TW202239943A - Liquid crystal composition and uses thereof and liquid crystal display element wherein the liquid crystal composition fully meets at least one of the properties of high upper limit temperature, low lower limit temperature, low viscosity, large optical anisotropy, large dielectric anisotropy, high specific resistance, high stability to light, high stability to heat, large elasticity constant, and the like - Google Patents

Abstract

The invention provides a liquid crystal composition and an active matrix element comprising the composition. The liquid crystal composition fully meets at least one of the properties of high upper limit temperature, low lower limit temperature, low viscosity, large optical anisotropy, large dielectric anisotropy, high specific resistance, high stability to light, high stability to heat, large elasticity constant, and the like, or relates to at least two of the properties with an appropriate balance. A liquid crystal composition which comprises: a specific compound, used as component A, having large optical anisotropy and dielectric anisotropy; a specific compound, used as component B, having large dielectric anisotropy; and a specific compound, used as component C, having small viscosity or high upper limit temperature, the liquid crystal composition can also comprise a specific compound, used as component D, having large dielectric anisotropy or a specific compound, used as component E, having large dielectric anisotropy in the minor axis direction.

Description

Liquid crystal composition and its application 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. In particular, it relates to a liquid crystal composition with positive dielectric anisotropy, and the composition containing said composition and having twisted nematic (twisted nematic, TN), electrically controlled birefringence (electrically controlled birefringence, ECB), optical compensation bending ( Active matrix in optically compensated bend (OCB), in-plane switching (IPS), fringe field switching (FFS) or field-induced photo-reactive alignment (FPA) modes (active matrix, AM) element.

In liquid crystal display elements, the classification based on the operation mode of liquid crystal molecules is phase change (phase change, PC), twisted nematic (twisted nematic, TN), super twisted nematic (super twisted nematic, STN), electrically controlled birefringence ( Electrically controlled birefringence (ECB), optically compensated bend (OCB), in-plane switching (IPS), vertical alignment (vertical alignment, VA), fringe field switching (fringe field switching, FFS), Field-induced photo-reactive alignment (FPA) and other modes. The classification of component-based driving methods is passive matrix (passive matrix, PM) and active matrix (active matrix, AM). PM is classified into static type (static), multiplex type (multiplex), etc., AM is classified into thin film transistor (thin film transistor, TFT), metal-insulator-metal (metal insulator metal, MIM), etc. The classification of TFT is amorphous silicon (amorphous silicon) and polycrystalline silicon (polycrystalline silicon). The latter are classified into high temperature type and low temperature type according to the manufacturing steps. The classification based on the light source is a reflective type using natural light, a transmissive type using backlight, and a transflective type using both natural light and backlight.

A 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 with good properties can be obtained. The correlation among these characteristics is summarized in Table 1 below. The characteristics of the composition will be further described based on a commercially available AM device. The temperature range of the nematic phase correlates with the usable temperature range of the element. A preferable upper limit temperature of the nematic phase is about 60°C or higher, and a preferable lower limit temperature of the nematic phase is about -10°C or lower. The viscosity of the composition correlates with the response time of the component. In order to display a moving image with a device, it is preferable that the response time is short. A response time of less than 1 millisecond is ideal. Therefore, it is preferable that the viscosity of a composition is small. Furthermore, it is preferable that the viscosity at low temperature is small. The elastic constant of the composition is related to the contrast of the element. In the device, in order to increase the contrast, it is preferable that the elastic constant of the composition is large.

the Table 1. Characteristics of the composition and characteristics of the AM device the no properties of the composition Characteristics of AM components 1 The nematic phase has a wide temperature range Wide temperature range of usable components 2 low viscosity short response time 3 Appropriate optical anisotropy high contrast 4 Large positive or negative dielectric anisotropy Low threshold voltage and low power consumption high contrast 5 Greater than resistance High voltage retention rate and high contrast 6 UV or heat stable long life 7 Large elastic constant High contrast ratio and short response time

The optical anisotropy of the composition correlates with the contrast of the device. Depending on the mode of the element, large optical anisotropy or small optical anisotropy, that is, appropriate optical anisotropy is required. The product (Δn×d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed so as to maximize the contrast. An appropriate value of the product depends on the type of operation mode. In a TN mode device, the appropriate value is about 0.45 μm. In such a case, a composition having a large optical anisotropy is preferable for a device having a small cell gap. The large dielectric anisotropy of the composition contributes to the device's low threshold voltage, low power consumption, and high contrast. Therefore, a large dielectric anisotropy is preferable. The large specific resistance of the composition contributes to the high voltage retention and high contrast of the device. Therefore, a composition having a large specific resistance in the initial stage is preferable. A composition having a large specific resistance after long-term use is preferable. The stability of the composition to ultraviolet rays and heat is related to the lifetime of the liquid crystal display element. When these stabilities are high, the lifetime of the element is long. Such characteristics are preferable for AM elements used in liquid crystal monitors, liquid crystal televisions, and the like.

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

A compound having a cyano group (cyano compound) is known as a compound having a large positive dielectric anisotropy. For example, Patent Document 1 discloses a liquid crystal composition containing a cyano compound having an ester bond, and describes that a liquid crystal display device using the composition has a very short response time. On the other hand, Patent Document 2 describes that the voltage holding ratio (Voltage Holding Ratio, VHR) of a liquid crystal composition containing a cyano compound is lower than that of a liquid crystal composition not containing a cyano compound.

In recent years, a liquid crystal composition having a lower rotational viscosity has been demanded along with the high-speed response of liquid crystal display elements. In addition, in order to make the cell gap narrower, it is also necessary to have desired optical anisotropy. In order to be used in a liquid crystal display device, the liquid crystal composition must be a liquid crystal composition that has such characteristics and is practically able to withstand other characteristics such as voltage retention.

[Prior art literature] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 2004-204233 [Patent Document 2] International Publication No. 2011-062049

[Problem to be Solved by the Invention] The problem of the present invention is to provide a liquid crystal composition that fully satisfies the high upper limit temperature of the nematic phase, low lower limit temperature of the nematic phase, low viscosity, large optical anisotropy, large positive dielectric anisotropy, and high specific resistance. , high stability to light, high stability to heat, and at least one of properties such as a large elastic constant. Another problem is to provide a liquid crystal composition having an appropriate balance between at least two of these properties. Another problem is to provide a liquid crystal display device containing such a composition. Yet another problem is to provide an AM element having characteristics such as short response time, high voltage retention, low threshold voltage, high contrast, and long life.

式（1）中，R ¹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的烯氧基、或者至少一個氫經氟或氯取代的碳數1至12的烷基；X ¹、X ²、X ³、X ⁴及X ⁵為氫或氟，X ¹、X ²、X ³、X ⁴及X ⁵的至少一個為氟； 式（2）中，R ²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A ¹及環A ²為1,4-伸苯基、2-氟-1,4-伸苯基、2,3-二氟-1,4-伸苯基或2,6-二氟-1,4-伸苯基；Z ¹及Z ²為單鍵、伸乙基、伸乙烯基、伸甲氧基、羰氧基或二氟伸甲氧基；X ⁶及X ⁷為氫或氟；Y ¹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的烯氧基；m為1、2或3； 式（3）中，R ³及R ⁴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；Z ³為單鍵、伸乙基、伸乙烯基、伸甲氧基或羰氧基；n為1、2或3。 [Technical means to solve the problem] The present invention relates to a liquid crystal composition containing at least one compound selected from compounds represented by formula (1) as component A, and a liquid crystal display element containing the composition , at least one compound selected from the compounds represented by the formula (2) as the component B and at least one compound selected from the compounds represented by the formula (3) as the component C do not contain a polymerizable compound and a polymer, And has positive dielectric anisotropy.

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 C1-12 alkyl group with at least one hydrogen replaced by fluorine or chlorine; X ¹ , X ² , X ³ , X ⁴ and X ⁵ are hydrogen or fluorine, X ¹ , X ² , X ³ , X ⁴ and X At least one of ⁵ is fluorine; In formula (2), R ² is an alkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons, or an alkenyl group with 2 to 12 carbons; Ring A ¹ and Ring A ² is 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene or 2,6-difluoro-1,4-phenylene Base; Z ¹ and Z ² are single bond, ethylene, vinylene, methoxy, carbonyloxy or difluoromethoxy; X ⁶ and X ⁷ are hydrogen or fluorine; Y ¹ is fluorine, Chlorine, an alkyl group with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, an alkoxy group with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, or a carbon in which at least one hydrogen is substituted by fluorine or chlorine alkenyloxy group with a number of 2 to 12; m is 1, 2 or 3; in formula (3), R ³ and R ⁴ are alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or alkoxy with 1 to 12 carbons 2 to 12 alkenyl, or at least one hydrogen substituted by fluorine or chlorine alkenyl with carbon number 2 to 12; ring B and ring C are 1,4-cyclohexyl, 1,4-phenylene, 2- Fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ³ is a single bond, ethylene, vinylene, methoxyl or carbonyloxy; n is 1, 2 or 3.

