TWI763832B - Liquid crystal display element, liquid crystal composition and use thereof - Google Patents

Abstract

The present invention provides a liquid crystal composition and an AM device comprising the composition, wherein the liquid crystal composition satisfies the requirements of high upper limit temperature, low lower limit temperature, low viscosity, appropriate optical anisotropy, and large negative dielectric anisotropy. at least one of the properties, or a suitable balance between at least two of these properties. A liquid crystal composition comprising a specific compound having a large dielectric anisotropy as a first component, a specific compound having a small viscosity or a large elastic constant as a second component, and a third component having A specific compound having a large dielectric anisotropy, a specific compound having a high upper limit temperature as a fourth component, or a specific compound having a polymerizable group as a first additive.

Description

Liquid crystal display element, liquid crystal composition and use thereof

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 negative dielectric anisotropy, and a liquid crystal display element containing the composition and having modes such as IPS, VA, FFS, and FPA. The present invention 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 more, and the preferable lower limit temperature of the nematic phase is about -10°C or less. The viscosity of the composition correlates with the response time of the component. In order to display a moving image by the device, it is preferable that the response time is short. The ideal is a response time of less than 1 millisecond. Therefore, the viscosity of the composition is preferably small. It is especially preferable that the viscosity at low temperature is small.

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 the element of the VA mode, the value is in the range of about 0.30 μm to about 0.40 μm, and in the element of the IPS mode or the FFS mode, the value is in the range of about 0.20 μm to about 0.30 μm. In these cases, 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 low threshold voltage, small power consumption and large contrast in the device. Therefore, a large dielectric anisotropy is preferred. The large specific resistance of the composition contributes to the large voltage holding ratio and the large contrast ratio of the element. Therefore, a composition having a large specific resistance in the initial stage is preferable. A composition having a large specific resistance even after long-term use is preferred. The stability of the composition to ultraviolet light or heat correlates with the lifetime of the element. When the stability is high, the life of the device is long. Such characteristics are preferable for AM elements used in liquid crystal monitors, liquid crystal televisions, and the like.

In general liquid crystal display elements, the vertical alignment of liquid crystal molecules can be achieved by using a specific polyimide alignment film. In a polymer sustained alignment (PSA) type liquid crystal display element, a polymer and an alignment film are combined. First, a composition to which a small amount of a polymerizable compound is added is injected into the element. Next, while a voltage is applied between the substrates of the element, the composition is irradiated with ultraviolet rays. The polymerizable compound is polymerized to generate a polymer network structure in the composition. In this composition, the polymer can be used to control the alignment of the liquid crystal molecules, so the response time of the element is shortened, and the afterimage of the image is improved. Such effects of polymers can be expected in elements having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

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. A composition having positive or negative dielectric anisotropy is used in a polymer-stabilized alignment type AM device. In Patent Document 1 and Patent Document 2, compounds similar to those contained in the first component of the present invention are disclosed. [Prior Art Document] [Patent Document]

[Patent Document 1] International Publication No. 2015/129412 [Patent Document 2] International Publication No. 2012/86437

[Problems to be Solved by the Invention] An object of the present invention is to provide a liquid crystal composition that satisfies the requirements of high upper limit temperature of nematic phase, low minimum temperature of nematic phase, low viscosity, suitable optical anisotropy, and negative dielectric properties. At least one of characteristics such as high anisotropy, high specific resistance, high stability to ultraviolet rays, and high thermal stability. Another subject is to provide a liquid crystal composition having an appropriate balance between at least two of these properties. Another subject is to provide a liquid crystal display element containing such a composition. Another subject is to provide an AM element having characteristics such as short response time (especially at low temperature), high voltage holding ratio, low threshold voltage, high contrast ratio, and long life. [Means of Solving Problems]

