkyl group having 1 to 12 carbons substituted with at least one hydrogen by fluorine or chlorine; R ² is an alkyl group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, at least one hydrogen substituted by fluorine or chlorine Alkyl having 1 to 12 carbon atoms, among these groups, at least one -CH ₂ - may be substituted by -O-, -COO-, or -OCO-; Ring A is 1,4-cyclohexylene, 1,4 -Cyclohexenyl, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl , naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl , in these rings, at least one hydrogen can be substituted by fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least one hydrogen with 1 to 12 carbons substituted by fluorine or chlorine Alkyl-substituted; a is 1 or 2; b is 0, 1, 2, 3, or 4. [Effect of invention]

An advantage of the present invention is to provide a liquid crystal composition with high stability to ultraviolet light. Another advantage is to provide a liquid crystal composition, which fully satisfies the requirements of high upper limit temperature of nematic phase, low lower limit temperature of nematic phase, low viscosity, suitable optical anisotropy, large dielectric anisotropy, large specific resistance, and high specific resistance for the nematic phase. It is at least one of characteristics such as high thermal stability and poor suppression of afterimages. Yet another advantage is to provide a liquid crystal composition with an appropriate balance between at least two of these properties. In addition, another advantage is to provide a compound that can be added to a liquid crystal composition to improve the stability of the liquid crystal composition to ultraviolet rays. Furthermore, another advantage is to provide a liquid crystal display element containing such a composition and having characteristics such as short response time, high voltage holding ratio, low threshold voltage, high contrast ratio, and long life.

How to use the terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "composition" and "element", respectively. A "liquid crystal display element" is a general term for a liquid crystal display panel and a liquid crystal display module. "Liquid crystal compound" is a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and a compound that does not have a liquid crystal phase, but is used for the purpose of adjusting the temperature range, viscosity, and dielectric anisotropy of the nematic phase. On the other hand, a general term for compounds mixed in the composition. This compound has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod-like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. The liquid crystal compound having an alkenyl group is not polymerizable in its meaning.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are added to the liquid crystal composition as necessary. Even when an additive is added, the ratio of the liquid crystal compound is represented by the mass percentage (mass %) based on the mass of the liquid crystal composition not containing the additive. The ratio of the additive is represented by the mass percentage (mass %) based on the mass of the additive-free liquid crystal composition. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total mass of the liquid crystal compound. Parts per million by mass (ppm) are sometimes used. The ratios of the polymerization initiator and the polymerization inhibitor are expressed based on the mass of the polymerizable compound exceptionally.

The "upper limit temperature of the nematic phase" is sometimes abbreviated as "upper limit temperature". The "lower limit temperature of the nematic phase" is sometimes simply referred to as the "lower limit temperature". "Large specific resistance" means that the composition has a large specific resistance in the initial stage, and has a large specific resistance after being used for a long time. "Large voltage retention rate" means that the device has a large voltage retention rate not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and after long-term use, not only at room temperature but also at It also has a large voltage holding ratio at a temperature close to the upper limit temperature. The properties of a composition or element are sometimes investigated by a time-dependent test. The expression "improving the dielectric anisotropy" refers to a positive increase in the value of a composition with a positive dielectric anisotropy, and a negative value in the case of a composition with a negative dielectric anisotropy increase to the ground.

Expressions such as "at least one -CH ₂ - may be substituted with -O-" are used in this specification. In this case, -CH ₂ -CH ₂ -CH ₂ - can be converted to -O-CH ₂ -O- by substituting a non-adjacent -CH ₂ - with -O-. However, the adjacent _-CH2- is not substituted with -O-. This is because -OO-CH ₂ - (peroxide) is generated in this substitution. That is, the expression refers to both "one -CH ₂ - may be substituted with -O-" and "at least two non-adjacent -CH ₂ - may be substituted with -O-". This rule applies not only in the case of substitution with -O-, but also in the case of substitution with divalent groups such as -CH=CH- or -COO-.

In the chemical formulae of the component compounds, the notation of the terminal group R ³ is used for various compounds. In these compounds, the two groups represented by any two R ³ may be the same or different. For example, there is a case where R ³ of the compound (2-1) is an ethyl group, and R ³ of the compound (2-2) is an ethyl group. There are also cases where R ³ of compound (2-1) is ethyl and R ³ of compound (2-2) is propyl. This rule also applies to the notation of other terminal groups, etc. In formula (1), when the subscript 'a' is 2, there are two rings A. In this compound, the two rings represented by the two rings A may be the same or different. This rule also applies to any two rings A when the subscript 'a' is greater than 2. This rule also applies to symbols such as Z ¹ , ring B, etc. This rule also applies to the case of two -Sp ² -P ⁵ in compound (5-27).

Symbols such as A, B, C, and D surrounded by hexagons correspond to rings such as ring A, ring B, ring C, and ring D, respectively, and represent rings such as six-membered rings and condensed rings. In the compound (1) and the compound (5), the oblique line crossing one side of the hexagon indicates that any hydrogen on the ring may be substituted with a group such as R ² , -Sp ¹ -P ¹ or the like. Subscripts such as 'b' indicate the number of substituted groups. When the subscript 'b' is 0 (zero), there is no such substitution. When the subscript 'b' is 2 or more, a plurality of R ² exist on the ring. A plurality of groups represented by R ² may be the same or different. In the expression "Ring A and Ring B are independently X, Y, or Z", since there are plural subjects, "independently" is used. When the subject is "Ring A", since the subject is singular, "independently" is not used.

The 2-fluoro-1,4-phenylene group refers to the following two divalent groups. In the chemical formula, fluorine can be left (L) or right (R). This rule also applies to left-right asymmetric divalent radicals such as tetrahydropyran-2,5-diyl, which are formed by removing two hydrogens from the ring. This rule also applies to divalent bonding groups such as carbonyloxy (-COO- or -OCO-).

The alkyl group of the liquid crystal compound is linear or branched, and does not contain a cyclic alkyl group. Straight chain alkyl groups are preferred over branched alkyl groups. The same applies to terminal groups such as an alkoxy group and an alkenyl group. In order to increase the upper temperature limit, the steric configuration associated with 1,4-cyclohexylene is the trans configuration over the cis configuration.

The present invention is the following items and the like.

式（1）中，R¹ 為氫、碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、碳數2至12的烯基氧基、或者至少一個氫經氟或氯取代的碳數1至12的烷基；R² 為碳數1至12的烷基、碳數2至12的烯基、至少一個氫經氟或氯取代的碳數1至12的烷基，該些基中，至少一個-CH₂ -可經-O-、-COO-、或-OCO-取代，或者為式（A-1）所表示的基；環A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，至少一個氫可經氟、氯、碳數1至12的烷基、碳數1至12的烷氧基、或者至少一個氫經氟或氯取代的碳數1至12的烷基取代；a為1或2；b為0、1、2、3、或4；

式（A-1）中，R^a 為氟、氯、碳數1至12的烷基、碳數2至12的烯基、或者至少一個氫經氟或氯取代的碳數1至12的烷基，該些基中，至少一個-CH₂ -可經-O-、-COO-、或-OCO-取代；Z^a 為碳數1至20的亦可分支的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-COO-、或-OCO-取代，至少一個-CH₂ -CH₂ -可經-CH=CH-取代；s為0或1；t為0、1、2、3、4、或5。Item 1. A liquid crystal composition comprising at least one compound selected from the compounds represented by formula (1) as a first additive, and having a nematic phase.

In formula (1), R ¹ is hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, Or at least one alkyl group with 1 to 12 carbons substituted by fluorine or chlorine; R ² is alkyl with 1 to 12 carbons, alkenyl with 2 to 12 carbons, at least one carbon substituted with fluorine or chlorine The alkyl group of numbers 1 to 12, among these groups, at least one -CH ₂ - may be substituted by -O-, -COO-, or -OCO-, or a group represented by formula (A-1); Ring A 1,4-cyclohexylene, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4 -diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene -2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl Diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen may be fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen C 1-12 alkyl substituted by fluorine or chlorine; a is 1 or 2; b is 0, 1, 2, 3, or 4;

In formula (A-1), R ^a is fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkane having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine group, among these groups, at least one -CH ₂ - can be substituted by -O-, -COO-, or -OCO-; Z ^a is a branched alkylene with 1 to 20 carbon atoms, the alkylene In, at least one -CH ₂ - can be substituted by -O-, -COO-, or -OCO-, and at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH-; s is 0 or 1; t is 0, 1, 2, 3, 4, or 5.

Item 2. The liquid crystal composition according to Item 1, wherein in the compound represented by the formula (1), R ² is a methyl group, a tertiary butyl group, a tertiary pentyl group, a tertiary octyl group, or an α-pentyl group , b is 1, 2, 3, or 4.

式（1-1）至式（1-4）中，R² 為甲基、第三丁基、第三戊基、第三辛基、或α-戊基。Item 3. The liquid crystal composition according to Item 1 or Item 2, which contains at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-4) as the first additive .

In the formula (1-1) to the formula (1-4), R ² is a methyl group, a tertiary butyl group, a tertiary pentyl group, a tertiary octyl group, or an α-pentyl group.

Item 4. The liquid crystal composition according to any one of Items 1 to 3, wherein the ratio of the first additive is in the range of 0.005 mass % to 2 mass %.

式（2）中，R³ 及R⁴ 獨立地為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、或者至少一個氫經氟或氯取代的碳數2至12的烯基；環B及環C獨立地為1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、或2,5-二氟-1,4-伸苯基；Z¹ 為單鍵、伸乙基、羰基氧基、或亞甲基氧基；c為1、2、或3。Item 5. The liquid crystal composition according to any one of Items 1 to 4, which contains, as a first component, at least one compound selected from the group consisting of compounds represented by formula (2).

In formula (2), R ³ and R ⁴ are independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or at least one hydrogen substituted by fluorine or chlorine Substituted alkenyl having 2 to 12 carbon atoms; Ring B and Ring C are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2, 5-difluoro-1,4-phenylene; Z ¹ is a single bond, ethylene, carbonyloxy, or methyleneoxy; c is 1, 2, or 3.

式（2-1）至式（2-13）中，R³ 及R⁴ 獨立地為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、或者至少一個氫經氟或氯取代的碳數2至12的烯基。Item 6. The liquid crystal composition according to any one of Items 1 to 5, which contains at least one compound selected from the group of compounds represented by Formula (2-1) to Formula (2-13) as first ingredient.

In formula (2-1) to formula (2-13), R ³ and R ⁴ are independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. , or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine.

Item 7. The liquid crystal composition according to Item 5 or Item 6, wherein the ratio of the first component is in the range of 10% by mass to 85% by mass.

式（3）中，R⁵ 為碳數1至12的烷基、碳數1至12的烷氧基、或碳數2至12的烯基；環D為1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、2,3-二氟-1,4-伸苯基、2,6-二氟-1,4-伸苯基、嘧啶-2,5-二基、1,3-二噁烷-2,5-二基、或四氫吡喃-2,5-二基；Z² 為單鍵、伸乙基、羰基氧基、或二氟亞甲基氧基；X¹ 及X² 獨立地為氫或氟；Y¹ 為氟、氯、至少一個氫經氟或氯取代的碳數1至12的烷基、至少一個氫經氟或氯取代的碳數1至12的烷氧基、或者至少一個氫經氟或氯取代的碳數2至12的烯基氧基；d為1、2、3、或4。Item 8. The liquid crystal composition according to any one of Items 1 to 7, which contains, as a second component, at least one compound selected from the group consisting of compounds represented by formula (3).