[Effect of the invention] The advantage of the present invention 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, large optical anisotropy, large positive dielectric anisotropy, and large specific resistance , high stability to light, high stability to heat, and at least one of properties such as a large elastic constant. Another advantage would be to provide a liquid crystal composition having an appropriate balance between at least two of these properties. Another advantage is to provide a liquid crystal display device containing such a composition. Still another advantage is to provide an AM element having characteristics such as short response time, high voltage retention, low threshold voltage, high contrast, and long life.

The usage of terms in this manual is as follows. The terms "liquid crystal composition" and "liquid crystal display device" are sometimes abbreviated as "composition" and "device", respectively. "Liquid crystal display device" is a general term for liquid crystal display panels and liquid crystal display modules. "Liquid crystal compound" is a compound that has a liquid crystal phase such as a nematic phase or a smectic phase, and a compound that does not have a liquid crystal phase but is used to adjust the temperature range, viscosity, and dielectric anisotropy of the nematic phase. A general term for compounds mixed in compositions for the purpose. The compound has, for example, a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecule (liquid crystal molecule) is rod-like. A "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. A liquid crystal compound having an alkenyl group is not classified as a polymerizable compound in terms of its meaning.

The liquid crystal composition is prepared by mixing various liquid crystal compounds. Additives such as optically active compounds are optionally added to the liquid crystal composition. Even when additives are added, the ratio of the liquid crystal compound is represented by mass percentage (mass %) based on the mass of the liquid crystal composition not containing the additives. The ratio of the additives is represented by the mass percentage (mass %) based on the mass of the liquid crystal composition not containing the additives. That is, the ratio of liquid crystal compounds or additives is calculated based on the total mass of liquid crystal compounds.

The "upper limit temperature of the nematic phase" is sometimes simply referred to as the "upper limit temperature". The "lower limit temperature of the nematic phase" is sometimes simply referred to as the "lower limit temperature". The expression "enhancing the dielectric anisotropy" means that the value increases positively in the case of a composition with positive dielectric anisotropy, and means that the value increases negatively in the case of a composition with negative dielectric anisotropy. increase to the ground. "Large voltage retention" means that the device has a large voltage retention not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and after a long period of use not only at room temperature but also It also has a large voltage retention at a temperature close to the upper limit temperature. Sometimes the characteristics of the composition or element are studied by the time-varying test.

以所述化合物（1z）為例進行說明。式（1z）中，以六邊形包圍的α及β的記號分別與環α及環β對應，表示六元環、縮合環之類的環。在下標‘x’為2時，存在兩個環α。兩個環α所表示的兩個基可相同，或也可不同。所述規則適用於下標‘x’大於2時的任意兩個環α。所述規則也適用於鍵結基Z之類的其他記號。將環β的一邊橫切的斜線表示環β上的任意氫可經取代基（-Sp-P）取代。下標‘y’表示所取代的取代基的數量。在下標‘y’為0時，不存在此種取代。在下標‘y’為2以上時，在環β上存在多個取代基（-Sp-P）。在所述情況下，「可相同，或也可不同」的規則也適用。再者，所述規則也適用於將Ra的記號用於多種化合物的情況。

The compound (1z) will be described as an example. In formula (1z), the symbols α and β surrounded by a hexagon correspond to ring α and ring β, respectively, and represent rings such as six-membered rings and condensed rings. When the subscript 'x' is 2, there are two loops α. The two groups represented by the two rings α may be the same or different. The rule applies to any two rings α when the subscript 'x' is greater than 2. The rule also applies to other notations such as the bonding group Z. The oblique line crossing one side of the ring β indicates that any hydrogen on the ring β may be replaced by a substituent (-Sp-P). The subscript 'y' indicates the number of substituents substituted. When the subscript 'y' is 0, there is no such substitution. When the subscript 'y' is 2 or more, there are multiple substituents (-Sp-P) on the ring β. In the cases described, the "may be the same, or may be different" rule also applies. In addition, the said rule is also applicable to the case where the symbol of Ra is used for several compounds.

In formula (1z), for example, expressions such as "Ra and Rb are alkyl, alkoxy or alkenyl" mean that Ra and Rb are independently selected from the group of alkyl, alkoxy and alkenyl. Here, the group represented by Ra and the group represented by Rb may be the same or different.

At least one compound selected from the compounds represented by formula (1z) may be simply referred to as "compound (1z)". "Compound (1z)" refers to a compound represented by formula (1z), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas. The expression "at least one compound selected from the compounds represented by the formula (1z) and the formula (2z)" refers to at least one compound selected from the group of the compound (1z) and the compound (2z).

The expression "at least one 'A'" means that the number of 'A' is arbitrary. The expression "at least one 'A' may be replaced by 'B'" means that when the number of 'A' is one, the position of 'A' is arbitrary, and when the number of 'A' is two or more, their positions Unrestricted selection is also possible. Sometimes the expression "at least one _-CH2- may be substituted by -O-" is used. In such cases, _-CH2 - _CH2 -CH2- can be converted to -O- _CH2 - _O- by substituting non-adjacent _-CH2- with -O-. However, there is no substitution of adjacent _-CH2- with -O-. The reason is that -OO-CH ₂ - (peroxide) is generated in the substitution.

四氫吡喃-2,5-二基之類的二價基中，也相同。羰氧基之類的鍵結基（-COO-或-OCO-）也相同。 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 ones. These conditions are also the same for terminal groups such as alkoxy and alkenyl. Regarding the stereo configuration (configuration) related to 1,4-cyclohexylene, in order to increase the upper limit temperature, the trans configuration is better than the cis configuration. Since 2-fluoro-1,4-phenylene is left-right asymmetric, there are left (L) and right (R).

The same applies to divalent groups such as tetrahydropyran-2,5-diyl. The same applies to bonding groups such as carbonyloxy (-COO- or -OCO-).

The present invention includes the following items and the like.

式（1）中，R ¹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的烯氧基、或者至少一個氫經氟或氯取代的碳數1至12的烷基；X ¹、X ²、X ³、X ⁴及X ⁵為氫或氟，X ¹、X ²、X ³、X ⁴及X ⁵的至少一個為氟； 式（2）中，R ²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A ¹及環A ²為1,4-伸苯基、2-氟-1,4-伸苯基、2,3-二氟-1,4-伸苯基或2,6-二氟-1,4-伸苯基；Z ¹及Z ²為單鍵、伸乙基、伸乙烯基、伸甲氧基、羰氧基或二氟伸甲氧基；X ⁶及X ⁷為氫或氟；Y ¹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的烯氧基；m為1、2或3； 式（3）中，R ³及R ⁴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；Z ³為單鍵、伸乙基、伸乙烯基、伸甲氧基或羰氧基；n為1、2或3。 Item 1. A liquid crystal composition comprising at least one compound selected from compounds represented by formula (1) as component A, at least one compound selected from compounds represented by formula (2) as component B, and Component C is at least one compound selected from compounds represented by formula (3), does not contain a polymerizable compound and a polymer, and has positive dielectric anisotropy.

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 C1-12 alkyl group with at least one hydrogen replaced by fluorine or chlorine; X ¹ , X ² , X ³ , X ⁴ and X ⁵ are hydrogen or fluorine, X ¹ , X ² , X ³ , X ⁴ and X At least one of ⁵ is fluorine; In formula (2), R ² is an alkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons, or an alkenyl group with 2 to 12 carbons; Ring A ¹ and Ring A ² is 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene or 2,6-difluoro-1,4-phenylene Base; Z ¹ and Z ² are single bond, ethylene, vinylene, methoxy, carbonyloxy or difluoromethoxy; X ⁶ and X ⁷ are hydrogen or fluorine; Y ¹ is fluorine, Chlorine, an alkyl group with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, an alkoxy group with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, or a carbon in which at least one hydrogen is substituted by fluorine or chlorine alkenyloxy group with a number of 2 to 12; m is 1, 2 or 3; in formula (3), R ³ and R ⁴ are alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or alkoxy with 1 to 12 carbons 2 to 12 alkenyl, or at least one hydrogen substituted by fluorine or chlorine alkenyl with carbon number 2 to 12; ring B and ring C are 1,4-cyclohexyl, 1,4-phenylene, 2- Fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ³ is a single bond, ethylene, vinylene, methoxyl or carbonyloxy; n is 1, 2 or 3.

式（1-1）至式（1-6）中，R ¹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的烯氧基、或者至少一個氫經氟或氯取代的碳數1至12的烷基。 Item 2. The liquid crystal composition according to Item 1, containing at least one compound selected from the compounds represented by formula (1-1) to formula (1-6) as component A.