式（1）及式（2）中，R¹ 及R² 獨立地為氫、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；R³ 及R⁴ 獨立地為碳數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2至12的烯基；環A及環C獨立地為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；環B為茀-2,7-二基、二苯并噻吩-3,7-二基、菲-2,7-二基、9,10-二氫菲-2,7-二基、二苯并哌喃-2,6-二基或二氫茚-2,5-二基，該些環中，至少一個氫可經氟或氯取代；Z¹ 及Z² 獨立地為單鍵、伸乙基、羰基氧基或亞甲基氧基；a為0、1、2或3，b為0或1，而且a與b的和為3以下。 [發明的效果]The present invention relates to a liquid crystal composition containing, as a first component, at least one compound selected from the compounds represented by the formula (1), and a liquid crystal display element containing the same, and as a second component of at least one compound selected from the compounds represented by the formula (2) and having negative dielectric anisotropy.

In formula (1) and formula (2), R ¹ and R ² are independently hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon Alkenyloxy with 2 to 12 carbons, or alkyl with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; R ³ and R ⁴ are independently alkenyl with 2 to 12 carbons, 2 to 12 carbons Alkenyloxy of 12, or alkenyl of carbon number 2 to 12 in which at least one hydrogen is substituted by fluorine or chlorine; Ring A and Ring C are independently 1,4-cyclohexylene, 1,4-cyclohexene base, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine; ring B is perylene-2,7-diyl , dibenzothiophene-3,7-diyl, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, dibenzopyran-2,6-diyl or Dihydroindene-2,5-diyl, in these rings, at least one hydrogen can be substituted by fluorine or chlorine; Z ¹ and Z ² are independently a single bond, ethylidene, carbonyloxy or methyleneoxy ; a is 0, 1, 2 or 3, b is 0 or 1, and the sum of a and b is 3 or less. [Effect of invention]

The advantages of the present invention are to provide a liquid crystal composition that satisfies the requirements of high upper limit temperature of nematic phase, low lower limit temperature of nematic phase, low viscosity, appropriate optical anisotropy, large negative dielectric anisotropy, large specific resistance, At least one of properties such as high stability to ultraviolet rays and high thermal stability. Another advantage is to provide a liquid crystal composition with an appropriate balance between at least two of these properties. Another advantage is to provide a liquid crystal display element containing such a composition. Yet another advantage is to provide an AM element with 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. In some examples, the terms "liquid crystal composition" and "liquid crystal display element" are abbreviated as "composition" and "element", respectively. "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. The 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 producing 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, quenchers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are optionally added to the liquid crystal composition. Even when an additive is added, the ratio of the liquid crystal compound is represented by the weight percentage (% by weight) based on the weight of the liquid crystal composition not containing the additive. The ratio of the additive is represented by the weight percentage (% by weight) based on the weight of the liquid crystal composition not containing the additive. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total weight of the liquid crystal compound. Some examples use parts per million by weight (ppm). The ratios of the polymerization initiator and the polymerization inhibitor are expressed based on the weight of the polymerizable compound exceptionally.

In some examples, "the upper limit temperature of the nematic phase" is abbreviated as "the upper limit temperature". In some examples, the "lower limit temperature of the nematic phase" is 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 also has a large specific resistance after being used for a long time. "Large voltage retention ratio" means that the device has a large voltage retention ratio not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and not only at room temperature but also after long-term use. It also has a large voltage holding ratio at a temperature close to the upper limit temperature. In some of the examples, the properties of compositions or components were investigated before and after time-dependent tests (including accelerated degradation tests). 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.

In some examples, the compound represented by formula (1) is abbreviated as "compound (1)". In some examples, at least one compound selected from the compounds represented by formula (1) is abbreviated as "compound (1)". "Compound (1)" refers to one compound represented by formula (1), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulae. The expression "at least one 'A'" means that the number of 'As' is arbitrary. The expression "at least one 'A' may be substituted 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 There are also unlimited options. This rule also applies to the expression "at least one 'A' is replaced by a 'B'".