In formula (3), R ⁵ is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms; ring D is 1,4-cyclohexylene, 1 ,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine -2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z ² is a single bond, ethylidene, carbonyloxy, or difluoromethyleneoxy; X ¹ and X ² are independently hydrogen or fluorine; Y ¹ is fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine, and at least one hydrogen is an alkoxy group having 1 to 12 carbons substituted with fluorine or chlorine, or an alkenyloxy group having 2 to 12 carbons substituted with at least one hydrogen by fluorine or chlorine; d is 1, 2, 3, or 4.

式（3-1）至式（3-35）中，R⁵ 為碳數1至12的烷基、碳數1至12的烷氧基、或碳數2至12的烯基。Item 9. The liquid crystal composition according to any one of Items 1 to 8, which contains at least one compound selected from the group of compounds represented by Formula (3-1) to Formula (3-35) as Second ingredient.

In formulas (3-1) to (3-35), R ⁵ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons.

Item 10. The liquid crystal composition according to Item 8 or Item 9, wherein the ratio of the second component is in the range of 10% by mass to 85% by mass.

式（4）中，R⁶ 及R⁷ 獨立地為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、或碳數2至12的烯基氧基；環E及環G獨立地為1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、至少一個氫經氟或氯取代的1,4-伸苯基、或四氫吡喃-2,5-二基；環F為2,3-二氟-1,4-伸苯基、2-氯-3-氟-1,4-伸苯基、2,3-二氟-5-甲基-1,4-伸苯基、3,4,5-三氟萘-2,6-二基、或7,8-二氟色原烷-2,6-二基；Z³ 及Z⁴ 獨立地為單鍵、伸乙基、羰基氧基、或亞甲基氧基；e為1、2、或3，f為0或1；e與f之和為3以下。Item 11. The liquid crystal composition according to any one of Items 1 to 10, which contains at least one compound selected from the group consisting of compounds represented by formula (4) as a third component.

In formula (4), R ⁶ and R ⁷ are independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or an alkene having 2 to 12 carbons yloxy; Ring E and Ring G are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4 wherein at least one hydrogen is substituted with fluorine or chlorine -phenylene, or tetrahydropyran-2,5-diyl; ring F is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene group, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochromane- 2,6-diyl; Z ³ and Z ⁴ are independently a single bond, ethylidene, carbonyloxy, or methyleneoxy; e is 1, 2, or 3, and f is 0 or 1; e and The sum of f is 3 or less.

式（4-1）至式（4-27）中，R⁶ 及R⁷ 獨立地為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、或碳數2至12的烯基氧基。Item 12. The liquid crystal composition according to any one of Items 1 to 11, which contains at least one compound selected from the group of compounds represented by Formula (4-1) to Formula (4-27) as third ingredient.

In formula (4-1) to formula (4-27), R ⁶ and R ⁷ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons , or an alkenyloxy group having 2 to 12 carbons.

Item 13. The liquid crystal composition according to Item 11 or Item 12, wherein the ratio of the third component is in the range of 5% by mass to 80% by mass.

式（5）中，環I及環K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，至少一個氫可經氟、氯、碳數1至12的烷基、碳數1至12的烷氧基、或者至少一個氫經氟或氯取代的碳數1至12的烷基取代；環J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，至少一個氫可經氟、氯、碳數1至12的烷基、碳數1至12的烷氧基、或者至少一個氫經氟或氯取代的碳數1至12的烷基取代；Z⁵ 及Z⁶ 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；P¹ 、P² 、及P³ 獨立地為聚合性基；Sp¹ 、Sp² 、及Sp³ 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；g為0、1、或2；h、i、及j獨立地為0、1、2、3、或4；而且h、i、及j之和為1以上。Item 14. The liquid crystal composition according to any one of Items 1 to 13, which contains at least one compound selected from the group consisting of polymerizable compounds represented by formula (5) as a second additive.

In formula (5), ring I and ring K are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxanyl Alkyl-2-yl, pyrimidin-2-yl, or pyridin-2-yl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons group, or at least one hydrogen is substituted by fluorine or chlorine substituted alkyl with 1 to 12 carbon atoms; ring J is 1,4-cyclohexylene, 1,4-cyclohexenyl, 1,4-phenylene , naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1, 7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5- Diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine , an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; Z ⁵ and Z ⁶ are independently a single bond Or alkylene with 1 to 10 carbon atoms, in the alkylene, at least one -CH ₂ - can be substituted by -O-, -CO-, -COO-, or -OCO-, and at least one -CH ₂ -CH ₂ - may be substituted by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )-, or -C(CH ₃ )=C(CH ₃ )-, in which , at least one hydrogen can be substituted by fluorine or chlorine; P ¹ , P ² , and P ³ are independently polymerizable groups; Sp ¹ , Sp ² , and Sp ³ are independently a single bond, or an extension of carbon number 1 to 10 Alkyl, in the alkylene, at least one -CH ₂ - can be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH - or -C≡C-substituted, in these groups, at least one hydrogen may be substituted with fluorine or chlorine; g is 0, 1, or 2; h, i, and j are independently 0, 1, 2, 3, or 4; and the sum of h, i, and j is 1 or more.

式（P-1）至式（P-5）中，M¹ 、M² 、及M³ 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。Item 15. The liquid crystal composition according to Item 14, wherein in formula (5), P ¹ , P ² , and P ³ are independently represented by formula (P-1) to formula (P-5) A group in the group of polymerizable groups.

In formula (P-1) to formula (P-5), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen substituted by fluorine or chlorine Alkyl having 1 to 5 carbons.

式（5-1）至式（5-29）中，P⁴ 、P⁵ 、及P⁶ 獨立地為選自式（P-1）至式（P-3）所表示的聚合性基的群組中的基，M¹ 、M² 、及M³ 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；

Sp¹ 、Sp² 、及Sp³ 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。Item 16. The liquid crystal composition according to any one of Items 1 to 15, which contains at least one selected from the group of polymerizable compounds represented by Formula (5-1) to Formula (5-29) compound as a second additive.

In formula (5-1) to formula (5-29), P ⁴ , P ⁵ , and P ⁶ are independently selected from the group of polymerizable groups represented by formula (P-1) to formula (P-3) The groups in the group, M ¹ , M ² , and M ³ are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is substituted with fluorine or chlorine;

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

Item 17. The liquid crystal composition according to any one of Items 14 to 16, wherein the ratio of the second additive is in the range of 0.03 mass % to 10 mass %.

Item 18. A liquid crystal display element comprising the liquid crystal composition according to any one of Items 1 to 17.

Item 19. The liquid crystal display element of item 18, wherein the operation mode of the liquid crystal display element is TN mode, ECB mode, OCB mode, IPS mode, VA mode, FFS mode, or FPA mode, and the driving mode of the liquid crystal display element is Active matrix approach.

Item 20. A polymer-stabilized alignment-type liquid crystal display element comprising the liquid crystal composition according to any one of Items 14 to 17, wherein the polymerizable compound in the liquid crystal composition is polymerized.

Item 21. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of items 1 to 17, which is used in a liquid crystal display element.

Item 22. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of items 14 to 17, which is used in a polymer-stabilized alignment type liquid crystal display element.

式（1'）中，R¹ 為氫、碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、碳數2至12的烯基氧基、或者至少一個氫經氟或氯取代的碳數1至12的烷基；R² 為碳數1至12的烷基、碳數2至12的烯基、至少一個氫經氟或氯取代的碳數1至12的烷基，該些基中，至少一個-CH₂ -可經-O-、-COO-、或-OCO-取代；環A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，至少一個氫可經氟、氯、碳數1至12的烷基、碳數1至12的烷氧基、或者至少一個氫經氟或氯取代的碳數1至12的烷基取代；a為1或2；b為0、1、2、3、或4。Item 23. A compound represented by formula (1').

In formula (1'), R ¹ is hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons , or an alkyl group having 1 to 12 carbons substituted with at least one hydrogen by fluorine or chlorine; R ² is an alkyl group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, at least one hydrogen substituted by fluorine or chlorine Alkyl having 1 to 12 carbon atoms, among these groups, at least one -CH ₂ - may be substituted by -O-, -COO-, or -OCO-; Ring A is 1,4-cyclohexylene, 1,4 -Cyclohexenyl, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl , naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl , in these rings, at least one hydrogen can be substituted by fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least one hydrogen with 1 to 12 carbons substituted by fluorine or chlorine Alkyl-substituted; a is 1 or 2; b is 0, 1, 2, 3, or 4.

Item 24. The compound of Item 23, wherein R ² is methyl, tertiary butyl, tertiary pentyl, or tertiary octyl, and b is 1, 2, 3, or 4.

式（1'-1）至式（1'-4）中，R² 為甲基、第三丁基、第三戊基、或第三辛基。Item 25. The compound according to Item 24, which is represented by formula (1'-1), formula (1'-2), formula (1'-3), or formula (1'-4).

In the formula (1'-1) to the formula (1'-4), R ² is a methyl group, a tertiary butyl group, a 3rd pentyl group, or a 3rd octyl group.

The present invention also includes the following items. (a) The composition containing additives selected from the group consisting of optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, and polymerization inhibitors One compound, two compounds, or three or more compounds. (b) An AM device including the composition. (c) The composition and a polymer-stabilized alignment (PSA) type AM device containing the composition, the composition further containing a polymerizable compound. (d) A polymer-stabilized alignment (PSA) type AM device comprising the composition, wherein the polymerizable compound in the composition is polymerized. (e) An element comprising the composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA. (f) A transmissive element comprising the composition. (g) Use of the composition as a composition having a nematic phase. (h) Use as an optically active composition by adding an optically active compound to the composition.

The composition of the present invention will be described in the following order. First, the constitution of the component compounds in the composition will be described. Second, the main properties of the component compounds and the main effects of the compounds on the composition will be described. Third, the combination of the components in the composition, the preferred ratio of the components, and the basis thereof will be described. Fourth, preferred forms of the component compounds will be described. Fifth, preferred constituent compounds are shown. Sixth, additives that can be added to the composition will be described. Seventh, the synthesis method of the component compounds will be described. Finally, the use of the composition will be described.

First, the constitution of the composition will be described. The composition contains various liquid crystal compounds. The composition may also contain additives. The additives are optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. From the viewpoint of the liquid crystal compound, the composition is classified into composition A and composition B. The composition A may further contain other liquid crystal compounds, additives, and the like in addition to the liquid crystal compound selected from the group consisting of compound (2), compound (3), and compound (4). The "other liquid crystal compound" is a liquid crystal compound different from the compound (2), the compound (3), and the compound (4). Such a compound is mixed in the composition for the purpose of further adjusting the properties.

Composition B contains substantially only the liquid crystal compound selected from the group consisting of compound (2), compound (3), and compound (4). "Substantially" means that although the composition B may contain additives, it does not contain other liquid crystal compounds. Compared with the composition A, the number of components of the composition B is small. Composition B is superior to Composition A from the viewpoint of cost reduction. The composition A is superior to the composition B in that the characteristics can be further adjusted by mixing other liquid crystal compounds.

Second, the main characteristics of the component compounds and the main effects that the compounds bring to the composition or element are explained. Based on the effects of the present invention, the main characteristics of the component compounds are summarized in Table 2. In the notation in Table 2, L means large or high, M means medium, and S means small or low. The notations L, M, S are classifications based on qualitative comparisons between the constituent compounds, and 0 (zero) means extremely small.

[Table 2]

The main effects of the component compounds are as follows. The compound (1) functions as an ultraviolet absorber and contributes to high stability against heat or ultraviolet rays. Since the amount of compound (1) added is very small, it does not affect properties such as the upper limit temperature, optical anisotropy, and dielectric anisotropy in many cases. Compound (2) lowers the viscosity, or raises the upper limit temperature. Compound (3) increases the positive dielectric anisotropy and lowers the lower limit temperature. Compound (4) increases the negative dielectric anisotropy and lowers the lower limit temperature. Since compound (5) is polymerizable, it is polymerized to provide a polymer. Since this polymer stabilizes the alignment of liquid crystal molecules, the response time of the element is shortened, and the afterimage of the image is improved.