In formula (1-1) to formula (1-6), R ¹ is hydrogen, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, or 2 to 12 alkenyloxy, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.

Item 3. The liquid crystal composition according to Item 1 or Item 2, wherein the proportion of component A is in the range of 1% by mass to 50% by mass.

式（2-1）至式（2-11）中，R ²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 4. The liquid crystal composition according to any one of Items 1 to 3, containing at least one compound selected from the compounds represented by formula (2-1) to formula (2-11) as component B.

In formula (2-1) to formula (2-11), R ² 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 5. The liquid crystal composition according to any one of Items 1 to 4, wherein the proportion of Component B is in the range of 1% by mass to 50% by mass.

式（3-1）至式（3-13）中，R ³及R ⁴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, containing at least one compound selected from the compounds represented by formula (3-1) to formula (3-13) as component C.

In formula (3-1) to formula (3-13), R ³ and R ⁴ are alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, or Alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.

Item 7. The liquid crystal composition according to any one of Items 1 to 6, wherein the proportion of Component C is in the range of 20% by mass to 90% by mass.

式（4）中，R ⁵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，環D的至少一個為1,4-伸環己基、嘧啶-2,5-二基、1,3-二噁烷-2,5-二基或四氫吡喃-2,5-二基；Z ⁴為單鍵、伸乙基、伸乙烯基、伸甲氧基、羰氧基或二氟伸甲氧基；X ⁸及X ⁹為氫或氟；Y ²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的烯氧基；a為1、2、3或4。 Item 8. The liquid crystal composition according to any one of Items 1 to 7, containing at least one compound selected from the group of compounds represented by formula (4) as the component D.

In formula (4), R ⁵ is an alkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons, or an alkenyl group with 2 to 12 carbons; 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, at least one ring D is 1,4-cyclohexyl, pyrimidine- 2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; Z ⁴ is a single bond, ethylidene, vinylidene, methylene Oxygen, carbonyloxy or difluoromethoxyl; X ⁸ and X ⁹ are hydrogen or fluorine; Y ² is fluorine, chlorine, at least one hydrogen is substituted by fluorine or chlorine, an alkyl group with 1 to 12 carbons, at least An alkoxy group with 1 to 12 carbons in which one hydrogen is replaced by fluorine or chlorine, or an alkenyloxy group with 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine; a is 1, 2, 3 or 4.

式（4-1）至式（4-24）中，R ⁵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, comprising at least one compound selected from the group of compounds represented by formula (4-1) to formula (4-24) as a component d.

In formula (4-1) to formula (4-24), 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 proportion of component D is in the range of 1% by mass to 50% by mass.

式（5）中，R ⁶及R ⁷為氫、碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基或碳數2至12的烯氧基；環E及環G為1,4-伸環己基、1,4-伸環己烯基、四氫吡喃-2,5-二基、1,4-伸苯基、至少一個氫經氟或氯取代的1,4-伸苯基、萘-2,6-二基、至少一個氫經氟或氯取代的萘-2,6-二基、色原烷-2,6-二基、或者至少一個氫經氟或氯取代的色原烷-2,6-二基；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、7,8-二氟色原烷-2,6-二基、3,4,5,6-四氟芴-2,7-二基、4,6-二氟二苯並呋喃-3,7-二基、4,6-二氟二苯並噻吩-3,7-二基或1,1,6,7-四氟茚滿-2,5-二基；Z ⁵及Z ⁶為單鍵、伸乙基、伸乙烯基、伸甲氧基或羰氧基；c為0、1、2或3，d為0或1，而且c與d的和為3以下。 Item 11. The liquid crystal composition according to any one of Items 1 to 10, containing at least one compound selected from the compounds represented by formula (5) as the component E.

In formula ( ⁵ ), R6 and ^R7 are hydrogen, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons or alkenyloxy with 2 to 12 carbons base; ring E and ring G are 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen Fluorine or chlorine substituted 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen substituted by fluorine or chlorine naphthalene-2,6-diyl, chroman-2,6-diyl , or chromane-2,6-diyl with at least one hydrogen replaced by fluorine or chlorine; 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, 7,8-difluorochrome Ortho-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6 -Difluorodibenzothiophene-3,7-diyl or 1,1,6,7-tetrafluoroindan-2,5-diyl; Z ⁵ and Z ⁶ are single bonds, ethylene, vinylene group, methoxy or carbonyloxy; c is 0, 1, 2 or 3, d is 0 or 1, and the sum of c and d is 3 or less.

式（5-1）至式（5-35）中，R ⁶及R ⁷為氫、碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基或碳數2至12的烯氧基。 Item 12. The liquid crystal composition according to any one of Items 1 to 11, containing at least one compound selected from the compounds represented by formula (5-1) to formula (5-35) as component E.

In formula (5-1) to formula (5-35), R ⁶ and R ⁷ are hydrogen, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons or an alkenyloxy group having 2 to 12 carbon atoms.

Item 13. The liquid crystal composition according to Item 11 or Item 12, wherein the proportion of component E is in the range of 3% by mass to 45% by mass.

Item 14. The liquid crystal composition according to any one of Items 1 to 13, which has a nematic phase at least in the range of 0°C to 60°C.

Item 15. The liquid crystal composition according to any one of Items 1 to 14, wherein the upper limit temperature of the nematic phase is 60° C. or higher, and the optical anisotropy at a wavelength of 589 nm (measured at 25° C.) It is 0.07 or more, and the dielectric anisotropy (measured at 25° C.) at a frequency of 1 kHz is 2 or more.

Item 16. A liquid crystal display element comprising the liquid crystal composition according to any one of Items 1 to 15.

Item 17. The liquid crystal display element according to item 16, wherein the operation mode of the liquid crystal display element is TN mode, ECB mode, OCB mode, IPS mode, FFS mode or FPA mode, and the driving mode of the liquid crystal display element is an active matrix Way.

Item 18. Use of a liquid crystal composition, the liquid crystal composition being the liquid crystal composition according to any one of Items 1 to 15, which is used in a liquid crystal display element.

The present invention also includes the following items. (a) The composition, which contains one compound, two compounds, or three or more compounds selected from additives such as optically active compounds, antioxidants, ultraviolet absorbers, matting agents, pigments, defoamers, and polar compounds compound of. (b) An AM device including the composition. (c) An element containing the composition and having a pattern of PC, TN, STN, ECB, OCB, IPS, VA, FFS or FPA. (d) A transmissive device containing the composition. (e) Use of the composition as a composition having a nematic phase. (f) Use of an optically active composition obtained by adding an optically active compound to the composition.

The liquid crystal composition of the present invention does not contain polymerizable compounds and polymers, so it is compatible with "Polymer Dispersed Liquid Crystal (PDLC)" or "Polymer Dispersed Liquid Crystal" or "Polymer "Polymer Network Liquid Crystal (PNLC)" is different.

The composition of the present invention will be described in the following order. First, the structure of the composition will be described. Second, the main characteristics of the component compounds and the main effects of the compounds on the composition or device will be described. Thirdly, combinations of component compounds in the composition, preferred ratios, and their grounds will be described. Fourth, preferred forms of the component compounds will be described. Fifth, preferred component 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 structure of the composition will be described. The composition contains various liquid crystal compounds. The composition may also contain additives. Additives are optically active compounds, antioxidants, UV absorbers, matting agents, pigments, defoamers, polar compounds, and the like. These compositions are classified into composition A and composition B from the viewpoint of liquid crystal compounds. Composition A may contain other liquid crystal compounds, additives, etc. . "Other liquid crystal compounds" are liquid crystal compounds different from compound (1), compound (2), compound (3), compound (4) and compound (5). Such compounds are mixed into the composition for the purpose of further adjusting properties.

Composition B substantially contains only liquid crystal compounds selected from compound (1), compound (2), compound (3), compound (4) and compound (5). "Substantially" means that the composition B may contain additives, but does not contain other liquid crystal compounds. Compared with composition A, the number of components of composition B is small. Composition B is superior to composition A from the viewpoint of cost reduction. Composition A is superior to composition B from the viewpoint that characteristics can be further adjusted by mixing other liquid crystal compounds.

Second, the main characteristics of the component compounds and the main effects of the compounds on the composition or device will be described. The main properties of the component compounds are summarized in Table 2. In the symbols in Table 2, L means large or high, M means medium, and S means small or low. Symbols L, M, and S are classifications based on qualitative comparison among component compounds, and symbol 0 (zero) means less than S.