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 ¹ is used for various compounds. In these compounds, the two groups represented by any two R ¹ may be the same or different. For example, there is a case where R ¹ of the compound (1-1) is an ethyl group and R ¹ of the compound (1-2) is an ethyl group. There are also cases where R ¹ of compound (1-1) is ethyl and R ¹ of compound (1-2) is propyl. This rule also applies to the notation of other terminal groups, etc. In formula (3), when the subscript 'c' is 2, there are two rings D. In this compound, the two rings represented by the two rings D may be the same or different. This rule also applies to any two rings D when the subscript 'c' is greater than 2. This rule also applies to symbols such as Z ⁴ , ring G, 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 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 -Sp ¹ -P ¹ . Subscripts such as 'g' indicate the number of substituted groups. When the subscript 'g' is 0 (zero), there is no such substitution. When the subscript 'g' is 2 or more, a plurality of -Sp ¹ -P ¹ exist on the ring J. The plural bases represented by -Sp ¹ -P ¹ 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）及式（2）中，R¹ 及R² 獨立地為氫、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；R³ 及R⁴ 獨立地為碳數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2至12的烯基；環A及環C獨立地為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；環B為茀-2,7-二基、二苯并噻吩-3,7-二基、菲-2,7-二基、9,10-二氫菲-2,7-二基、二苯并哌喃-2,6-二基或二氫茚-2,5-二基，該些環中，至少一個氫可經氟或氯取代；Z¹ 及Z² 獨立地為單鍵、伸乙基、羰基氧基或亞甲基氧基；a為0、1、2或3，b為0或1，而且a與b的和為3以下。Item 1. A liquid crystal composition comprising at least one compound selected from the compounds represented by the formula (1) as the first component and at least one compound selected from the compounds represented by the formula (2) as the second component compound with negative dielectric anisotropy,

In formula (1) and formula (2), R ¹ and R ² are independently hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon Alkenyloxy with 2 to 12 carbons, or alkyl with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; R ³ and R ⁴ are independently alkenyl with 2 to 12 carbons, 2 to 12 carbons Alkenyloxy of 12, or alkenyl of carbon number 2 to 12 in which at least one hydrogen is substituted by fluorine or chlorine; Ring A and Ring C are independently 1,4-cyclohexylene, 1,4-cyclohexene base, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine; ring B is perylene-2,7-diyl , dibenzothiophene-3,7-diyl, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, dibenzopyran-2,6-diyl or Dihydroindene-2,5-diyl, in these rings, at least one hydrogen can be substituted by fluorine or chlorine; Z ¹ and Z ² are independently a single bond, ethylidene, carbonyloxy or methyleneoxy ; a is 0, 1, 2 or 3, b is 0 or 1, and the sum of a and b is 3 or less.

式（1-1）至式（1-38）中，R¹ 及R² 獨立地為氫、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；X¹ 及X² 獨立地為氫或氟。Item 2. The liquid crystal composition according to Item 1, which contains, as the first component, at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-38),

In formula (1-1) to formula (1-38), R ¹ and R ² are independently hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkoxy having 1 to 12 carbons alkenyl, 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; X ¹ and X ² are independently hydrogen or fluorine.

Item 3. The liquid crystal composition according to Item 1 or Item 2, which contains, as a second component, at least one compound selected from the group of compounds represented by formula (2-1) to formula (2-13) .

Item 4. The liquid crystal composition according to any one of Items 1 to 3, wherein the ratio of the first component is in the range of 3% by weight to 20% by weight.

Item 5. The liquid crystal composition according to any one of Items 1 to 4, wherein the ratio of the second component is in the range of 10% by weight to 70% by weight.