The ultraviolet absorber absorbs ultraviolet rays in place of liquid crystal molecules by being added to the liquid crystal composition. By absorbing light energy, the UV absorber transitions from the ground state to the excited state. Excited state molecules undergo structural changes due to intramolecular proton transfer processes, which release heat to return to the ground state. As another mechanism, it returns to the ground state by radiating light of lower energy than absorbed light. By adding the ultraviolet absorber to the liquid crystal composition, deterioration of the liquid crystal molecules due to ultraviolet absorption can be suppressed.

The ultraviolet absorber preferably has an absorption wavelength range that broadly covers the absorption wavelength of the liquid crystal composition or the wavelength of exposed ultraviolet light. UV absorbers vary in absorption wavelength range and efficiency depending on their structure. From this point of view, the compound (1) is a useful ultraviolet absorber.

Third, the combination of components in the composition, the preferred ratio of the component compounds, and the basis thereof will be described. The preferred combination of components in the composition is compound (1)+compound (2), compound (1)+compound (3), compound (1)+compound (4), compound (1)+compound (2)+ Compound (3), Compound (1) + Compound (2) + Compound (4), Compound (1) + Compound (2) + Compound (3) + Compound (4), or Compound (1) + Compound (2) +Compound (4)+Compound (5). A particularly preferred combination is compound (1)+compound (2)+compound (3).

The preferable ratio of compound (1) is about 0.005 mass % or more in order to improve the stability against heat or ultraviolet rays, and the preferable ratio of compound (1) is about 2 mass % or less in order to lower the minimum temperature. A more preferable ratio is in the range of about 0.01 mass % to about 1 mass %. A particularly preferable ratio is in the range of about 0.03 mass % to about 0.5 mass %.

In order to increase the upper limit temperature or to reduce the viscosity, the preferred ratio of the compound (2) is about 10 mass % or more, and the preferred ratio of the compound (2) is about 85 mass % or less in order to increase the dielectric anisotropy. A more preferable ratio is in the range of about 20% by mass to about 80% by mass. A particularly preferable ratio is in the range of about 30% by mass to about 70% by mass.

In order to increase the positive dielectric anisotropy, the preferable ratio of the compound (3) is about 10 mass % or more, and the preferable ratio of the compound (3) is about 85 mass % or less in order to lower the minimum temperature. A more preferable ratio is in the range of about 20% by mass to about 80% by mass. A particularly preferable ratio is in the range of about 30% by mass to about 70% by mass.

In order to increase the negative dielectric anisotropy, the preferable ratio of the compound (4) is about 5 mass % or more, and the preferable ratio of the compound (4) is about 80 mass % or less in order to lower the minimum temperature. A more preferable ratio is in the range of about 5% by mass to about 75% by mass. A particularly preferable ratio is in the range of about 10% by mass to about 70% by mass.

The compound (5) may be added to the composition for the purpose of being suitable for a polymer-stabilized alignment-type element. In order to align the liquid crystal molecules, the preferable ratio of the compound (5) is about 0.03 mass % or more, and the preferable ratio of the compound (5) is about 10 mass % or less in order to prevent the display failure of the device. A more preferable ratio is in the range of about 0.1 mass % to about 2 mass %. A particularly preferable ratio is in the range of about 0.2 mass % to about 1.0 mass %.

Fourth, preferred forms of the component compounds will be described. In formula (1), formula (2), formula (3), and formula (4), R ¹ is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkyl group having 2 to 12 carbon atoms. Alkenyl of 12, alkenyloxy of 2 to 12 carbons, or alkyl of 1 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine. Preferred R ¹ is hydrogen or an alkyl group having 1 to 12 carbons. R ² is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms having at least one hydrogen replaced by fluorine or chlorine, and among these groups, at least one -CH ₂ - It may be substituted with -O-, -COO-, or -OCO-, or a group represented by formula (A-1). In order to improve the effect of contributing to the stability of the liquid crystal, preferable R ² is a methyl group, a tertiary butyl group, a tertiary pentyl group, a tertiary octyl group, or an α-pentyl group. R ³ and R ⁴ are independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or an alkyl group having 2 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine. 12 alkenyl. In order to reduce viscosity, preferably R ³ or R ⁴ is an alkenyl group having 2 to 12 carbon atoms, and in order to improve stability, preferably R ³ or R ⁴ is an alkyl group having 1 to 12 carbon atoms. R ⁵ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons. In order to improve stability, preferable R ⁵ is an alkyl group having 1 to 12 carbons. R ⁶ and R ⁷ are independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or an alkenyloxy group having 2 to 12 carbons. In order to improve stability, preferably R ⁶ or R ⁷ is an alkyl group having 1 to 12 carbon atoms, and in order to improve dielectric anisotropy, preferably R ⁶ or R ⁷ is an alkoxy group having 1 to 12 carbon atoms.

In formula (A-1), R ^a is fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkane having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine group, among these groups, at least one -CH ₂ - may be substituted with -O-, -COO-, or -OCO-. Preferred R ^a is an alkyl group having 1 to 12 carbons or an alkoxy group having 1 to 12 carbons. Z ^a is a branched alkylene group having 1 to 20 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be substituted with -O-, -COO-, or -OCO-. In addition, at least one -CH ₂ -CH ₂ - in the alkylene group may be substituted with -CH=CH-. Preferred Z ^a is an alkylene group having 1 to 3 carbons which can also be branched. Particularly preferred Z ^a is methylene or dimethylmethylene. s is either 0 or 1. A preferable s is 1. t is 0, 1, 2, 3, 4, or 5. Preferred t is 0 or 1.

Preferred alkyl groups are methyl, ethyl, propyl, butyl, tertiary butyl, pentyl, tertiary pentyl, hexyl, heptyl, octyl, or tertiary octyl. In order to reduce viscosity, further preferred alkyl groups are methyl, ethyl, propyl, butyl, or pentyl.

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. In order to reduce the viscosity, further preferable alkoxy groups are methoxy groups or ethoxy groups.

Preferred alkenyl groups are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-butenyl -Pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. Further preferred alkenyl groups are vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl in order to reduce viscosity. The preferred stereoconfiguration of -CH=CH- in these alkenyl groups depends on the position of the double bond. Among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl, for reasons such as viscosity reduction, trans configuration. Among alkenyl groups such as 2-butenyl, 2-pentenyl, and 2-hexenyl, the cis configuration is preferred.

Preferred alkenyloxy groups are vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. Further preferred alkenyloxy is allyloxy or 3-butenyloxy in order to reduce viscosity.

Preferred examples of the alkyl group in which at least one hydrogen is substituted with fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7 -Fluoroheptyl, or 8-fluorooctyl. In order to increase the dielectric anisotropy, more preferable examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl.

Preferred examples of the alkenyl group in which at least one hydrogen is substituted with fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro-4-pentenyl, or 6,6-difluoro-5-hexenyl. In order to reduce the viscosity, a more preferable example is 2,2-difluorovinyl or 4,4-difluoro-3-butenyl.

Ring A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1 ,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl , naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen may be fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least One hydrogen is substituted with an alkyl group having 1 to 12 carbons substituted with fluorine or chlorine. Preferred ring A is 1,4-phenylene or naphthalene-2,6-diyl.

Ring B and Ring C are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene base. In order to lower the viscosity or to increase the upper limit temperature, preferable ring B or ring C is 1,4-cyclohexylene, and in order to lower the lower limit temperature, preferable ring B or ring C is 1,4-phenylene.

或

，較佳為

。Ring D is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6- Difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl. In order to increase the upper limit temperature, the preferred ring D is 1,4-cyclohexylene. In order to increase the optical anisotropy, the preferred ring D is 1,4-phenylene. In order to increase the dielectric anisotropy, the preferred Ring D is 2,6-difluoro-1,4-phenylene. Tetrahydropyran-2,5-diyl is

or

, preferably

.

Ring E and Ring G are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is substituted with fluorine or chlorine , or tetrahydropyran-2,5-diyl. Preferred examples of "1,4-phenylene in which at least one hydrogen is substituted with fluorine or chlorine" are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene or 2-Chloro-3-fluoro-1,4-phenylene. In order to reduce the viscosity, the preferred ring E or G is 1,4-cyclohexylene, and in order to improve the dielectric anisotropy, the preferred ring E or G is tetrahydropyran-2,5-diyl, In order to increase optical anisotropy, preferable ring E or ring G is 1,4-phenylene.

Ring F is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4- phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl. In order to reduce the viscosity, the preferred ring F is 2,3-difluoro-1,4-phenylene, and in order to reduce the optical anisotropy, the preferred ring F is 2-chloro-3-fluoro-1,4- For the phenylene group, in order to improve the dielectric anisotropy, the preferred ring F is 7,8-difluorochroman-2,6-diyl.

Z ¹ is a single bond, ethylidene, carbonyloxy, or methyleneoxy. In order to reduce the viscosity, the preferred Z ¹ is a single bond. Z ² is a single bond, ethylidene, carbonyloxy, or difluoromethyleneoxy. In order to reduce the viscosity, the preferred Z ² is a single bond, and in order to improve the dielectric anisotropy, the preferred Z ² is a difluoromethyleneoxy group. Z ³ and Z ⁴ are independently a single bond, ethylidene, carbonyloxy, or methyleneoxy. In order to reduce the viscosity, the preferred Z ³ or Z ⁴ is a single bond, in order to reduce the lower limit temperature, the preferred Z ³ or Z ⁴ is an ethylidene group, in order to improve the dielectric anisotropy, the preferred Z ³ or Z ⁴ is methyleneoxy.

X ¹ and X ² are independently hydrogen or fluorine. In order to increase the dielectric anisotropy, preferable X ¹ or X ² is fluorine.

Y ¹ is fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine, an alkoxy group having 1 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine, or at least one hydrogen is substituted by fluorine or chlorine-substituted alkenyloxy having 2 to 12 carbons. In order to increase the dielectric anisotropy, the preferable Y ¹ is fluorine. A preferred example of the alkyl group in which at least one hydrogen is substituted with fluorine or chlorine is trifluoromethyl. A preferred example of the alkoxy group in which at least one hydrogen is substituted with fluorine or chlorine is trifluoromethoxy. A preferred example of the alkenyloxy group in which at least one hydrogen is substituted with fluorine or chlorine is trifluorovinyloxy.

a is 1 or 2, and b is 0, 1, 2, 3, or 4. The preferable a is 1, and the preferable b is 1. c is 1, 2, or 3. In order to reduce the viscosity, the preferred c is 1, and in order to increase the upper limit temperature, the preferred c is 2 or 3. d is 1, 2, 3, or 4. Desirable d is 2 or 3 in order to increase the dielectric anisotropy. e is 1, 2, or 3. In order to reduce the viscosity, the preferred e is 1, and in order to increase the upper limit temperature, the preferred e is 2 or 3. f is 0 or 1. In order to reduce the viscosity, the preferred f is 0, and the preferred f is 1 in order to reduce the lower limit temperature. The sum of e and f is 3 or less.

In formula (5), P ¹ , P ² , and P ³ are independently polymerizable groups. Preferred P ¹ , P ² , or P ³ are groups selected from the group of polymerizable groups represented by formula (P-1) to formula (P-5). Further preferable P ¹ , P ² , or P ³ is a group (P-1) or a group (P-2). A particularly preferred group (P-1) is -OCO-CH=CH ₂ or -OCO-C(CH ₃ )=CH ₂ . The wavy line from the base (P-1) to the base (P-5) indicates the bonded portion.