Table 2. Properties of Liquid Crystalline Compounds characteristic Compound (1) Compound (2) Compound (3) Compound (4) Compound (5) upper limit temperature M~L M~L S～L S～L S～L viscosity M~L M~L S~M M~L M~L optical anisotropy L L S～L M~L M~L Dielectric anisotropy L M~L 0 M~L M~L specific resistance L L L L L

The main effects of the component compounds are as follows. Compound (1) improves dielectric anisotropy and optical anisotropy. Compound (2) improves optical anisotropy and dielectric anisotropy. Compound (3) reduces the viscosity or increases the upper limit temperature. Compound (4) increases dielectric anisotropy. Compound (5) increases the dielectric constant in the minor axis direction.

Thirdly, combinations of component compounds in the composition, preferred ratios, and reasons thereof will be described. A preferable combination of the component compounds in the composition is compound (1)+compound (2)+compound (3), compound (1)+compound (2)+compound (3)+compound (4), compound (1) + Compound (2) + Compound (3) + Compound (5) or Compound (1) + Compound (2) + Compound (3) + Compound (4) + Compound (5). A particularly preferred combination is compound (1)+compound (2)+compound (3).

In order to improve the dielectric anisotropy and optical anisotropy, the preferable ratio of the compound (1) is about 1 mass % or more, and in order to lower the minimum temperature, the preferable ratio of the compound (1) is about 50 mass % or less. A more preferable ratio is in the range of about 1% by mass to about 30% by mass. A particularly preferable ratio is in the range of about 2% by mass to about 15% by mass.

In order to improve the optical anisotropy and dielectric anisotropy, the preferable ratio of the compound (2) is about 1 mass % or more, and in order to lower the minimum temperature, the preferable ratio of the compound (2) is about 50 mass % or less. A more preferable ratio is in the range of about 5% by mass to about 30% by mass. A particularly preferable ratio is in the range of about 5% by mass to about 20% by mass.

In order to reduce the viscosity or increase the upper limit temperature, the preferable ratio of the compound (3) is about 20% by mass or more, and in order to increase the dielectric anisotropy, the preferable ratio of the compound (3) is about 90% by mass or less. A more preferable ratio is in the range of about 30% by mass to about 90% by mass. A particularly preferable ratio is in the range of about 50% by mass to about 90% by mass.

In order to increase the dielectric anisotropy, the preferable ratio of the compound (4) is about 1 mass % or more, and in order to lower the minimum temperature, the preferable ratio of the compound (4) is about 50 mass % or less. A more preferable ratio is in the range of about 1% by mass to about 30% by mass. A particularly preferable ratio is in the range of about 1% by mass to about 20% by mass.

In order to increase the dielectric constant in the minor axis direction, the preferable ratio of the compound (5) is about 3 mass % or more, and in order to lower the minimum temperature, the preferable ratio of the compound (5) is about 45 mass % or less. A more preferable ratio is in the range of about 3% by mass to about 30% by mass. A particularly preferable ratio is in the range of about 3% by mass to about 20% by mass.

Fourth, preferred forms of the component compounds will be described. In formula (1), formula (2), formula (3), formula (4) and formula (5), R ¹ is hydrogen, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, Alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine. Preferred R ¹ is an alkyl group having 1 to 12 carbons or an alkenyl group having 2 to 12 carbons. Particularly preferred R ¹ is an alkyl group having 3 to 5 carbons or an alkenyl group having 2 to 4 carbons. R ² is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons. In order to improve stability, preferred R ² is an alkyl group with 1 to 12 carbons. ^R3 and R4 are alkyl with ¹ to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, or C2 to 12 with at least one hydrogen replaced by fluorine or chlorine Alkenyl. In order to reduce the viscosity, the preferred ^R3 or R4 is an alkenyl group with ² to 12 carbons, and in order to improve the stability, the preferred ^R3 or R4 is an alkyl group with ¹ to 12 carbons. R ⁵ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons. In order to improve stability, preferred R ⁵ is an alkyl group with 1 to 12 carbons. R6 and ^R7 are 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. In order to improve stability, preferred R ⁶ or R ⁷ is an alkyl group with 1 to 12 carbons, in order to reduce the viscosity, preferred R ⁶ or R ⁷ is an alkenyl group with 2 to 12 carbons, in order to improve the dielectric properties Anisotropy, preferred R ⁶ or R ⁷ is an alkoxy group with 1 to 12 carbons.

Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. In order to reduce the viscosity, more preferable alkyl groups are methyl groups, ethyl groups, propyl groups, butyl groups or pentyl groups.

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

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

Preferred alkenyloxy is ethyleneoxy, allyloxy, 3-butenyloxy, 3-pentenyloxy or 4-pentenyloxy. In order to reduce the viscosity, more preferable alkenyloxy group is allyloxy group or 3-butenyloxy group.

Preferred examples of alkyl in which at least one hydrogen is substituted by 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, further preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl or 5-fluoropentyl.

Preferred examples of alkenyl in which at least one hydrogen is substituted by 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 further preferred example is 2,2-difluorovinyl or 4,4-difluoro-3-butenyl.

Ring A ¹ and Ring A ² are 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene or 2,6-difluoro- 1,4-phenylene. In order to reduce the viscosity, preferred ring ^A is 1,4-phenylene. In order to increase the dielectric anisotropy, preferable ring A2 is ² -fluoro-1,4-phenylene or 2,6-difluoro-1,4-phenylene.

Ring B and ring C are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene. In order to reduce the viscosity or to increase the upper limit temperature, the preferred ring B or ring C is 1,4-cyclohexylene, in order to improve the optical anisotropy or to lower the lower limit temperature, the preferred ring B or ring C is 1,4 -phenylene or 2-fluoro-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, ring D At least one is 1,4-cyclohexylene, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl. Desirable ring D is 1,4-cyclohexylene for increasing the upper limit temperature. In addition, when there are two or more rings D, 1,4-diphenylene is also preferable in order to increase optical anisotropy, and 1,3-diphenylene is also preferable in order to increase dielectric anisotropy. Oxane-2,5-diyl, 2-fluoro-1,4-phenylene or 2,6-difluoro-1,4-phenylene. Tetrahydropyran-2,5-diyl is

or

preferably

.

Ring E and ring G are 1,4-cyclohexylene, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen through fluorine or Chlorine-substituted 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen substituted by fluorine or chlorine naphthalene-2,6-diyl, chroman-2,6-diyl, or A chroman-2,6-diyl group in which at least one hydrogen has been replaced by fluorine or chlorine. A preferred example of 1,4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine is 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene or 2- Chloro-3-fluoro-1,4-phenylene. An example of naphthalene-2,6-diyl in which at least one hydrogen is substituted by fluorine or chlorine is 3,4,5-trifluoronaphthalene-2,6-diyl. An example of a chroman-2,6-diyl group in which at least one hydrogen is substituted by fluorine or chlorine is 7,8-difluorochroman-2,6-diyl. In order to reduce the viscosity, the preferred ring E or ring G is 1,4-cyclohexylene, and in order to improve the dielectric anisotropy, the preferred ring E or ring G is tetrahydropyran-2,5-diyl, In order to increase the optical anisotropy, preferable ring E or ring G is 1,4-phenylene group.

為了降低黏度，較佳的環F為2,3-二氟-1,4-伸苯基，為了提高介電各向異性，較佳的環F為4,6-二氟二苯並呋喃-3,7-二基。 Ring F is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4- Phenylylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochromane-2,6-diyl, 3,4,5,6-tetrafluorofluorene- 2,7-diyl (FLF4), 4,6-difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2 ) or 1,1,6,7-tetrafluoroindan-2,5-diyl (InF4).

In order to reduce the viscosity, the preferred ring F is 2,3-difluoro-1,4-phenylene, and in order to improve the dielectric anisotropy, the preferred ring F is 4,6-difluorodibenzofuran- 3,7-diradical.

Z ¹ and Z ² are single bonds, ethylene, vinylene, methoxy, carbonyloxy or difluoromethoxy. In order to reduce the viscosity, preferred Z ¹ is a single bond. In order to reduce the viscosity, the preferred Z ² is a single bond, and in order to increase the dielectric anisotropy, the preferred Z ² is difluoromethoxyl. Z ³ is a single bond, ethylene, vinylene, methoxy or carbonyloxy. ^In order to reduce the viscosity, preferred Z3 is a single bond. Z ⁴ is a single bond, ethylene, vinylene, methoxy, carbonyloxy or difluoromethoxy. In order to reduce the viscosity, the preferred Z ⁴ is a single bond, and in order to increase the dielectric anisotropy, the preferred Z ⁴ is difluoromethoxyl. Z ⁵ and Z ⁶ are single bonds, ethylene, vinylene, methoxy or carbonyloxy. In order to reduce the viscosity, the preferred Z ⁵ or Z ⁶ is a single bond, in order to increase the elastic constant, the preferred Z ⁵ or Z ⁶ is ethylenyl group, in order to increase the dielectric constant in the minor axis direction, the preferred Z ⁵ Or ^Z6 is methoxyl.