式（3）中，R⁵ 及R⁶ 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、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；環D及環F獨立地為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、或者至少一個氫經氟或氯取代的1,4-伸苯基；環E為2,3-二氟-1,4-伸苯基、2-氯-3-氟-1,4-伸苯基或2,3-二氟-5-甲基-1,4-伸苯基；Z³ 及Z⁴ 獨立地為單鍵、伸乙基、羰基氧基或亞甲基氧基；c為1、2或3，d為0或1，而且c與d的和為3以下。Item 6. The liquid crystal composition according to any one of Items 1 to 5, which contains as the third component at least one compound selected from the compounds represented by the formula (3),

In formula (3), R ⁵ and R ⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyl having 2 to 12 carbons Oxy group, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; Ring D and Ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydro Pyran-2,5-diyl, 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is substituted with fluorine or chlorine; ring E is 2,3-difluoro-1,4- phenylene, 2-chloro-3-fluoro-1,4-phenylene or 2,3-difluoro-5-methyl-1,4-phenylene; Z ³ and Z ⁴ are independently single bonds , ethylidene, carbonyloxy or methyleneoxy; c is 1, 2 or 3, d is 0 or 1, and the sum of c and d is 3 or less.

式（3-1）至式（3-25）中，R⁵ 及R⁶ 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、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。Item 7. The liquid crystal composition according to any one of Items 1 to 6, which contains, as a third component, a compound selected from the group consisting of compounds represented by formula (3-1) to formula (3-25) at least one compound of

In formula (3-1) to formula (3-25), R ⁵ and R ⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons , an alkenyloxy group having 2 to 12 carbons, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine.

Item 8. The liquid crystal composition according to Item 6 or Item 7, wherein the ratio of the third component is in the range of 10% by weight to 70% by weight.

式（4）中，R⁷ 及R⁸ 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、至少一個氫經氟或氯取代的碳數1至12的烷基、或者至少一個氫經氟或氯取代的碳數2至12的烯基；環G及環I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；Z⁵ 為單鍵、伸乙基或羰基氧基；e為1、2或3；於e為1時，環I為1,4-伸苯基。Item 9. The liquid crystal composition according to any one of Items 1 to 8, which contains as the fourth component at least one compound selected from the compounds represented by the formula (4),

In formula (4), R ⁷ and R ⁸ 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, and at least one hydrogen is substituted by fluorine or chlorine The alkyl group with 1 to 12 carbon atoms, or the alkenyl group with 2 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; Ring G and Ring I are independently 1,4-cyclohexylene, 1,4-cyclohexylene phenyl, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ⁵ is a single bond, ethylene or carbonyloxy; e is 1, 2 or 3; when e is 1, ring I is 1,4-phenylene.

式（4-1）至式（4-12）中，R⁷ 及R⁸ 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、至少一個氫經氟或氯取代的碳數1至12的烷基、或者至少一個氫經氟或氯取代的碳數2至12的烯基。Item 10. The liquid crystal composition according to any one of Items 1 to 9, which contains, as the fourth component, a compound selected from the group consisting of compounds represented by Formula (4-1) to Formula (4-12) at least one compound of

In formula (4-1) to formula (4-12), R ⁷ and R ⁸ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons , an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine.

Item 11. The liquid crystal composition according to Item 9 or Item 10, wherein the ratio of the fourth component is in the range of 2% by weight to 50% by weight.

式（5）中，環J及環L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K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；Z⁶ 及Z⁷ 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；f為0、1或2；g、h及i獨立地為0、1、2、3或4，而且g、h及i的和為1以上。Item 12. The liquid crystal composition according to any one of Items 1 to 11, which contains, as a first additive, at least one compound selected from the polymerizable compounds represented by formula (5),

In formula (5), ring J and ring L 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 , or at least one hydrogen is substituted by an alkyl group having 1 to 12 carbon atoms substituted by fluorine or chlorine; ring K 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 base, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, carbon Alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or alkyl with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; Z ⁶ and Z ⁷ are independently a single bond or carbon The alkylene group of numbers 1 to 10, in the alkylene group, at least one -CH ₂ - may be substituted by -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ -CH ₂ - may be substituted Substituted by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ )-, in these groups, 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 alkylene group having 1 to 10 carbon atoms, the alkylene group Among them, 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- , in these groups, at least one hydrogen may be substituted by fluorine or chlorine; f is 0, 1 or 2; g, h and i are independently 0, 1, 2, 3 or 4, and the sum of g, h and i 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 13. The liquid crystal composition according to Item 12, wherein in formula (5), P ¹ , P ² and P ³ are independently polymers selected from the group consisting of polymers represented by formula (P-1) to formula (P-5). The base in the sex-based group,