In the groups (P-1) to (P-5), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen substituted by fluorine or chlorine Alkyl having 1 to 5 carbons. In order to improve reactivity, preferable M ¹ , M ² , or M ³ is hydrogen or methyl. Further preferred M ¹ is methyl, and further preferred M ² or M ³ is hydrogen.

In Formulas (5-1) to (5-29), P ⁴ , P ⁵ , and P ⁶ are independently groups represented by Formulas (P-1) to (P-3). Preferred P ⁴ , P ⁵ , or P ⁶ are radicals (P-1) or radicals (P-2). A further preferable group (P-1) is -OCO-CH=CH ₂ or -OCO-C(CH ₃ )=CH ₂ . The wavy line from the base (P-1) to the base (P-3) indicates the bonded portion.

In formula (5), Sp ¹ , Sp ² , and Sp ³ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be passed through -O-, - COO-, -OCO-, or -OCOO- substituted, at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by fluorine or chlorine replace. Preferred Sp ¹ , Sp ² , or Sp ³ are single bonds, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CO-CH=CH-, or -CH=CH-CO-. Further preferable Sp ¹ , Sp ² , or Sp ³ are single bonds.

Ring I and Ring K 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 can be fluorine or chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen Substituted with alkyl having 1 to 12 carbons substituted with fluorine or chlorine. Preferred ring I or ring K is phenyl. Ring J is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1 ,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl , naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen can be fluorine or chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least One hydrogen is substituted with an alkyl group having 1 to 12 carbons substituted with fluorine or chlorine. Preferred ring J is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁵ and Z ⁶ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be through -O-, -CO-, -COO-, or -OCO -Substituted, at least one -CH ₂ -CH ₂ - may be via -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )-, or -C(CH ₃ )=C( _CH3 )-substituted, in these groups, at least one hydrogen may be replaced by fluorine or chlorine. Preferred Z ⁵ or Z ⁶ is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, or -OCO-. Furthermore, preferably Z ⁵ or Z ⁶ is a single bond.

g is 0, 1, or 2. Desirable g is 0 or 1. h, i, and j are independently 0, 1, 2, 3, or 4, and the sum of h, i, and j is 1 or more. Preferred h, i, or j are 1 or 2.

Fifth, preferred constituent compounds are shown. Preferable compound (1) is compound (1-1) to compound (1-4) described in item 3, and more preferable compound (1) is compound (1'-1) to compound (1) described in item 25 1'-4).

Preferred compounds (2) are the compounds (2-1) to (2-13) described in item 6. Among these compounds, preferably at least one of the first components is compound (2-1), compound (2-3), compound (2-5), compound (2-6), or compound (2-8) . A particularly preferred compound (2) is a compound (2-1) wherein at least one of R ³ and R ⁴ is an alkenyl group, and particularly preferred is 3-HH-V. And preferably at least two of the first components are compound (2-1) and compound (2-3), compound (2-1) and compound (2-5), or compound (2-1) and compound ( 2-6) combination.

Preferred compounds (3) are the compounds (3-1) to (3-35) described in item 9. Among these compounds, preferably at least one of the second components is compound (3-4), compound (3-12), compound (3-14), compound (3-15), compound (3-18), Compound (3-23), compound (3-24), compound (3-27), compound (3-29), or compound (3-30). And preferably at least two of the second components are compound (3-12) and compound (3-15), compound (3-14) and compound (3-27), compound (3-18) and compound (3) -24), compound (3-18) and compound (3-29), compound (3-24) and compound (3-29), or a combination of compound (3-29) and compound (3-30).

Preferred compounds (4) are the compounds (4-1) to (4-27) described in Item 12. Among these compounds, preferably at least one of the third components is compound (4-1), compound (4-3), compound (4-6), compound (4-8), compound (4-10), or compounds (4-14). And preferably at least two of the third components are compound (4-1) and compound (4-8), compound (4-3) and compound (4-8), compound (4-3) and compound (4) -14), compound (4-6) and compound (4-8), compound (4-6) and compound (4-10), or a combination of compound (4-8) and compound (4-14).

Preferred compounds (5) are the compounds (5-1) to (5-29) described in item 16. Among these compounds, preferably at least one of the second additives is compound (5-1), compound (5-2), compound (5-24), compound (5-25), compound (5-26) , or compound (5-27). And preferably at least two kinds of second additives are compound (5-1) and compound (5-2), compound (5-1) and compound (5-18), compound (5-2) and compound ( 5-24), compound (5-2) and compound (5-25), compound (5-2) and compound (5-26), compound (5-25) and compound (5-26), or compound ( 5-18) and a combination of compounds (5-24).

Sixth, additives that can be added to the composition will be described. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, matting agents, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. The optically active compound is added to the composition for the purpose of imparting a torsion angle by inducing a helical structure of liquid crystal molecules. Examples of such compounds are compounds (6-1) to (6-5). A preferable ratio of the optically active compound is about 5% by mass or less. A more preferable ratio is in the range of about 0.01 mass % to about 2 mass %.

Antioxidants are added to prevent a decrease in specific resistance caused by heating in the atmosphere, or to maintain a large voltage holding ratio not only at room temperature but also at temperatures close to the upper limit temperature after using the element for a long time. in the composition. Preferable examples of the antioxidant are compounds (7-1) to (7-3) and the like.

Since the compound (7-2) has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after the device is used for a long time. In order to obtain the effect, the preferable ratio of the antioxidant is about 50 ppm or more, and in order not to lower the upper limit temperature, or not to increase the lower limit temperature, the preferable ratio of the antioxidant is about 600 ppm or less. A further preferred ratio is in the range of about 100 ppm to about 300 ppm.

Compound (1) is a benzotriazole derivative useful as an ultraviolet absorber. This benzotriazole derivative may be added to the composition together with other ultraviolet absorbers. Preferable examples of such ultraviolet absorbers are benzophenone derivatives, benzoate derivatives, and the like. In addition, light stabilizers such as amines having steric hindrance are also preferred. Preferred examples of the light stabilizer are compound (8-1) to compound (8-16) and the like. In order to obtain the effect, the preferred ratio of these absorbents or stabilizers is about 50 ppm or more, in order not to lower the upper limit temperature, or in order not to increase the lower limit temperature, the preferred ratio of these absorbents or stabilizers is about 10000 ppm ppm or less. A further preferred ratio is in the range of about 100 ppm to about 10,000 ppm.

The matting agent is a compound that prevents decomposition of the liquid crystal compound by receiving light energy absorbed by the liquid crystal compound and converting it into heat energy. Preferable examples of the matting agent are compound (9-1) to compound (9-7) and the like. In order to obtain the above effect, the preferred proportion of these matting agents is about 50 ppm or more, and in order not to increase the lower limit temperature, the preferred proportion of these matting agents is about 20000 ppm or less. A further preferred ratio is in the range of about 100 ppm to about 10,000 ppm.

Dichroic dyes such as azo-based dyes and anthraquinone-based dyes are added to the composition in order to be suitable for a guest host (GH) mode device. A preferable ratio of the pigment is in the range of about 0.01% by mass to about 10% by mass. In order to prevent foaming, antifoaming agents such as dimethyl silicone oil and methyl phenyl silicone oil are added to the composition. In order to obtain the above-mentioned effects, the preferable ratio of the antifoaming agent is about 1 ppm or more, and the preferable ratio of the antifoaming agent is about 1000 ppm or less in order to prevent poor display. A further preferred ratio is in the range of about 1 ppm to about 500 ppm.

A polymerizable compound is used in order to be suitable for a polymer-stabilized alignment (PSA) type element. Compound (5) is suitable for this purpose. Compound (5) and a polymerizable compound different from compound (5) may be added to the composition together. Preferable examples of such polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes), vinyl compounds ketones and other compounds. Further preferred examples are derivatives of acrylate or methacrylate. The preferable ratio of compound (5) is 10 mass % or more based on the total mass of a polymerizable compound. A more preferable ratio is 50 mass % or more. A particularly preferable ratio is 80% by mass or more. The optimum ratio is 100% by mass.

Polymerizable compounds such as compound (5) are polymerized by ultraviolet irradiation. The polymerization can also be carried out in the presence of an appropriate initiator such as a photopolymerization initiator. Appropriate conditions for carrying out the polymerization, appropriate types of initiators, and appropriate amounts are known to those of ordinary skill in the art and described in the literature. For example, as a photopolymerization initiator, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 ( registered trademark; BASF (BASF)) suitable for free radical polymerization. A preferable ratio of the photopolymerization initiator is in the range of about 0.1% by mass to about 5% by mass based on the total mass of the polymerizable compound. A more preferable ratio is in the range of about 1% by mass to about 3% by mass.

When storing a polymerizable compound such as compound (5), a polymerization inhibitor may be added in order to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of the polymerization inhibitor are hydroquinone, hydroquinone derivatives such as methyl hydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine, and the like.

Seventh, the synthesis method of the component compounds will be described. These compounds can be synthesized by known methods. Synthetic methods are exemplified. Synthesis examples of compound (1) are described in the section of Examples. Compound (2-1) was synthesized by the method described in Japanese Patent Laid-Open No. Sho 59-176221. Compound (3-4) was synthesized by the method described in Japanese Patent Laid-Open No. 10-204016. Compound (4-1) was synthesized by the method described in Japanese Patent Laid-Open No. 2000-053602. Compound (5-18) was synthesized by the method described in Japanese Patent Laid-Open No. 7-101900. Antioxidants are commercially available. Compounds of formula (7) wherein n is 1 are available from Sigma-Aldrich Corporation. Compound (7) and the like in which n is 7 are synthesized by the method described in the specification of US Pat. No. 3,660,505.

Compounds whose synthesis methods are not described can be synthesized by the methods described in the following books: "Organic Syntheses" (John Wiley & Sons, Inc), "Organic Reactions" )" (John Wiley & Sons, Inc), "Comprehensive Organic Synthesis" (Pergamon Press), "New Experimental Chemistry Lectures" (Maruzen) Wait. The composition is prepared from the compound obtained in the above-described manner by a known method. For example, the component compounds are mixed and then dissolved in each other by heating.

Finally, the use of the composition will be described. Most of the compositions have a lower limit temperature of about -10°C or lower, an upper limit temperature of about 70°C or higher, and an optical anisotropy in the range of about 0.07 to about 0.20. A composition having an optical anisotropy in the range of about 0.08 to about 0.25 can be prepared by controlling the ratio of the component compounds, or by mixing other liquid crystal compounds. Furthermore, a composition having an optical anisotropy in the range of about 0.10 to about 0.30 can also be prepared by trial and error. A device containing this composition has a large voltage holding ratio. This composition is suitable for AM devices. This composition is particularly suitable for a transmission type AM device. The composition can be used as a composition having a nematic phase, or can be used as an optically active composition by adding an optically active compound.

This composition can be used for AM devices. Furthermore, it can also be used for PM elements. The composition can be used for AM elements and PM elements having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, and FPA. Especially preferred for AM devices with VA mode, OCB mode, IPS mode or FFS mode. In an AM device having an IPS mode or an FFS mode, when no voltage is applied, the alignment of the liquid crystal molecules may be parallel or perpendicular to the glass substrate. The elements can be reflective, transmissive or transflective. It is preferably used for a transmission type element. It can also be used for amorphous silicon-TFT elements or polysilicon-TFT elements. It can also be used for nematic curvilinear aligned phase (NCAP) type elements made by microencapsulating the composition or polymer dispersed (polymer dispersed) formed by forming three-dimensional network polymers in the composition. , PD) type components. [Example]

The present invention will be further described in detail by means of examples. The present invention is not limited by these Examples. The present invention includes a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes mixtures obtained by mixing at least two of the compositions of the examples. The synthesized compounds were identified by methods such as nuclear magnetic resonance (NMR) analysis. The properties of compounds, compositions, and elements were measured by the methods described below.