Divalent groups such as methoxyl groups are left-right asymmetric. Among the methoxyl groups, -CH ₂ O- is better than -OCH ₂ -. Among carbonyloxy groups, -COO- is preferable to -OCO-. Among difluoromethoxyl groups, -CF ₂ O- is preferable to -OCF ₂ -.

X ¹ , X ² , X ³ , X ⁴ and X ⁵ are hydrogen or fluorine, and at least one of X ¹ , X ² , X ³ , X ⁴ and X ⁵ is fluorine. In order to increase the dielectric anisotropy, preferably at least two of X ¹ , X ² , X ³ , X ⁴ and X ⁵ are fluorine. In order to lower the minimum temperature, at least one of X ¹ , X ² and X ³ is preferably fluorine. X ⁶ , X ⁷ , X ⁸ and X ⁹ are hydrogen or fluorine. In order to increase the dielectric anisotropy, preferred X ⁶ , X ⁷ , X ⁸ or X ⁹ is fluorine.

^Y1 and ^Y2 are fluorine, chlorine, an alkyl group with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, an alkoxy group with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, or at least one Alkenyloxy having 2 to 12 carbons in which hydrogen is substituted by fluorine or chlorine. In order to increase the dielectric anisotropy, preferred ^Y1 or ^Y2 is fluorine, an alkyl group with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, or an alkyl group with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine. to 12 alkoxy groups. A preferable example of an alkyl group in which at least one hydrogen is substituted by fluorine or chlorine is trifluoromethyl. A preferable example of an alkoxy group in which at least one hydrogen is replaced by fluorine or chlorine is trifluoromethoxy.

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

Fifth, preferred component compounds are shown. Preferred compound (1) is compound (1-1) to compound (1-6) described in Item 2. Preferably, at least one of the components A is compound (1-1), compound (1-4), compound (1-5) and compound (1-6).

Preferred compound (2) is compound (2-1) to compound (2-11) described in Item 4. Among these compounds, at least one of the component B is preferably compound (2-1), compound (2-2), compound (2-4), compound (2-6) or compound (2-7). Preferably, at least two of component B are compound (2-1) and compound (2-2), compound (2-1) and compound (2-4), compound (2-1) and compound (2-6) ), compound (2-2) and compound (2-6), compound (2-2) and compound (2-7), compound (2-4) and compound (2-6), compound (2-4) And compound (2-7) or the combination of compound (2-6) and compound (2-7).

Preferred compound (3) is compound (3-1) to compound (3-13) described in Item 6. Among these compounds, preferably at least one of component C is compound (3-1), compound (3-3), compound (3-5), compound (3-6), compound (3-7), compound ( 3-8), compound (3-10) or compound (3-13). More preferably, at least one of the components C is compound (3-1), compound (3-3), compound (3-6) or compound (3-8). Preferably, at least two of component C are compound (3-1) and compound (3-3), compound (3-1) and compound (3-6), compound (3-1) and compound (3-8) ), compound (3-3) and compound (3-6), compound (3-3) and compound (3-8) or a combination of compound (3-6) and compound (3-8).

Preferred compound (4) is compound (4-1) to compound (4-24) described in Item 9. Among these compounds, preferably at least one of component D is compound (4-2), compound (4-4), compound (4-8), compound (4-14), compound (4-15), compound ( 4-20) or compound (4-23).

Preferred compound (5) is compound (5-1) to compound (5-35) described in Item 12. Among these compounds, preferably at least one of component E is compound (5-1), compound (5-2), compound (5-3), compound (5-6), compound (5-8), compound ( 5-9), compound (5-10), compound (5-14) or compound (5-16).

Sixth, additives that can be added to the composition will be described. Such additives are optically active compounds, antioxidants, UV absorbers, matting agents, pigments, defoamers, polar compounds, and the like. An optically active compound is added to the composition for the purpose of imparting a twist angle (torsion angle) by inducing a helical structure of liquid crystal molecules. Examples of such compounds are compound (6-1) to compound (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% by mass to about 2% by mass.

In order to prevent the reduction of the specific resistance caused by heating in the atmosphere or to maintain a large voltage retention not only at room temperature but also at a temperature close to the upper limit temperature after the element has been used for a long time, it is also possible to further Antioxidants such as compound (7-1) to compound (7-3) are added to the composition.

Compound (7-2) is effective in maintaining a large voltage retention 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 due to its low volatility. In order to obtain the above effect, the preferable ratio of the antioxidant is about 50 ppm or more, and the preferable ratio of the antioxidant is about 600 ppm or less in order not to lower the upper limit temperature or not to increase the lower limit temperature. A further preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferable examples of ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, triazole derivatives, and the like. In addition, light stabilizers such as sterically hindered amines are also preferable. Preferable examples of the photostabilizer include compound (8-1) to compound (8-16) and the like. The preferred ratio of these absorbents or stabilizers is about 50 ppm or more in order to obtain the above effects, and about 10000 ppm or less in order not to lower the upper limit temperature or not to increase the lower limit temperature. A further preferred ratio is in the range of about 100 ppm to about 10000 ppm.

The matting agent is a compound that prevents the decomposition of the liquid crystal compound by receiving light energy absorbed by the liquid crystal compound and converting it into thermal energy. Preferable examples of the matting agent include compound (9-1) to compound (9-7) and the like. In order to obtain the above effect, the preferred ratio of these matting agents is about 50 ppm or more, and in order not to raise the lower limit temperature, the preferable ratio of these matting agents is about 20000 ppm or less. A further preferred ratio is in the range of about 100 ppm to about 10000 ppm.

A dichroic dye such as an azo dye, an anthraquinone dye, or the like is added to the composition in order to be suitable for a guest host (GH) mode element. 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 effect, the preferable ratio of the antifoaming agent is about 1 ppm or more, and in order to prevent display defects, the preferable ratio of the antifoaming agent is about 1000 ppm or less. A further preferred ratio is in the range of about 1 ppm to about 500 ppm.

A polar compound is an organic compound having polarity. Here, compounds having ionic bonds are not included. Atoms such as oxygen, sulfur, and nitrogen are electronegative and tend to have a partial negative charge. Carbon and hydrogen are neutral or tend to have a partial positive charge. Polarity arises from the unequal distribution of partial charges among the different kinds of atoms in a compound. For example, the polar compound has at least one partial structure of -OH, -COOH, -SH, -NH ₂ , >NH, >N-.

Seventh, the synthesis method of the component compounds will be described. These compounds can be synthesized by known methods. Synthetic methods are exemplified. Compound (1-1) was synthesized by the method described in JP-A-10-114733. Compound (2-4) was synthesized by the method described in JP-A-10-251186. Compound (3-1) was synthesized by the method described in JP-A-59-176221. Compound (4-2) was synthesized by the method described in Japanese Patent Application Laid-Open No. 2-233626. Antioxidants are commercially available. Compound (5-1) was synthesized by the method described in JP-A-2-503441. Compound (7-1) is available from Sigma-Aldrich Corporation. Compound (7-2) and the like were synthesized by the method described in US Pat. No. 3,660,505.

Compounds whose synthetic methods are not described can be synthesized by the methods described in the following books: Organic Syntheses (John Wiley & Sons, Inc), Organic Reactions (Organic Syntheses) Reactions, John Wiley & Sons (John Wiley & Sons, Inc)), "Comprehensive Organic Synthesis" (Comprehensive Organic Synthesis, Pergamon Press), "New Experimental Chemistry Lecture" (Maruzen), etc. The composition is produced from the compound thus obtained 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. The composition mainly has a lower limit temperature of about -10°C or lower, an upper limit temperature of about 60°C or higher, and an optical anisotropy ranging from 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 also be prepared by controlling the ratio of the component compounds or by mixing other liquid crystal compounds. 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 the composition has a large voltage retention. The composition is suitable for AM devices. The composition is particularly suitable for a transmissive AM device. The composition can be used as a composition having a nematic phase, and can be used as an optically active composition by adding an optically active compound.

The composition can be used for AM devices. Furthermore, it can also be used for a PM element. 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. It is especially preferred for AM elements with TN, OCB, 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 liquid crystal molecules may be parallel to or perpendicular to the glass substrate. These 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. The composition can also be used for a nematic curvilinear aligned phase (NCAP) type element produced by microencapsulation, or a three-dimensional network polymer formed in the composition Polymer dispersed (polymer dispersed, PD) type components.

[Example] The present invention is further described in detail by means of examples. The present invention is not limited by these examples. The present invention comprises a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes a mixture obtained by mixing at least two of the compositions of the examples. The synthesized compounds were identified by nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) analysis and other methods. The properties of compounds, compositions, and devices were measured by the methods described below.