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

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；

此處，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 14. The liquid crystal composition according to any one of Items 1 to 13, which contains as a first additive a polymerizable compound selected from the group consisting of polymerizable compounds represented by formula (5-1) to formula (5-29) at least one compound in the group,

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) base in;

Here, M ¹ , M ² and M ³ are independently hydrogen, fluorine, an alkyl group with 1 to 5 carbon atoms, or an alkyl group with 1 to 5 carbon atoms 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 substituted by -O-, -COO-, -OCO- or -OCOO- , at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C-, and in these groups, at least one hydrogen can be substituted by fluorine or chlorine.

Item 15. The liquid crystal composition according to any one of Items 12 to 14, wherein the ratio of the first additive is in the range of 0.03 wt % to 10 wt %.

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 IPS mode, VA mode, FFS mode or FPA mode, and the driving mode of the liquid crystal display element is an active matrix mode.

Item 18. A polymer-stabilized alignment type liquid crystal display element comprising the liquid crystal composition according to any one of items 12 to 15, and the first additive contained in the liquid crystal composition is polymerized.

Item 19. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of items 1 to 15, which is used in a liquid crystal display element.

Item 20. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of items 1 to 15, which is used in a polymer-stabilized alignment type liquid crystal display element.

The present invention also includes the following items. (a) As a second additive, the composition further contains an optically active compound, an antioxidant, an ultraviolet absorber, a quencher, a pigment, an antifoaming agent, a polymerizable compound different from the compound (5), a polymer At least one of additives such as initiators, polymerization inhibitors, and polar compounds. (b) An AM device including the composition. (c) A polymer-stabilized alignment (PSA) type AM device comprising the composition. (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 of a composition prepared 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 composition will be described. Second, the main characteristics 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 (1), compound (2), compound (3), and compound (4). "Other liquid crystal compounds" are liquid crystal compounds different from compound (1), compound (2), compound (3), and compound (4). Such a compound is mixed in the composition for the purpose of further adjusting the properties.

The composition B contains substantially only the liquid crystal compound selected from the group consisting of the compound (1), the compound (2), the compound (3), and the 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 will be described. 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. Notations L, M, S are classifications based on qualitative comparisons between constituent compounds, and notation 0 (zero) means minimal.

The main effects of the component compounds on the properties of the composition are as follows. Compound (1) increases the dielectric anisotropy. Compound (2) increases the elastic constant, or decreases the viscosity. Compound (3) increases the dielectric anisotropy and lowers the lower limit temperature. Compound (4) increases the upper limit temperature, or decreases the viscosity. Compound (5) is polymerized to provide a polymer which shortens the response time of the element and improves the afterimage of the image.

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 (2)+compound (3), compound (1)+compound (2)+compound (4), Compound (1) + Compound (2) + Compound (5), Compound (1) + Compound (2) + Compound (3) + Compound (4), Compound (1) + Compound (2) + Compound (3) + Compound (5), compound (1)+compound (2)+compound (4)+compound (5) or compound (1)+compound (2)+compound (3)+compound (4)+compound (5). A particularly preferred combination is compound (1)+compound (2)+compound (3)+compound (4) or compound (1)+compound (2)+compound (3)+compound (4)+compound (5).

In order to increase the dielectric anisotropy, the preferred ratio of the compound (1) is about 3% by weight or more, and the preferred ratio of the compound (1) is about 20% by weight or less in order to lower the minimum temperature. A particularly preferred ratio is in the range of about 3% by weight to about 18% by weight. A particularly preferred ratio is in the range of about 3% by weight to about 15% by weight.

The preferred ratio of compound (2) is about 10 wt % or more in order to increase the elastic constant or to reduce the viscosity, and the preferred ratio of compound (2) is about 70 wt % or less in order to increase the dielectric anisotropy. A particularly preferred ratio is in the range of about 15% by weight to about 60% by weight. A particularly preferred ratio is in the range of about 20% by weight to about 50% by weight.