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

Gas chromatography analysis: A GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for the measurement. The carrier gas was helium (2 mL/min). The sample vaporization chamber was set to 280°C, and the detector (flame ionization detector (FID)) was set to 300°C. For the separation of component compounds, a capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc. was used; the stationary liquid phase was dimethyl polysiloxane. oxane; non-polar). After the column was held at 200°C for 2 minutes, the temperature was raised to 280°C at a rate of 5°C/min. After the sample was prepared as an acetone solution (0.1 mass %), 1 μL of the solution was injected into the sample vaporization chamber. The recorder was a C-R5A type chromatograph kit (Chromatopac) manufactured by Shimadzu Corporation or its equivalent. The obtained gas chromatogram showed the retention time of the peak and the area of the peak corresponding to the component compounds.

As a solvent for diluting the sample, chloroform, hexane, or the like can be used. In order to separate the component compounds, the following capillary columns can be used. HP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc., Rtx-1 (length 30 m, inner diameter 0.25 μm) manufactured by Restek Corporation diameter 0.32 mm, film thickness 0.25 μm), BP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by SGE International Pty. Ltd, Australia. To prevent overlapping of compound peaks, a capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Shimadzu Corporation was used.

The ratio of the liquid crystal compound contained in the composition can be calculated by the following method. The mixture of liquid crystal compounds was analyzed by gas chromatography (FID). The area ratio of the peaks in the gas chromatogram corresponds to the ratio (mass ratio) of the liquid crystalline compounds. When the capillary column described above is used, the correction coefficient of each liquid crystal compound can be regarded as 1. Therefore, the ratio (mass %) of the liquid crystal compound can be calculated from the area ratio of the peaks.

Absorbance: U-2001 double-beam spectrophotometer manufactured by Hitachi High-Tech Science was used in the measurement. The measuring cell was T-23-UV-10 using a quartz glass cell manufactured by Tosoh Quartz, and only cyclohexane for spectroscopic analysis manufactured by Wako Pure Chemical Industries was placed in the reference cell and in the sample cell. A measurement solution prepared with cyclohexane for spectroscopic analysis so that the concentration of the sample becomes 2.00 μmol/g. Absorbance was scanned over a region of wavelengths from 800 nm to 200 nm in unit widths of 1 nm.

Measurement sample: When measuring the properties of a composition or element, the composition is directly used as a sample. When the properties of the compound were measured, a sample for measurement was prepared by mixing the compound (15% by mass) with the mother liquid crystal (85% by mass). From the value obtained by the measurement, the characteristic value of the compound was calculated by an extrapolation method. (Extrapolated value)={(Measured value of sample)-0.85×(Measured value of mother liquid crystal)}/0.15. In this ratio, when the smectic phase (or crystal) is precipitated at 25°C, the ratio of the compound to the mother liquid crystal is 10 mass %: 90 mass %, 5 mass %: 95 mass %, and 1 mass %: 99 mass % The order of % is changed. The values of the upper limit temperature, optical anisotropy, viscosity, and dielectric anisotropy related to the compound are obtained by this extrapolation method.

The following mother liquid crystals were used. The ratio of the component compounds is represented by mass %.

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

In the liquid crystal composition having positive dielectric anisotropy, the measurement methods (1) to (15) described below were used.

(1) Upper limit temperature of nematic phase (NI; °C): The sample was placed on a hot plate of a melting point measuring device equipped with a polarizing microscope, and heated at a rate of 1 °C/min. The temperature at which a part of the sample changes from the nematic phase to the isotropic liquid is measured. The upper limit temperature of the nematic phase is sometimes abbreviated as "upper limit temperature".

(2) Lower limit temperature of nematic phase (TC; ° _C ): put the sample with nematic phase into a glass bottle, and set the temperature at 0 °C, -10 °C, -20 °C, -30 °C, and -40 °C The liquid crystal phase was observed after 10 days of storage in the refrigerator. For example, when the sample is in the state of nematic phase at -20°C, and changes to crystalline or smectic phase at -30°C, T _C is described as <-20°C. The lower limit temperature of the nematic phase is sometimes abbreviated as "lower limit temperature".

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

(4) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s): According to M. Imai et al. "Molecular Crystals and Liquid Crystals" No. 259 Measured by the method described in p. 37 (1995). A sample was placed in a TN element with a twist angle of 0° and a gap (cell gap) between two glass substrates of 5 μm. A voltage in the range of 16 V to 19.5 V is applied to the element in steps of 0.5 V. After no voltage application for 0.2 seconds, application of only one rectangular wave (rectangular pulse; 0.2 seconds) and no voltage application (2 seconds) were repeated. The peak current (peak current) and peak time (peak time) of the transient current (transient current) generated by the application were measured. The value of the rotational viscosity was obtained from these measured values and the calculation formula (8) described on page 40 of the paper by M. Imai et al. The value of the dielectric anisotropy required for the calculation was obtained by the method described below using an element for measuring the rotational viscosity.

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

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

(7) Threshold voltage (Vth; measured at 25° C.; V): An LCD5100 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 TN element in a normally white mode with an interval (cell gap) between two glass substrates of 0.45/Δn (μm) and a twist angle of 80 degrees. The voltage (32 Hz, rectangular wave) applied to the element was increased in steps from 0 V to 10 V in units of 0.02 V. At this time, the element was irradiated with light from a vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was prepared in which the transmittance was 100% when the light amount reached the maximum, and the transmittance was 0% when the light amount was the minimum. The threshold voltage is represented by the voltage at which the transmittance reaches 90%.

(8) Voltage holding ratio (VHR-1; measured at 25° C.; %): The TN element used in the measurement had a polyimide alignment film, and the distance (cell gap) between the two glass substrates was 5 μm. After the element is placed in the sample, it is sealed with an adhesive that hardens with UV light. The TN element was charged by applying a pulse voltage (1 V, 60 microseconds). Using a high-speed voltmeter, the decayed voltage was measured for 166.7 milliseconds, and the area A between the voltage curve in a unit cycle and the horizontal axis was obtained. Area B is the area without attenuation. Voltage retention is expressed as the percentage of area A relative to area B.

(9) Voltage holding ratio (VHR-2; measured at 60°C; %): The voltage holding ratio was measured in the same procedure as described above, except that the measurement was performed at 60°C instead of 25°C. The obtained value is represented by VHR-2.

(10) Voltage holding ratio (VHR-3; measured at 60° C.; %): After irradiation with ultraviolet rays, the voltage holding ratio was measured, and the stability against ultraviolet rays was evaluated. The TN element used in the measurement has a polyimide alignment film and has a cell gap of 5 μm. A sample was injected into this element and irradiated with ultraviolet rays of 5 mW/cm ² for 167 minutes. The light source was a black light, F40T10/BL (peak wavelength 369 nm) manufactured by EYEGRAPHICS Co., Ltd., and the distance between the element and the light source was 5 mm. In the measurement of VHR-3, the decayed voltage was measured during 166.7 milliseconds. Compositions with large VHR-3 have large UV stability.

(11) Voltage holding ratio (VHR-4; measured at 60°C; %): After heating the TN element injected with the sample in a constant temperature bath at 120°C for 20 hours, the voltage holding ratio was measured, and the resistance to heat was evaluated. stability. In the measurement of VHR-4, the decayed voltage was measured during 166.7 milliseconds. Compositions with large VHR-4 have large thermal stability.

(12) Response time (τ; measured at 25° C.; ms): 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 element with a gap (cell gap) between two glass substrates of 5.0 μm and a twist angle of 80 degrees. A rectangular wave (60 Hz, 5 V, 0.5 sec) was applied to the element. At this time, the element was irradiated with light from a vertical direction, and the amount of light transmitted through the element was measured. When the light amount reached the maximum, the transmittance was regarded as 100%, and when the light amount was the minimum, the transmittance was regarded as 0%. Rise time (τr: rise time; milliseconds) is the time required for the transmittance to change from 90% to 10%. The fall time (τf: fall time; milliseconds) is the time required to change the transmittance from 10% to 90%. The response time is represented by the sum of the rise time and fall time obtained in the manner described above.

(13) Elastic constant (K; measured at 25° C.; pN): HP4284A type LCR tester 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) between two glass substrates of 20 μm. A charge of 0 to 20 volts was applied to the element, and the capacitance and the applied voltage were measured. Using equations (2.98) and (2.101) on page 75 of the "Handbook of Liquid Crystal Devices" (Nikkan Kogyo Shimbun Co., Ltd.), the measured electrostatic capacitance (C) was fitted to the value of the applied voltage (V), and according to the equation ( 2.99) to obtain the values of K11 and K33. Next, K22 is calculated using the previously obtained values of K11 and K33 in equation (3.18) on page 171 of the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun Co., Ltd.). The elastic constant is represented by the average value of K11, K22, and K33 obtained as described above.

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

(15) Dielectric constant in the short-axis direction (ε⊥; measured at 25°C): A sample was placed in a TN device with a gap (cell gap) between two glass substrates of 9 μm and a twist angle of 80 degrees . A sine wave (0.5 V, 1 kHz) was applied to this element, and after 2 seconds, the dielectric constant (ε⊥) in the short axis direction of the liquid crystal molecules was measured.

In the liquid crystal composition having negative dielectric anisotropy, the measurement methods (16) to (28) described below were used.

(16) Upper limit temperature of nematic phase (NI; °C): The sample was placed on a hot plate of a melting point measuring device equipped with a polarizing microscope, and heated at a rate of 1 °C/min. The temperature at which a part of the sample changes from a nematic phase to an isotropic liquid is measured. The upper limit temperature of the nematic phase is sometimes abbreviated as "upper limit temperature".

(17) Lower limit temperature of nematic phase (T _C ; °C): put the sample with nematic phase into a glass bottle, at 0 °C, -10 °C, -20 °C, -30 °C, and -40 °C The liquid crystal phase was observed after 10 days of storage in the refrigerator. For example, when the sample is in the state of nematic phase at -20°C, and changes to crystalline or smectic phase at -30°C, T _C is described as <-20°C. The lower limit temperature of the nematic phase is sometimes abbreviated as "lower limit temperature".

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

(19) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa s): According to M. Imai et al. "Molecular Crystals and Liquid Crystals" No. 259 Measured by the method described in p. 37 (1995). A sample was placed in a VA element with a gap (cell gap) between two glass substrates of 20 μm. The element was applied stepwise in units of 1 volt in the range of 39 volts to 50 volts. After no voltage application for 0.2 seconds, application of only one rectangular wave (rectangular pulse; 0.2 seconds) and no voltage application (2 seconds) were repeated. The peak current (peak current) and peak time (peak time) of the transient current (transient current) generated by the application were measured. The value of rotational viscosity was obtained from these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al. The dielectric anisotropy required for this calculation is determined using item (6).

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

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

(22) Threshold voltage (Vth; measured at 25° C.; V): 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 black mode VA element in which the distance (cell gap) between two glass substrates was 4 μm and the rubbing direction was anti-parallel, and the adhesive was cured with ultraviolet rays. Elements are sealed. The voltage (60 Hz, rectangular wave) applied to the element was increased in steps from 0 V to 20 V in units of 0.02 V. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was prepared in which the transmittance was 100% when the light amount reached the maximum, and the transmittance was 0% when the light amount was the minimum. The threshold voltage is represented by the voltage at which the transmittance reaches 10%.