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

Gas chromatographic analysis: GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for measurement. The carrier gas was helium (2 mL/min). The sample gasification chamber was set at 280°C, and the detector (flame ionization detector (FID)) was set at 300°C. 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 for the separation of component compounds; the stationary liquid phase was dimethyl polysiloxane ; no polarity). After the column was kept 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% by mass), 1 μL of it was injected into the sample vaporization chamber. The recorder is a chromatography unit (Chromatopac) manufactured by Shimadzu Corporation or its equivalent. The obtained gas chromatogram shows the peak retention time and the peak area corresponding to the component compounds.

As a solvent for diluting the sample, chloroform, hexane, etc. can be used. In order to separate 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), and BP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by SGE International Pty. Ltd in Australia. For the purpose of preventing 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 method described below. The liquid crystal compound mixture was analyzed by gas chromatography (FID). The area ratio of the peaks in the gas chromatogram corresponds to the ratio of liquid crystal 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.

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

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

Measuring method: The characteristic was measured by the following method. Most of these methods are the methods described in the JEITA standard (JEITA·ED-2521B) deliberated and established by the Japan Electronics and Information Technology Industries Association (JEITA) or modified methods. Thin-film transistors (TFTs) are not mounted on the TN element used for measurement.

(1) Upper limit temperature of the 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 simply referred to as "upper limit temperature".

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

(4) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa s): According to "Molecular Crystals and Liquid Crystals" by M. Imai et al., Vol. 259 , 37 (1995) described in the method to determine. The 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. In the range of 16 V to 19.5 V, a voltage was applied to the element in steps of 0.5 V. After no voltage was applied for 0.2 seconds, the voltage was repeatedly applied under the conditions of applying only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current (peak current) and peak time (peak time) of the transient current (transient current) generated by the application were measured. The value of the rotational viscosity was obtained from these measured values and the calculation formula (10) 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 prism in one direction, the sample is dropped onto the main prism. The refractive index n∥ is measured when the direction of polarization is parallel to the direction of rubbing. The refractive index n⊥ is measured when the direction of polarization is 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 the device, and the dielectric constant (ε∥) in the long-axis direction of the liquid crystal molecules was measured after 2 seconds. A sine wave (0.5 V, 1 kHz) was applied to the device, and the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured after 2 seconds. The value of the dielectric anisotropy is calculated according to the formula Δε=ε∥−ε⊥.

(7-1) Threshold voltage (Vth (25); measured at 25° C.; V): For measurement, a Liquid Crystal Display (LCD) Model 5200 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source is a halogen lamp. The sample was placed in an FFS device with a distance (cell gap) between two glass substrates of 3.2 (μm). The voltage (32 Hz, rectangular wave) applied to the element was increased stepwise from 0 V to 10 V in units of 0.01 V. At this time, the device was irradiated with light from a vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was prepared in which the transmittance was 100% when the light amount was at the maximum and the transmittance was 0% when the light amount was at the minimum. The threshold voltage is represented by the voltage at which the transmittance becomes 95%.

(7-2) Threshold voltage (Vth (-30); measured at -30°C; V): same as (7-1) except that measurement was performed at -30°C.

(8) Voltage retention rate (VHR-1; measured at 25°C; %): The TN device used for the measurement has a polyimide alignment film, and the distance (cell gap) between the two glass substrates is 5 μm. After placing a sample in the device by vacuum injection, the injection port is sealed with an adhesive hardened by ultraviolet rays. The TN element was charged by applying a pulse voltage (1 V, 60 microseconds). The decaying voltage was measured with a high-speed voltmeter for 166.7 milliseconds, and the area A between the voltage curve per unit cycle and the horizontal axis was obtained. Area B is the area when not attenuated. The voltage retention rate is represented by the percentage of the area A to the area B.

(9) Voltage retention rate (VHR-2; measured at 60° C.; %): The voltage retention rate 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 retention rate (VHR-3; measured at 60°C; %): After irradiating ultraviolet rays, the voltage retention rate was measured to evaluate the stability against ultraviolet rays. The TN element used for the measurement has a polyimide alignment film and a cell gap of 5 μm. A sample was injected into the element, and 5 mW/cm ² of ultraviolet rays was irradiated for 167 minutes. The light source is black light (black light) manufactured by Iwasaki (EYEGRAPHICS) Co., Ltd., F40T10/BL (peak wavelength 369 nm), and the distance between the element and the light source is 5 mm. In the measurement of VHR-3, the decaying voltage was measured for a period of 166.7 milliseconds. A composition having a large VHR-3 has a large stability against ultraviolet rays.

(11) Voltage retention rate (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, measure the voltage retention rate to evaluate the thermal resistance stability. In the measurement of VHR-4, the decaying voltage was measured for a period of 166.7 milliseconds. A composition having a large VHR-4 has a large stability to heat.

(12) Voltage retention rate (VHR-5; measured at 60°C; %): After the TN element injected with the sample was left standing on the backlight for two weeks, the voltage retention rate was measured to evaluate the stability against the backlight. In the measurement of VHR-5, the decaying voltage was measured for a period of 166.7 milliseconds. A composition having a large VHR-5 has great stability against backlight.

(13) Response time (τ; measured at 25° C.; ms): An LCD5200 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source is a halogen lamp. Set the Low-pass filter to 5 kHz. A sample is placed in an FFS element with a gap (cell gap) between two glass substrates of 3.2 μm. A rectangular wave (60 Hz, Vth(25), 0.5 seconds) was applied to the element. At this time, the device was irradiated with light from a vertical direction, and the amount of light transmitted through the device was measured. The transmittance is regarded as 100% when the light quantity becomes the maximum, and the transmittance is regarded as 0% when the light quantity becomes the minimum. Rise time (τr: rise time; milliseconds) is the time required for the transmittance to change from 90% to 10%. Fall time (τf: fall time; milliseconds) is the time required for the transmittance to change from 10% to 90%. The response time is represented by the sum of the rise time and fall time obtained as described above.

(14) Elastic constant (K; measured at 25° C.; pN): An LCR meter HP4284A manufactured by Yokogawa Hewlett Packard Co., Ltd. was used for measurement. The sample was placed in a horizontal alignment element with a distance (cell gap) between two glass substrates of 20 μm. A charge of 0 volts to 20 volts was applied to the element, and the electrostatic capacitance and applied voltage were measured. Values of capacitance (C) and applied voltage (V) measured using equation (2.98) and equation (2.101) on page 75 of "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun) Carry out fitting, and obtain the values of K11 and K33 according to formula (2.99). Next, K22 is calculated by applying the values of K11 and K33 obtained just now to the formula (3.18) on page 171 of the "Liquid Crystal Device Handbook". The elastic constant is represented by the average value of K11, K22, and K33 obtained as described above.

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

(16) Pitch (P; measured at room temperature; μm): The pitch is measured using the wedge method. See page 196 of "Liquid Crystal Handbook" (published in 2000, Maruzen). Inject the sample into the wedge-shaped cell, and after standing at room temperature for 2 hours, observe the interval of the disclination line with a polarizing microscope (Nikon (stock), trade name MM40/60 series) (d2-d1). The pitch (P) is calculated from the following formula where the angle of the wedge element is expressed as θ. P=2×(d2-d1)×tanθ.

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

(18) Frequency dependence of dielectric anisotropy (F10; measured at -20°C): Put the sample. A sine wave (0.5 V, 20 Hz·50 Hz·100 Hz·1 kHz·5 kHz·10 kHz·50 kHz·100 kHz·500 kHz·1000 kHz) is applied to the element, and the short-term value of the liquid crystal molecules is measured after 2 seconds. Permittivity (ε⊥) in the axial direction. Let the frequency at which the dielectric anisotropy decreases by 10% relative to the dielectric anisotropy at 20 Hz be F10. The larger the F10, the smaller the frequency dependence.

Examples of compositions are shown below. Component compounds are represented by symbols based on definitions in Table 3 below. In Table 3, the configuration related to 1,4-cyclohexylene is trans configuration. A number in parentheses following a symbolized compound indicates the formula to which the compound belongs. The mark of (-) means another liquid crystal compound. The proportion (percentage) of the liquid crystal compound is the mass percentage (mass %) based on the mass of the liquid crystal composition not including additives. Finally, the characteristic values of the composition are summarized.

[Comparative example 1] A composition not containing compound (1) was prepared. 3-BB(F)B(F,F)-CF3 （2-2） 5% 3-BB(F)B(F,F)XB(F,F)-F （2-6） 3% 4-BB(F)B(F,F)XB(F,F)-F （2-6） 7% 3-HH-V (3-1) 38% 3-HH-V1 (3-1) 7% V2-BB-1 (3-3) 6% V-HBB-2 (3-6) 6% 1-BB(F)B-2V （3-8） 8% 2-BB(F)B-2V (3-8) 11% 3-BB(F)B-2V (3-8) 9% NI=82.0℃; Tc＜-10℃; Δn=0.147; Δε=3.3; γ1=47.0 mPa s; τ=16.5 ms; VHR-1=99.5%.