In order to increase the dielectric anisotropy, the preferred ratio of the compound (3) is about 10% by weight or more, and the preferred ratio of the compound (3) is about 70% by weight or less in order to lower the minimum temperature. A particularly preferred ratio is in the range of about 15% by weight to about 65% by weight. A particularly preferred ratio is in the range of about 20% by weight to about 60% by weight.

In order to increase the upper limit temperature or to reduce the viscosity, the preferred ratio of the compound (4) is about 2 wt% or more, and the preferred ratio of the compound (4) is about 50 wt% or less in order to increase the dielectric anisotropy. A particularly preferred ratio is in the range of about 2% by weight to about 40% by weight. A particularly preferred ratio is in the range of about 4% by weight to about 30% by weight.

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

Fourth, preferred forms of the component compounds will be described. In formula (1), formula (2), formula (3) and formula (4), R ¹ and R ² are independently hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, An alkenyl group having 2 to 12 carbons, an alkenyloxy group having 2 to 12 carbons, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine. In order to improve the stability to ultraviolet light or heat, preferably R ¹ or R ² is an alkyl group having 1 to 12 carbon atoms, and in order to improve dielectric anisotropy, preferably R ¹ or R ² is an alkyl group having 1 to 12 carbon atoms alkoxy. R ³ and R ⁴ are independently an alkenyl group having 2 to 12 carbons, an alkenyloxy group having 2 to 12 carbons, or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine. In order to reduce viscosity, preferable R ³ or R ⁴ is an alkenyl group having 2 to 12 carbons. R ⁵ and R ⁶ are independently 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 An alkyl group having 1 to 12 carbons in which hydrogen is substituted with fluorine or chlorine. In order to improve the stability to ultraviolet light or heat, preferably R ⁵ or R ⁶ is an alkyl group having 1 to 12 carbon atoms, and in order to improve the dielectric anisotropy, preferably R ⁵ or R ⁶ is an alkyl group having 1 to 12 carbon atoms alkoxy. R ⁷ and R ⁸ 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, a carbon number 1 to 12 wherein at least one hydrogen is substituted by fluorine or chlorine , or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine. In order to improve the stability against ultraviolet rays or heat, preferable R ⁷ or R ⁸ is an alkyl group having 1 to 12 carbons.

Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. In order to reduce viscosity, particularly 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 viscosity, particularly preferred alkoxy groups are methoxy or ethoxy.

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. In order to reduce viscosity, particularly preferred alkenyl groups are vinyl, 1-propenyl, 3-butenyl or 3-pentenyl. 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 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, particularly preferred 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 particularly preferred example is 2,2-difluorovinyl or 4,4-difluoro-3-butenyl.

或

， 較佳為

。Ring A and Ring C are independently 1,4-cyclohexylene, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen Fluorine or chlorine substituted 1,4-phenylene. In order to reduce the viscosity, the preferred ring A or ring C is 1,4-cyclohexylene, and in order to improve the dielectric anisotropy, the preferred ring A or ring C is tetrahydropyran-2,5-diyl, In order to increase optical anisotropy, preferable ring A or ring C is 1,4-phenylene. Ring B is phenyl-2,7-diyl, dibenzothiophene-3,7-diyl, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, diphenyl and pyran-2,6-diyl or dihydroindene-2,5-diyl, in these rings, at least one hydrogen may be substituted by fluorine or chlorine. In order to improve the dielectric anisotropy, the preferred ring B is phenanthrene-2,7-diyl in which at least one hydrogen is substituted by fluorine, phenanthrene-2,7-diyl in which at least one hydrogen is substituted by fluorine, and at least one hydrogen is substituted by fluorine. Fluorine-substituted 9,10-dihydrophenanthrene-2,7-diyl, dibenzopyran-2,6-diyl with at least one hydrogen substituted with fluorine, or dihydroindene-2 with at least one hydrogen substituted with fluorine , 5-diyl. A particularly preferred ring B is perylene-2,7-diyl in which at least one hydrogen is substituted with fluorine. Tetrahydropyran-2,5-diyl is

or

, preferably

.