(23) Voltage holding ratio (VHR-1; measured at 25° C.; %): The TN element used in the measurement had a polyimide alignment film, and the distance (cell gap) between the two glass substrates was 5 μm. After the element is placed in the sample, it is sealed with an adhesive that hardens with UV light. The TN element was charged by applying a pulse voltage (1 V, 60 microseconds). Using a high-speed voltmeter, the decayed voltage was measured for 166.7 milliseconds, and the area A between the voltage curve in a unit cycle and the horizontal axis was obtained. Area B is the area without attenuation. Voltage retention is expressed as the percentage of area A relative to area B.

(24) Voltage holding ratio (VHR-2; measured at 60°C; %): The voltage holding ratio was measured in the same procedure as described above, except that the measurement was performed at 60°C instead of 25°C. The obtained value is represented by VHR-2.

(25) Voltage holding ratio (VHR-3; measured at 60° C.; %): After irradiation with ultraviolet rays, the voltage holding ratio was measured, and the stability against ultraviolet rays was evaluated. The TN element used in the measurement has a polyimide alignment film and has a cell gap of 5 μm. A sample was injected into this element and irradiated with ultraviolet rays of 5 mW/cm ² for 167 minutes. The light source was a black light, F40T10/BL (peak wavelength 369 nm) manufactured by EYEGRAPHICS Co., Ltd., and the distance between the element and the light source was 5 mm. In the measurement of VHR-3, the decayed voltage was measured during 166.7 milliseconds. Compositions with large VHR-3 have large UV stability.

(26) Voltage holding ratio (VHR-4; measured at 25°C; %): After heating the TN element injected with the sample in a constant temperature bath at 80°C for 500 hours, the voltage holding ratio was measured, and the resistance to heat was evaluated. stability. In the measurement of VHR-4, the decayed voltage was measured during 166.7 milliseconds. Compositions with large VHR-4 have large thermal stability.

(27) Response time (τ; measured at 25° C.; ms): 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 VA element in which the distance (cell gap) between the two glass substrates was 4 μm and the rubbing direction was antiparallel. The element is sealed with a UV-curable adhesive. A rectangular wave (60 Hz, 10 V, 0.5 sec) was applied to the element. At this time, the element was irradiated with light from a vertical direction, and the amount of light transmitted through the element was measured. When the light amount reached the maximum, the transmittance was regarded as 100%, and when the light amount was the minimum, the transmittance was regarded as 0%. The response time is the time required for the transmittance to change from 10% to 90% (rise time; rise time; milliseconds) and the time required for the transmittance to change from 90% to 10% (fall time; fall time; milliseconds) total to indicate.

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

Synthesis Example 1 Compound (1-1) was synthesized by the following route.

In a 1000 ml three-necked flask, put 2-(tert-butyl)-6-(5-chloro-2H-benzotriazol-2-yl)-4-methylphenol (40.0 g, 0.126 mol), Phenylboronic acid (15.598 g, 0.127 mol), PdCl ₂ (Amphos) ₂ (Pd-132, 0.179 g, 0.250 mmol), potassium carbonate (35.010 g, 0.253 mol), tetrabutylammonium bromide (12.520 g, 38.000 mmol), toluene (200 ml), isopropanol (200 ml), water (20 ml) and heated to reflux. After 3 hours, it was poured into water (200 ml), the aqueous layer was separated from the organic layer, and the aqueous layer was further extracted with toluene (200 ml). The mixed organic layer was washed with saturated brine (100 ml×2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified with a silica gel column using heptane/toluene=9/1 (volume ratio) as a developing solvent to obtain Compound (1-1) (26.1 g, 0.073 mol, 58% yield) ).

¹ H-NMR (ppm; CDCl ₃ ): δ 11.73 (s, 1H), 8.09 (dd, J=16.5 Hz, J=1.3 Hz, 2H), 7.98 (d, J=8.8 Hz, 1H), 7.74 ( dd, J=8.8 Hz, J=1.3 Hz, 1H), 7.69 (dd, J=16.5 Hz, J=1.3 Hz, 2H), 7.52-7.49 (m, 2H), 7.44-7.41 (m, 1H), 7.19 (d, J=1.9 Hz, 1H), 2.41 (s, 3H), 1.51 (s, 9H).

Absorbance (arbitrary unit): 0.216 (369 nm).

Synthesis Example 2 Compound (1-2) was synthesized by the following route.

In a 500 ml three-necked flask, put 2-(tert-butyl)-6-(5-chloro-2H-benzotriazol-2-yl)-4-methylphenol (50.0 g, 0.158 mol), 4-Propylphenylboronic acid (26.277 g, 0.160 mol), PdCl ₂ (Amphos) ₂ (Pd-132, 0.224 g, 0.320 mmol), potassium carbonate (43.762 g, 0.317 mol), tetrabutylammonium bromide ( 15.312 g, 47.50 mmol), isopropanol (250 ml) and heated to reflux. After 3 hours, it was poured into water (200 ml), the aqueous layer was separated from the organic layer, and the aqueous layer was further extracted with toluene (200 ml). The mixed organic layer was washed with saturated brine (100 ml×2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified with a silica gel column using heptane/toluene=9/1 (volume ratio) as a developing solvent to obtain Compound (1-2) (39.3 g, 0.0984 mol, 62% yield) ).

¹ H-NMR (ppm; CDCl ₃ ): δ 11.73 (s, 1H), 8.09 (d, J=1.3 Hz, 1H), 6.04 (dd, J=1.3 Hz, J=1.0 Hz, 1H), 7.94 ( d, J=8.8 Hz, 1H), 7.72 (dd, J=8.8 Hz, J=1.3 Hz, 1H), 7.58 (d, J=8.1 Hz, 2H), 7.30 (d, J=8.1 Hz, 2H) , 7.18 (d, J=1.9 Hz, 1H), 2.65 (t, J=7.5 Hz, 2H), 2.39 (s, 3H), 1.70 (sext, J=7.5 Hz, 2H), 1.51 (s, 9H) , 0.99 (t, J=7.4 Hz, 3H).

Absorbance (arbitrary unit): 0.216 (369 nm).

Synthesis Example 3 Compound (1-3) was synthesized by the following route.

In a 200 ml three-necked flask, put 2-(tert-butyl)-6-(5-chloro-2H-benzotriazol-2-yl)-4-methylphenol (5.00 g, 0.0158 mol), 4'-propyl-4-biphenylboronic acid (3.840 g, 0.0160 mol), PdCl ₂ (Amphos) ₂ (Pd-132, 0.0224 g, 0.0320 mmol), potassium carbonate (4.3762 g, 0.0317 mol), tetrabutyl Ammonium bromide (1.5312 g, 4.750 mmol), toluene (25 ml), isopropanol (25 ml), water (2.5 ml) and heated to reflux. After 3 hours, it was poured into water (20 ml), the aqueous layer and the organic layer were separated, and the aqueous layer was further extracted with toluene (20 ml). The mixed organic layer was washed with saturated brine (10 ml×2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified with a silica gel column using heptane/toluene=9/1 (volume ratio) as a developing solvent to obtain Compound (1-3) (3.30 g, 6.94 mmol, 44% yield) ).

¹ H-NMR (ppm; CDCl ₃ ): δ 11.74 (s, 1H), 8.12-8.11 (m, 2H), 8.03 (dd, J=8.9 Hz, J=0.75 Hz, 1H), 7.80 (dd, J =8.9 Hz, J=1.3 Hz, 1H), 7.77-7.72 (m, 4H), 7.59 (d, J=8.1 Hz, 2H), 7.29 (d, J=8.1 Hz, 2H), 7.19 (d, J =1.9 Hz, 1H), 2.65 (t, J=7.5 Hz, 2H), 2.40 (s, 3H), 1.70 (sext, J=7.5 Hz, 2H), 1.51 (s, 9H), 0.99 (t, J =7.4 Hz, 3H).

Absorbance (arbitrary unit): 0.294 (369 nm).

Synthesis Example 4 Compound (1-4) was synthesized by the following route.

In a 200 ml three-necked flask, put 2-(tert-butyl)-6-(5-chloro-2H-benzotriazol-2-yl)-4-methylphenol (5.00 g, 0.0158 mol), 2-Naphthaleneboronic acid (2.750 g, 0.0160 mol), PdCl ₂ (Amphos) ₂ (Pd-132, 0.0224 g, 0.0320 mmol), potassium carbonate (4.3762 g, 0.0317 mol), tetrabutylammonium bromide (1.5312 g, 4.750 mmol), toluene (25 ml), isopropanol (25 ml), water (2.5 ml) and heated to reflux. After 3 hours, it was poured into water (20 ml), the aqueous layer and the organic layer were separated, and the aqueous layer was further extracted with toluene (20 ml). The mixed organic layer was washed with saturated brine (10 ml×2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified with a silica gel column using heptane/toluene=9/1 (volume ratio) as a developing solvent to obtain Compound (1-4) (0.52 g, 1.28 mmol, 8.1% yield) ).

¹ H-NMR (ppm; CDCl ₃ ): δ 11.74 (s, 1H), 8.20 (s, 1H), 8.13 (d, J=6.6, J=1.3 Hz, 2H), 8.02 (d, J=8.9 Hz) , 1H), 7.98 (d, J=8.6 Hz, 1H), 7.94 (d, J=7.4 Hz, 1H), 7.89 (ddd, J=8.4 Hz, J=8.0 Hz, J=1.2 Hz, 2H), 7.82 (dd, J=8.4 Hz, J=1.7 Hz, 1H), 7.56-7.51 (m, 2H), 7.12 (d, J=1.9 Hz, 1H), 2.41 (s, 3H), 1.52 (s, 9H) ).

Absorbance (arbitrary unit): 0.176 (369 nm).

Examples of the composition are shown below. The component compounds are represented by symbols based on the definitions in Table 3 below. In Table 3, the steric configuration related to the 1,4-cyclohexylene group is the trans configuration. The number in parentheses following the notated compound indicates the formula to which the compound belongs. The symbol (-) refers to other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is the mass percentage (mass %) based on the mass of the liquid crystal composition not containing the additive. Finally, the characteristic values of the composition are summarized.

[table 3]

[Comparative Example 1] 3-HH-V (2-1) 44% V-HHB-1 (2-5) 6% 2-BB(F)B-3 (2-8) 2% 3-HHB(F ,F)-F (3-2) 4% 4-HHB(F,F)-F (3-2) 5% 3-HHXB(F,F)-F (3-4) 6%3-BB( F,F)XB(F,F)-F (3-18) 13% 3-HBBXB(F,F)-F (3-23) 3% 3-BB(F)B(F,F)XB( F,F)-F (3-29) 2%4-BB(F)B(F,F)XB(F,F)-F (3-29) 8%5-BB(F)B(F, F)XB(F,F)-F (3-29) 7%NI=79.8℃; Tc＜-20℃; Δn=0.106; Δε=8.5; Vth=2.18 V; η=11.6 mPa·s; γ1= 60.0 mPa·s; VHR-3=35.5%.

[Example 1] A composition obtained by adding the compound (1-1) to the composition of Comparative Example 1 was referred to as Example 1. 3-HH-V (2-1) 44% V-HHB-1 ( 2-5) 6% 2-BB(F)B-3 (2-8) 2% 3-HHB(F,F)-F (3-2) 4% 4-HHB(F,F)-F ( 3-2) 5% 3-HHXB(F,F)-F (3-4) 6% 3-BB(F,F)XB(F,F)-F (3-18) 13%3-HBBXB( F,F)-F (3-23) 3%3-BB(F)B(F,F)XB(F,F)-F (3-29) 2%4-BB(F)B(F, F)XB(F,F)-F (3-29) 8% 5-BB(F)B(F,F)XB(F,F)-F (3-29) 7% in a ratio of 0.5% by mass Compound (1-1) is added to this composition. NI=78.8℃; Tc＜-20℃; Δn=0.106; Δε=8.5; Vth=2.18 V; η=11.6 mPa·s; γ1=60.0 mPa·s; VHR-3=87.8%.