[Comparative example 2] A composition not containing the compound (1) but containing a cyano compound other than the compound (1) is prepared. 1V2-BEB(F,F)-C （-） 5% 3-BB(F)B(F,F)-CF3 （2-2） 3% 3-HH-V (3-1) 39% 3-HH-V1 (3-1) 7% V2-BB-1 (3-3) 3% V-HBB-2 (3-6) 6% 2-BB(F)B-3 (3-8) 6% 2-BB(F)B-5 （3-8） 6% 1-BB(F)B-2V （3-8） 8% 2-BB(F)B-2V (3-8) 11% 3-BB(F)B-2V (3-8) 6% NI=81.4℃; Δn=0.147; Δε=3.1; VHR-1=70.0%.

[Example 1] 3-BB(F)B(F,F)-C （1-6） 5% 3-BB(F)B(F,F)-CF3 （2-2） 4% 3-BB(F)B(F,F)XB(F,F)-F （2-6） 2% 3-HH-V (3-1) 39% 3-HH-V1 (3-1) 7% V2-BB-1 (3-3) 8% V-HBB-2 (3-6) 6% 1-BB(F)B-2V （3-8） 8% 2-BB(F)B-2V (3-8) 11% 3-BB(F)B-2V (3-8) 10% NI=79.8℃; Tc＜-10℃; Δn=0.148; Δε=3.2; γ1=42.3 mPa s; τ=14.6 ms; VHR-1=99.0%.

[Example 2] 3-BB(F)B-C (1-1) 5% 3-BB(F)B(F,F)-CF3 （2-2） 4% 3-BB(F)B(F,F)XB(F,F)-F （2-6） 3% 4-BB(F)B(F,F)XB(F,F)-F （2-6） 3% 3-HH-V (3-1) 39% 3-HH-V1 (3-1) 7% V2-BB-1 (3-3) 8% V-HBB-2 (3-6) 6% 1-BB(F)B-2V （3-8） 8% 2-BB(F)B-2V (3-8) 11% 3-BB(F)B-2V (3-8) 6% NI=81.1℃; Tc＜-10℃; Δn=0.148; Δε=3.4; γ1=45.6 mPa s; τ=15.6 ms; VHR-1=99.4%.

The results of Comparative Example 1, Comparative Example 2, Example 1 and Example 2 are summarized in Table 4. Table 4. Summary of physical properties Comparative example 1 Comparative example 2 Example 1 Example 2 γ1 (mPa·s) 47.0 - 42.3 45.6 τ (ms) 16.5 - 14.6 15.6 VHR-1 (%) 99.5 70.0 99.0 99.4

It can be seen that the compositions of Example 1 and Example 2 have a smaller rotational viscosity (γ1) and a shorter response time (τ) than the composition of Comparative Example 1, and have a larger voltage holding ratio than the composition of Comparative Example 2 (VHR-1). In addition, it can be seen that the compositions of Example 1 and Example 2 have the same voltage holding ratio as the composition of Comparative Example 1 which does not contain a cyano compound, although the compositions of Example 1 and Example 2 contain a cyano compound.

[Example 3] 3-BBB(F)-C (1-3) 2% 3-BB(F)B(F,F)-CF3 （2-2） 4% 3-BB(F)B(F,F)XB(F,F)-F （2-6） 3% 4-BB(F)B(F,F)XB(F,F)-F （2-6） 6% 3-HH-V (3-1) 39% 3-HH-V1 (3-1) 6% V2-BB-1 (3-3) 8% V-HBB-2 (3-6) 6% 1-BB(F)B-2V （3-8） 8% 2-BB(F)B-2V (3-8) 11% 3-BB(F)B-2V (3-8) 7% NI=80.6°C; Tc<0°C; Δn=0.146; Δε=3.6; γ1=45.6 mPa s; τ=15.5 ms; VHR-1=99.1%.

[Example 4] 3-BBB(F,F)-C (1-5) 2% 3-BB(F)B(F,F)-CF3 （2-2） 4% 3-BB(F)B(F,F)XB(F,F)-F （2-6） 3% 4-BB(F)B(F,F)XB(F,F)-F （2-6） 5% 3-HH-V (3-1) 39% 3-HH-V1 (3-1) 6% V2-BB-1 (3-3) 8% V-HBB-2 (3-6) 6% 1-BB(F)B-2V （3-8） 8% 2-BB(F)B-2V (3-8) 11% 3-BB(F)B-2V （3-8） 8% NI=80.4℃; Tc＜-10℃; Δn=0.148; Δε=3.4; γ1=43.3 mPa s; τ=15.0 ms; VHR-1=98.9%.

[Example 5] 5-BBB(F,F)-C （1-5） 5% 3-BB(F)B(F,F)-CF3 （2-2） 4% 3-BB(F)B(F,F)XB(F,F)-F （2-6） 4% 3-HH-V (3-1) 39% 3-HH-V1 （3-1） 8% V2-BB-1 (3-3) 8% V-HBB-2 (3-6) 5% 1-BB(F)B-2V （3-8） 8% 2-BB(F)B-2V (3-8) 11% 3-BB(F)B-2V （3-8） 8% NI=80.4℃; Tc＜0℃; Δn=0.147; Δε=3.4; γ1=41.8 mPa s; τ=14.5 ms; VHR-1=99.0%.

[Example 6] 3-BB(F)B(F)-C （1-4） 5% 3-BB(F)B(F,F)-CF3 （2-2） 4% 3-BB(F)B(F,F)XB(F,F)-F （2-6） 4% 3-HH-V （3-1） 40% 3-HH-V1 (3-1) 7% V2-BB-1 (3-3) 7% V-HBB-2 (3-6) 6% 1-BB(F)B-2V （3-8） 8% 2-BB(F)B-2V (3-8) 11% 3-BB(F)B-2V （3-8） 8% NI=81.1℃; Tc＜-10℃; Δn=0.146; Δε=3.2; γ1=42.3 mPa s; τ=15.2 ms; VHR-1=99.0%.

[Example 7] 3-BB(F)B(F)-C （1-4） 5% 3-BB(F)B(F,F)-CF3 （2-2） 4% 3-BB(F)B(F,F)XB(F,F)-F （2-6） 3% 3-HH-V (3-1) 43% 3-HH-V1 (3-1) 6% V2-BB-1 (3-3) 2% 1V2-BB-1 (3-3) 6% V-HBB-2 (3-6) 5% 1-BB(F)B-2V （3-8） 8% 2-BB(F)B-2V (3-8) 12% 1-B2BB-2V (3-9) 6% NI=78.9℃; Δn=0.142; Δε=2.6; γ1=42.0 mPa s; τ=14.9 ms; VHR-1=99.0%.

[Example 8] 3-BB(F)B(F)-C （1-4） 5% 3-BB(F)B(F,F)-CF3 （2-2） 4% 3-BB(F)B(F,F)XB(F,F)-F （2-6） 3% 3-HH-V （3-1） 40% 3-HH-V1 (3-1) 6% V2-BB-1 (3-3) 2% 1V2-BB-1 (3-3) 6% V-HBB-2 (3-6) 5% 1-BB(F)B-2V （3-8） 8% 2-BB(F)B-2V (3-8) 12% 1-B2BB-2V (3-9) 6% 3-dhBB(F,F)XB(F,F)-F （4-21） 3% NI=81.5℃; Δn=0.145; Δε=3.3; γ1=45.0 mPa s; τ=15.8 ms; VHR-1=99.0%.

[Example 9] 3-BB(F)B(F)-C （1-4） 4% 1-BB(F)B(F,F)-C (1-6) 1% 3-BB(F)B(F,F)-CF3 （2-2） 4% 3-BB(F)B(F,F)XB(F,F)-F （2-6） 3% 4-BB(F)B(F,F)XB(F,F)-F （2-6） 3% 3-HH-V (3-1) 39% 3-HH-V1 (3-1) 7% V2-BB-1 (3-3) 8% V-HBB-2 (3-6) 6% 1-BB(F)B-2V （3-8） 8% 2-BB(F)B-2V (3-8) 11% 3-BB(F)B-2V (3-8) 6% NI=80.8℃; Δn=0.149; Δε=4.4; γ1=46.0 mPa s; τ=16.1 ms; VHR-1=99.0%.

[Example 10] 3-BB(F)B(F)-C （1-4） 6% 3-BB(F)B(F,F)XB(F,F)-F （2-6） 4% 4-BB(F)B(F,F)XB(F,F)-F （2-6） 4% 3-HH-V （3-1） 45% V2-BB-1 (3-3) 8% 1-BB-3 (3-3) 4% 1-BB(F)B-2V (3-8) 11% 2-BB(F)B-2V (3-8) 10% 3-BB(F)B-2V （3-8） 8% NI=75.7℃; Δn=0.150; Δε=3.4; γ1=43.4 mPa s; τ=15.2 ms; VHR-1=99.0%.