[Comparative Example 2] 3-HH-V (2-1) 29% 1-BB-3 (2-3) 10% 3-HHB-1 (2-5) 8% 5-B(F)BB-2 (2-7) 6%3-BB(2F,3F)-O2 (4-6) 13%2-HH1OB(2F,3F)-O2 (4-10) 20%3-HH1OB(2F,3F)- O2 (4-10) 14%NI=74.5℃; Tc＜-20℃; Δn=0.106; Δε=-3.0; Vth=2.21 V; η=14.7 mPa·s; VHR-3=40.9%.

[Example 2] The composition obtained by adding the compound (1-1) to the composition of Comparative Example 2 was referred to as Example 2. 3-HH-V (2-1) 29% 1-BB-3 ( 2-3) 10% 3-HHB-1 (2-5) 8% 5-B(F)BB-2 (2-7) 6% 3-BB(2F,3F)-O2 (4-6) 13 %2-HH1OB(2F,3F)-O2 (4-10) 20% 3-HH1OB(2F,3F)-O2 (4-10) 14% Compound (1-1) was added in a ratio of 0.5% by mass in this composition. NI=73.5℃; Tc＜-20℃; Δn=0.106; Δε=-3.0; Vth=2.21 V; η=14.7 mPa·s; VHR-3=78.1%.

[Example 3] 3-HH-V (2-1) 23% 3-HH-V1 (2-1) 10% 1V2-HH-3 (2-1) 9% V2-HHB-1 (2-5 ) 8%3-HHXB(F,F)-CF3 (3-5) 12%3-GB(F,F)XB(F,F)-F (3-14) 8%3-GBB(F)B (F,F)-F (3-22) 3% 4-GBB(F)B(F,F)-F (3-22) 2% 3-HBBXB(F,F)-F (3-23) 3%4-GB(F)B(F,F)XB(F,F)-F (3-27) 5%5-GB(F)B(F,F)XB(F,F)-F ( 3-27) 5% 5-BB(F)B(F,F)XB(F,F)-F (3-29) 12% Compound (1-1) was added to the composition at a ratio of 0.5% by mass thing. NI=87.8℃; Tc＜-20℃; Δn=0.101; Δε=13.4; Vth=1.34 V; η=20.6 mPa·s; γ1=123.7 mPa·s; VHR-3=84.8%.

[Example 4] 3-HH-V (2-1) 18% 3-HH-4 (2-1) 11% 5-HB-O2 (2-2) 2% 3-HHB-1 (2-5 ) 5%3-HHB-3 (2-5) 5%3-HHB-O1 (2-5) 6%3-HHB(F,F)-F (3-2) 10%3-HHXB(F, F)-F (3-4) 2% 3-GHB(F,F)-F (3-7) 4% 3-BB(F)B(F,F)-F (3-15) 7%3 -BB(F,F)XB(F,F)-F (3-18) 14%4-BB(F)B(F,F)XB(F,F)-F (3-29) 10%5 -BB(F)B(F,F)XB(F,F)-F (3-29) 6% The compound (1-1) was added to this composition in the ratio of 0.5 mass %. NI=77.2℃; Tc＜-20℃; Δn=0.108; Δε=10.4; Vth=1.35 V; η=17.8 mPa·s; γ1=79.9 mPa·s; VHR-3=82.4%.

[Example 5] 3-HH-V (2-1) 18% 3-HH-4 (2-1) 11% 5-HB-O2 (2-2) 2% 3-HHB-1 (2-5 ) 5%3-HHB-3 (2-5) 5%3-HHB-O1 (2-5) 6%3-HHB(F,F)-F (3-2) 10%3-HHXB(F, F)-F (3-4) 2% 3-GHB(F,F)-F (3-7) 4% 3-BB(F)B(F,F)-F (3-15) 7%3 -BB(F,F)XB(F,F)-F (3-18) 14%4-BB(F)B(F,F)XB(F,F)-F (3-29) 10%5 -BB(F)B(F,F)XB(F,F)-F (3-29) 6% The compound (1-2) was added to this composition in the ratio of 0.5 mass %. NI=77.1℃; Tc＜-20℃; Δn=0.108; Δε=10.4; Vth=1.35 V; η=17.8 mPa·s; γ1=79.9 mPa·s; VHR-3=81.5%.

[Example 6] 3-HH-V (2-1) 44% V-HHB-1 (2-5) 6% 2-BB(F)B-3 (2-8) 2% 3-HHXB(F ,F)-F (3-4) 6% 3-BB(F,F)XB(F,F)-F (3-18) 13% 3-HHBB(F,F)-F (3-19) 4% 4-HHBB(F,F)-F (3-19) 5% 3-HBBXB(F,F)-F (3-23) 3% 3-BB(F)B(F,F)XB( F)-F (3-28) 2%4-BB(F)B(F,F)XB(F,F)-F (3-29) 8%5-BB(F)B(F,F) XB(F,F)-F(3-29) 7% The compound (1-3) was added to this composition in the ratio of 0.5 mass %. NI=79.3℃; Tc＜-20℃; Δn=0.106; Δε=8.5; Vth=1.45 V; η=11.6 mPa·s; γ1=60.0 mPa·s; VHR-3=80.2%.

[Example 7] 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 (2-2) 7% 4-HHEH-3 (2-4) 3% 1-BB(F)B-2V (2 -8) 3%5-HXB(F,F)-F (3-1) 6%3-HHXB(F,F)-F (3-4) 6%V-HB(F)B(F,F )-F (3-9) 5% 3-HHB(F)B(F,F)-F (3-20) 7% 2-BB(F)B(F,F)XB(F)-F ( 3-28) 3%3-BB(F)B(F,F)XB(F)-F (3-28) 3%4-BB(F)B(F,F)XB(F)-F ( 3-28) 4% 5-HB-CL (3) 5% 1O1-HBBH-3 (-) 5% The compound (1-4) was added to this composition in the ratio of 0.5 mass %. NI=78.0℃; Tc＜-20℃; Δn=0.095; Δε=3.4; Vth=1.50 V; η=8.4 mPa·s; γ1=54.2 mPa·s; VHR-3=78.3%.

[Example 8] 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 (2-2) 5%7-HB-1 (2-2) 5%VFF-HHB-O1 (2-5) 8%VFF-HHB-1 (2-5) 3 %3-HBB(F,F)-F (3-8) 5%5-HBB(F,F)-F (3-8) 4%3-BB(F)B(F,F)-F ( 3-15) 3%3-BB(F)B(F,F)XB(F,F)-F (3-29) 3%4-BB(F)B(F,F)XB(F,F )-F (3-29) 5%3-BB(F,F)XB(F)B(F,F)-F (3-30) 3%5-BB(F)B(F,F)XB (F)B(F,F)-F (3-31) 4% 3-HH2BB(F,F)-F (3) 3% 4-HH2BB(F,F)-F (3) 3% by 0.5 The compound (1-1) is added to this composition in the ratio of mass %. NI=78.8℃; Tc＜-20℃; Δn=0.101; Δε=4.6; Vth=1.71 V; η=11.0 mPa·s; γ1=47.2 mPa·s; VHR-3=80.1%.

[Example 9] 2-HH-5 (2-1) 8% 3-HH-V (2-1) 28% 4-HH-V1 (2-1) 7% 5-HB-O2 (2-2 ) 2%7-HB-1 (2-2) 5%VFF-HHB-O1 (2-5) 8%VFF-HHB-1 (2-5) 3%3-HBB(F,F)-F ( 3-8) 5% 5-HBB(F,F)-F (3-8) 4% 3-BB(F)B(F,F)-F (3-15) 3%3-BB(F) B(F,F)XB(F,F)-F (3-29) 3%4-BB(F)B(F,F)XB(F,F)-F (3-29) 5%3- BB(F,F)XB(F)B(F,F)-F (3-30) 3% 5-BB(F)B(F,F)XB(F)B(F,F)-F ( 3-31) 4%3-HH2BB(F,F)-F (3) 3%4-HH2BB(F,F)-F (3) 3%3-HBB(2F,3F)-O2 (4-14 ) 2% 2-BB(2F, 3F)B-3 (4-19) 4% Compound (1-1) was added to this composition in a ratio of 0.5% by mass. NI=80.7℃; Tc＜-20℃; Δn=0.109; Δε=4.8; Vth=3.01 V; η=13.3 mPa·s; γ1=57.4 mPa·s; VHR-3=79.8%.

[Example 10] 3-HH-V (2-1) 28%V2-BB-1 (2-3) 20%1-BB(F)B-2V (2-8) 7%2-BB(F )B-2V (2-8) 10% 3-BB(F)B-2V (2-8) 11% 2-BB(F)B-3 (2-8) 4% 3-BB(F,F )XB(F,F)-F (3-18) 9.5% 3-BB(F)B(F,F)XB(F,F)-F (3-29) 5%3-BB(F,F )XB(F)B(F,F)-F (3-30) 5.5% The compound (1-1) was added to this composition in the ratio of 0.3 mass %. Tc＜-20℃; Δn=0.161; Δε=4.1; Vth=2.15 V; η=13.6 mPa·s; γ1=44.0 mPa·s; VHR-3=72.1%.

[Example 11] 3-HH-V (2-1) 13% 5-HB-O2 (2-2) 2% V-HHB-1 (2-5) 10% 3-HHB-1 (2-5 ) 5% 3-HHB-O1 (2-5) 3.5% 2-BB(F)B-2V (2-8) 4% 3-BB(F)B-2V (2-8) 4% 2-HHB (F,F)-F (3-2) 10% 3-HHB(F,F)-F (3-2) 12% 3-HBB(F,F)-F (3-8) 8%3- BB(F)B(F,F)-F (3-15) 8.5% 3-BB(F,F)XB(F,F)-F (3-18) 16% 3-HHBB(F,F) -F (3-19) 4% The compound (1-1) was added to this composition in the ratio of 0.5 mass %. NI=83.0℃; Tc＜-20℃; Δn=0.120; Δε=8.4; Vth=1.54 V; VHR-3=70.2%.

[Example 12] 3-HH-V (2-1) 34% 3-HH-V1 (2-1) 5% 3-HH-VFF (2-1) 2% V-HHB-1 (2-5 ) 12%V2-HHB-1 (2-5) 11.5%3-HHB-1 (2-5) 2%1-BB(F)B-2V (2-8) 2%2-BB(F)B -2V (2-8) 6% 3-BB(F)B-2V (2-8) 4% 3-HHXB(F,F)-F (3-4) 3.5% 3-HBBXB(F,F) -F (3-23) 3%3-HBB(F,F)XB(F,F)-F (3-24) 7%4-BB(F)B(F,F)XB(F,F) -F (3-28) 2% 5-BB(F)B(F,F)XB(F,F)-F (3-28) 6% Compound (1-1) was added at a ratio of 0.4% by mass in this composition. NI=103.5℃; Tc＜-20℃; Δn=0.113; Δε=3.5; Vth=2.52 V; γ1=63.0 mPa·s; VHR-3=91.7%.