[Example 11] 3-BB(F)B-C (1-1) 3% 3-BB(2F)B-C (1-2) 2% 3-BB(F)B(F,F)-CF3 （2-2） 4% 3-BB(F)B(F,F)XB(F,F)-F （2-6） 3% 4-BB(F)B(F,F)XB(F,F)-F （2-6） 3% 3-HH-V (3-1) 39% 3-HH-V1 (3-1) 7% V2-BB-1 (3-3) 8% V-HBB-2 (3-6) 6% 1-BB(F)B-2V （3-8） 8% 2-BB(F)B-2V (3-8) 11% 3-BB(F)B-2V (3-8) 6% NI=82.3℃; Δn=0.148; Δε=3.4; γ1=46.0 mPa s; τ=15.8 ms; VHR-1=99.1%.

[Example 12] 3-BB(F)B-C (1-1) 5% 3-BB(F)B(F,F)-CF3 （2-2） 4% 3-BB(F,F)XB(F,F)-F （2-4） 2% 3-BB(F)B(F,F)XB(F,F)-F （2-6） 4% 3-HH-V (3-1) 39% 3-HH-V1 (3-1) 6% V2-BB-1 (3-3) 8% V-HBB-2 (3-6) 6% 1-BB(F)B-2V （3-8） 9% 2-BB(F)B-2V (3-8) 11% 3-BB(F)B-2V (3-8) 6% NI=80.9℃; Δn=0.148; Δε=3.3; γ1=46.0 mPa s; τ=15.8 ms; VHR-1=99.3%.

[Example 13] 3-BB(F)B-C (1-1) 5% 3-BB(F)B(F,F)-F (2-1) 2% 3-BB(F)B(F,F)-CF3 （2-2） 4% 3-BB(F)B(F,F)XB(F,F)-F （2-6） 4% 3-HH-V (3-1) 39% 3-HH-V1 (3-1) 7% V2-BB-1 (3-3) 8% V-HBB-2 (3-6) 6% 1-BB(F)B-2V （3-8） 8% 2-BB(F)B-2V (3-8) 11% 3-BB(F)B-2V (3-8) 6% NI=81.2℃; Δn=0.148; Δε=3.3; γ1=46.0 mPa s; τ=15.8 ms; VHR-1=99.3%.

It can be seen that the compositions of Example 3 and Example 13 also have smaller rotational viscosity (γ1) and shorter response time (τ) than the composition of Comparative Example 1, and have greater voltage retention than the composition of Comparative Example 2. rate (VHR-1).

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

Claims (18)

A liquid crystal composition comprising at least one compound selected from compounds represented by formula (1) as component A, at least one compound selected from compounds represented by formula (2) as component B, and At least one compound selected from the compounds represented by formula (3), does not contain polymerizable compounds and polymers, and has positive dielectric anisotropy;

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 C1-12 alkyl group with at least one hydrogen replaced by fluorine or chlorine; X ¹ , X ² , X ³ , X ⁴ and X ⁵ are hydrogen or fluorine, X ¹ , X ² , X ³ , X ⁴ and X At least one of ⁵ is fluorine; In formula (2), R ² is an alkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons, or an alkenyl group with 2 to 12 carbons; Ring A ¹ and Ring A ² is 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene or 2,6-difluoro-1,4-phenylene Base; Z ¹ and Z ² are single bond, ethylene, vinylene, methoxy, carbonyloxy or difluoromethoxy; X ⁶ and X ⁷ are hydrogen or fluorine; Y ¹ is fluorine, Chlorine, an alkyl group with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, an alkoxy group with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, or a carbon in which at least one hydrogen is substituted by fluorine or chlorine alkenyloxy group with a number of 2 to 12; m is 1, 2 or 3; in formula (3), R ³ and R ⁴ are alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or alkoxy with 1 to 12 carbons 2 to 12 alkenyl, or at least one hydrogen substituted by fluorine or chlorine alkenyl with carbon number 2 to 12; ring B and ring C are 1,4-cyclohexyl, 1,4-phenylene, 2- Fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ³ is a single bond, ethylene, vinylene, methoxyl or carbonyloxy; n is 1, 2 or 3. The liquid crystal composition according to claim 1, comprising at least one compound selected from the compounds represented by formula (1-1) to formula (1-6) as component A;

In formula (1-1) to formula (1-6), R ¹ is hydrogen, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, or 2 to 12 alkenyloxy, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. The liquid crystal composition according to claim 1 or claim 2, wherein the proportion of component A is in the range of 1% by mass to 50% by mass. The liquid crystal composition according to claim 1 or claim 2, comprising at least one compound selected from the compounds represented by formula (2-1) to formula (2-11) as component B;

In formula (2-1) to formula (2-11), R ² 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 1 or claim 2, wherein the proportion of component B is in the range of 1% by mass to 50% by mass. The liquid crystal composition according to claim 1 or claim 2, comprising at least one compound selected from the compounds represented by formula (3-1) to formula (3-13) as component C;

In formula (3-1) to formula (3-13), R ³ and R ⁴ are alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons, or Alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. The liquid crystal composition according to claim 1 or claim 2, wherein the proportion of component C is in the range of 20% by mass to 90% by mass. The liquid crystal composition according to claim 1 or claim 2, comprising at least one compound selected from the group of compounds represented by formula (4) as component D;

In formula (4), R ⁵ is an alkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons, or an alkenyl group with 2 to 12 carbons; 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, at least one ring D is 1,4-cyclohexyl, pyrimidine- 2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; Z ⁴ is a single bond, ethylidene, vinylidene, methylene Oxygen, carbonyloxy or difluoromethoxyl; X ⁸ and X ⁹ are hydrogen or fluorine; Y ² is fluorine, chlorine, at least one hydrogen is substituted by fluorine or chlorine, an alkyl group with 1 to 12 carbons, at least An alkoxy group with 1 to 12 carbons in which one hydrogen is replaced by fluorine or chlorine, or an alkenyloxy group with 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine; a is 1, 2, 3 or 4. The liquid crystal composition according to claim 1 or claim 2, comprising at least one compound selected from the group of compounds represented by formula (4-1) to formula (4-24) as component D;

In formula (4-1) to formula (4-24), 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 proportion of component D is in the range of 1% by mass to 50% by mass. The liquid crystal composition according to claim 1 or claim 2, comprising at least one compound selected from the compounds represented by formula (5) as component E;

In formula ( ⁵ ), R6 and ^R7 are hydrogen, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons or alkenyloxy with 2 to 12 carbons base; ring E and ring G are 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen Fluorine or chlorine substituted 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen substituted by fluorine or chlorine naphthalene-2,6-diyl, chroman-2,6-diyl , or chromane-2,6-diyl with at least one hydrogen replaced by fluorine or chlorine; 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, 7,8-difluorochrome Ortho-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6 -Difluorodibenzothiophene-3,7-diyl or 1,1,6,7-tetrafluoroindan-2,5-diyl; Z ⁵ and Z ⁶ are single bonds, ethylene, vinylene group, methoxy or carbonyloxy; c is 0, 1, 2 or 3, d is 0 or 1, and the sum of c and d is 3 or less. The liquid crystal composition according to claim 1 or claim 2, comprising at least one compound selected from the compounds represented by formula (5-1) to formula (5-35) as component E;

In formula (5-1) to formula (5-35), R ⁶ and R ⁷ are hydrogen, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, alkenyl with 2 to 12 carbons or an alkenyloxy group having 2 to 12 carbon atoms. The liquid crystal composition according to claim 11, wherein the proportion of component E is in the range of 3% by mass to 45% by mass. The liquid crystal composition according to Claim 1 or Claim 2 has a nematic phase at least in the range of 0°C to 60°C. The liquid crystal composition according to claim 1 or claim 2, wherein the upper limit temperature of the nematic phase is 60°C or higher, and the optical anisotropy at a wavelength of 589 nm is 0.07 or higher when measured at 25°C, and the frequency 1 The dielectric anisotropy at kHz is 2.0 or more as measured at 25°C. A liquid crystal display element, containing the liquid crystal composition according to any one of claim 1 to claim 15. The liquid crystal display element according to claim 16, wherein the operation mode of the liquid crystal display element is twisted nematic mode, electronically controlled birefringence mode, optically compensated bending mode, in-plane switching mode, fringe field switching mode or electric field-induced photoresponse Orientation mode, and the driving mode of the liquid crystal display element is an active matrix mode. A use of a liquid crystal composition, the liquid crystal composition is the liquid crystal composition described in any one of Claim 1 to Claim 15, which is used in a liquid crystal display element.