[Example 13] 3-HH-V (2-1) 34% 3-HH-V1 (2-1) 4% V-HHB-1 (2-5) 8% 3-HHB-O1 (2-5 ) 3%2-BB(F)B-3 (2-8) 3%1-BB(F)B-2V (2-8) 4%3-HHXB(F,F)-F (3-4) 11%3-GB(F)B(F,F)-F (3-12) 10%3-GB(F,F)XB(F,F)-F (3-14) 10%3-GB( F)B(F)B(F)-F (3-21) 3%4-GBB(F)B(F,F)-F (3-22) 2%2-HBB(2F,3F)-O2 (4-14) 2% 3-HBB(2F,3F)-O2 (4-14) 6% The compound (1-1) was added to this composition in the ratio of 0.5 mass %. NI=80.7℃; Tc＜-20℃; Δn=0.102; Δε=6.5; Vth=1.59 V; η=14.2 mPa·s; γ1=60.0 mPa·s; VHR-3=70.0%.

[Example 14] 3-HH-V (2-1) 34% 3-HHB-O1 (2-5) 3% 3-HHB-3 (2-5) 1% V-HHB-1 (2-5) ) 12%V2-HHB-1 (2-5) 14%1-BB(F)B-2V (2-8) 2%2-BB(F)B-2V (2-8) 5%3-BB (F)B-2V (2-8) 4%3-HHXB(F,F)-F (3-4) 1%3-GB(F)B(F)-F (3-11) 8%3 -GB(F)B(F,F)-F (3-12) 8%3-GB(F,F)XB(F,F)-F (3-14) 7%3-GBB(F)B (F,F)-F (3-22) 1% The compound (1-1) was added to this composition in the ratio of 0.5 mass %. NI=89.4℃; Tc＜-20℃; Δn=0.105; Δε=4.9; Vth=1.91 V; η=13.7 mPa·s; γ1=63.0 mPa·s; VHR-3=70.4%.

[Example 15] 3-HH-V (2-1) 34.5% 3-HH-V1 (2-1) 8% 3-HHB-1 (2-5) 3% V-HHB-1 (2-5) ) 12%3-HBB-2 (2-6) 4%V-HBB-2 (2-6) 5%1-BB(F)B-2V (2-8) 4%2-BB(F)B -2V (2-8) 4% 3-BB(F)B(F,F)-F (3-15) 5% 3-BB(F,F)XB(F,F)-F (3-18 ) 7% 4-GB(F)B(F,F)XB(F,F)-F (3-27) 3.5%3-BB(F)B(F,F)XB(F,F)-F (3-29) 3% 4-BB(F)B(F,F)XB(F,F)-F (3-29) 7% Compound (1-1) was added in the ratio of 0.5% by mass in the composition. NI=84.8℃; Tc＜-20℃; Δn=0.119; Δε=5.3; Vth=1.93 V; η=12.1 mPa·s; γ1=49.0 mPa·s; VHR-3=70.4%.

[Example 16] 3-HH-V (2-1) 34% 3-HH-V1 (2-1) 5.5% V-HHB-1 (2-5) 13% V-HBB-2 (2-6 ) 5% 2-BB(F)B-3 (2-8) 4% 1-BB(F)B-2V (2-8) 4% 2-BB(F)B-2V (2-8) 5 %3-BB(F)B-2V (2-8) 4%3-BB(F)B(F,F)-CF3 (3-16) 3%3-BB(F,F)XB(F, F)-F (3-18) 8.5% 3-HBB(F,F)XB(F,F)-F (3-24) 4% 3-BB(F)B(F,F)XB(F, F)-F (3-29) 3%4-BB(F)B(F,F)XB(F,F)-F (3-29) 4%3-BB(F,F)XB(F) B(F,F)-F(3-30) 3% The compound (1-1) was added to this composition in the ratio of 0.5 mass %. NI=84.9℃; Tc＜-20℃; Δn=0.130; Δε=5.2; Vth=2.06 V; η=13.6 mPa·s; γ1=55.0 mPa·s; VHR-3=85.2%.

[Example 17] 3-HH-V (2-1) 48% V2-BB-1 (2-3) 4% 1-BB(F)B-2V (2-8) 7% 2-BB(F )B-2V (2-8) 10% 3-BB(F)B-2V (2-8) 12% 3-BB(F)B(F,F)-CF3 (3-16) 4%3- BB(F,F)XB(F,F)-F (3-18) 13% 3-BB(F,F)XB(F)B(F,F)-F (3-30) 2% with 0.5 The compound (1-1) is added to this composition in the ratio of mass %. Tc＜-20℃; Δn=0.130; Δε=3.6; Vth=2.15 V; η=12.0 mPa·s; γ1=33.0 mPa·s; VHR-3=70.5%.

[Example 18] 3-HH-V (2-1) 20% V-HBB-2 (2-6) 11% 3-HBB-2 (2-6) 14% 3-HB (2F, 3F)- O2 (4-1) 13%5-HB(2F,3F)-O2 (4-1) 13%3-H2B(2F,3F)-O2 (4-2) 9%V-HHB(2F,3F) -O1 (4-8) 4%V-HHB(2F,3F)-O2 (4-8) 10%3-HHB(2F,3F)-O2 (4-8) 6% by 0.5% by mass Compound (1-1) is added to this composition. NI=73.8℃; Tc＜-20℃; Δn=0.103; Δε=-2.9; Vth=2.26 V; η=16.7 mPa·s; γ1=94.0 mPa·s; VHR-3=76.8%.

The voltage holding ratios (VHR-3) after ultraviolet irradiation of the compositions of Comparative Examples 1 and 2 were 35.5% and 40.9%. On the other hand, the VHR-3 of the compositions of Examples 1 and 2 were 87.8% and 78.1%. In this way, the composition of the example has a large VHR-3 compared to the composition of the comparative example. Therefore, it was concluded that the liquid crystal composition of the present invention has excellent characteristics. [Industrial Availability]

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

none

Claims (17)

A liquid crystal composition containing at least one compound selected from the compounds represented by formula (1) as a first additive, and having a nematic phase,

In formula (1), R ¹ is hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons ; R ² is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine, among these groups, at least one -CH ₂ - can be substituted by -O-, -COO-, or -OCO-; Ring A is 1,4-cyclohexylene, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-1 ,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl , naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1 ,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, carbon number 1 to 12 alkyl groups, alkoxy groups of carbon numbers 1 to 12, or alkyl groups of carbon numbers 1 to 12 in which at least one hydrogen is substituted by fluorine or chlorine; a is 1 or 2; b is 0, 1, 2, 3, or 4. The liquid crystal composition according to claim 1, wherein in the compound represented by formula (1), R ² is methyl, tertiary butyl, tertiary pentyl, or tertiary octyl, and b is 1 , 2, 3, or 4. The liquid crystal composition according to item 1 of the claimed scope, comprising at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-4) as the first additive,

In formula (1-1) to formula (1-4), R ² is methyl, tertiary butyl, tertiary pentyl, or tertiary octyl. The liquid crystal composition according to claim 1, wherein the ratio of the first additive is in the range of 0.005% by mass to 2% by mass. The liquid crystal composition according to claim 1, which contains at least one compound selected from the compounds represented by the formula (2) as the first component,

In the formula (2), R ³ and R ⁴ are independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or at least one hydrogen through fluorine or chlorine Substituted alkenyl having 2 to 12 carbon atoms; Ring B and Ring C are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2, 5-difluoro-1,4-phenylene; Z ¹ is a single bond, ethylene, carbonyloxy, or methyleneoxy; c is 1, 2, or 3. The liquid crystal composition according to item 1 of the claimed scope, comprising at least one compound selected from the group of compounds represented by formula (2-1) to formula (2-13) as a first component,

In formula (2-1) to formula (2-13), R ³ and R ⁴ are independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. , or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine. The liquid crystal composition according to claim 5, wherein the ratio of the first component is in the range of 10% by mass to 85% by mass. The liquid crystal composition according to item 5 of the scope of the application, comprising at least one compound selected from the compounds represented by the formula (3) as the second component,

In formula (3), R ⁵ is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms; ring D is 1,4-cyclohexylene, 1 ,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine -2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z ² is a single bond, ethylidene, carbonyloxy, or difluoromethyleneoxy; X ¹ and X ² are independently hydrogen or fluorine; Y ¹ is fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine, and at least one hydrogen is an alkoxy group having 1 to 12 carbons substituted with fluorine or chlorine, or an alkenyloxy group having 2 to 12 carbons substituted with at least one hydrogen by fluorine or chlorine; d is 1, 2, 3, or 4. The liquid crystal composition according to item 5 of the claimed scope, comprising at least one compound selected from the group of compounds represented by formula (3-1) to formula (3-35) as the second component,

In formulas (3-1) to (3-35), R ⁵ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons. The liquid crystal composition according to claim 8, wherein the ratio of the second component is in the range of 10% by mass to 85% by mass. The liquid crystal composition according to item 5 of the scope of the application, comprising at least one compound selected from the compounds represented by the formula (4) as the third component,

In formula (4), R ⁶ and R ⁷ are independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or an alkene having 2 to 12 carbons yloxy; Ring E and Ring G are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4 wherein at least one hydrogen is substituted with fluorine or chlorine -phenylene, or tetrahydropyran-2,5-diyl; ring F is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene group, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochromane- 2,6-diyl; Z ³ and Z ⁴ are independently a single bond, ethylidene, carbonyloxy, or methyleneoxy; e is 1, 2, or 3, and f is 0 or 1; e and The sum of f is 3 or less. The liquid crystal composition according to item 5 of the claimed scope, comprising at least one compound selected from the group of compounds represented by formula (4-1) to formula (4-27) as the third component,

In formula (4-1) to formula (4-27), R ⁶ and R ⁷ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons , or an alkenyloxy group having 2 to 12 carbons. The liquid crystal composition according to claim 11, wherein the ratio of the third component is in the range of 5% by mass to 80% by mass. The liquid crystal composition according to claim 11, which contains at least one compound selected from the polymerizable compounds represented by the formula (5) as the second additive,

In formula (5), ring I and ring K are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxanyl Alkyl-2-yl, pyrimidin-2-yl, or pyridin-2-yl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons group, or at least one hydrogen is substituted by fluorine or chlorine substituted alkyl with 1 to 12 carbon atoms; ring J is 1,4-cyclohexylene, 1,4-cyclohexenyl, 1,4-phenylene , naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1, 7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5- Diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine , an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; Z ⁵ and Z ⁶ are independently a single bond Or alkylene with 1 to 10 carbon atoms, in the alkylene, at least one -CH ₂ - can be substituted by -O-, -CO-, -COO-, or -OCO-, and at least one -CH ₂ - CH ₂ - can be substituted by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )-, or -C(CH ₃ )=C(CH ₃ )-, these radicals In, at least one hydrogen may be substituted by fluorine or chlorine; P ¹ , P ² , and P ³ are independently polymerizable groups; Sp ¹ , Sp ² , and Sp ³ are independently a single bond, or a carbon number of 1 to 10. Alkylene, in the alkylene, at least one -CH ₂ - can be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ -CH ₂ - can be substituted by -CH =CH- or -C≡C-substituted, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; g is 0, 1, or 2; h, i, and j are independently 0, 1, 2, 3, or 4; and the sum of h, i, and j is 1 or more. The liquid crystal composition according to claim 11, comprising at least one compound selected from the group of polymerizable compounds represented by formula (5-1) to formula (5-29) as a second additive ,

In formula (5-1) to formula (5-29), P ⁴ , P ⁵ , and P ⁶ are independently selected from the group of polymerizable groups represented by formula (P-1) to formula (P-3) The groups in the group, M ¹ , M ² , and M ³ are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is substituted with fluorine or chlorine;

Sp ¹ , Sp ² , and Sp ³ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be via -O-, -COO-, -OCO -, or -OCOO-, at least one -CH ₂ -CH ₂ - may be substituted with -CH=CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine. The liquid crystal composition according to claim 14, wherein the ratio of the second additive is in the range of 0.03% by mass to 10% by mass. A liquid crystal display element containing the liquid crystal composition according to claim 1.