Ring D and Ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen Fluorine or chlorine substituted 1,4-phenylene. In order to reduce the viscosity, the preferred ring D or ring F is 1,4-cyclohexylene, and in order to improve the dielectric anisotropy, the preferred ring D or ring F is tetrahydropyran-2,5-diyl, In order to increase the optical anisotropy, preferable ring D or ring F is 1,4-phenylene. Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene or 2,3-difluoro-5-methyl-1,4- extended phenyl. In order to increase the dielectric anisotropy, the preferred ring E is 2,3-difluoro-1,4-phenylene.

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

Z ¹ , Z ² , Z ³ and Z ⁴ are independently a single bond, ethylidene, carbonyloxy or methyleneoxy. In order to lower the viscosity, preferably Z ¹ , Z ² , Z ³ or Z ⁴ is a single bond, in order to lower the lower limit temperature, preferably Z ¹ , Z ² , Z ³ or Z ⁴ is an ethylidene group, in order to improve the dielectric Anisotropic, preferably Z ¹ , Z ² , Z ³ or Z ⁴ is a methyleneoxy group. Z ⁵ is a single bond, ethylidene or carbonyloxy. In order to improve the stability against ultraviolet rays or heat, preferably Z ⁵ is a single bond.

a is 0, 1, 2 or 3, b is 0 or 1, and the sum of a and b is 3 or less. Desirable a or b is 0 or 1 in order to lower the lower limit temperature. c is 1, 2 or 3, d is 0 or 1, and the sum of c and d is 3 or less. 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. In order to reduce the viscosity, the preferred d is 0, and in order to reduce the lower limit temperature, the preferred d is 1. 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.

In formula (5), P ¹ , P ² and P ³ are independently polymerizable groups. Preferable P ¹ , P ² or P ³ is a polymerizable group selected from the group of groups represented by formula (P-1) to formula (P-5). Particularly preferred P ¹ , P ² or P ³ is the formula (P-1) or the formula (P-2). A particularly preferred formula (P-1) is -OCO-CH=CH ₂ or -OCO-C(CH ₃ )=CH ₂ . The wavy lines in the formulas (P-1) to (P-5) indicate the bonding sites.

In formula (P-1) to formula (P-5), M ¹ , M ² and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or carbon wherein at least one hydrogen is substituted with fluorine or chlorine 1 to 5 alkyl groups. In order to increase reactivity, preferable M ¹ , M ² or M ³ is hydrogen or methyl. A particularly preferred M ¹ is methyl, and a particularly 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 formula (P-1) or formula (P-2). A particularly preferred formula (P-1) is -OCO-CH=CH ₂ or -OCO-C(CH ₃ )=CH ₂ . The wavy lines in the formulas (P-1) to (P-3) indicate the bonding sites.

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 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. Preferred Sp ¹ , Sp ² or Sp ³ are single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CO-CH=CH- or - CH=CH-CO-. Particularly preferred Sp ¹ , Sp ² or Sp ³ are single bonds.

Ring J and Ring L are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, Pyrimidine-2-yl or pyridin-2-yl, 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 Alkyl group having 1 to 12 carbon atoms substituted by fluorine or chlorine. Preferred ring J or ring L is phenyl. Ring K 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, chlorine, alkyl with 1 to 12 carbons, alkoxy with 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 K is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁶ and Z ⁷ 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-, -CO-, -COO- or -OCO- Substituted, at least one -CH ₂ -CH ₂ - may be via -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ )-substituted, in these groups, at least one hydrogen may be substituted with fluorine or chlorine. Preferred Z ⁶ or Z ⁷ is a single bond, -CH ₂ -CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-. The preferred Z ⁶ or Z ⁷ are single keys.

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

Fifth, preferred constituent compounds are shown. Preferred compounds (1) are the compounds (1-1) to (1-38) described in item 2. Among these compounds, preferably at least one of the first components is compound (1-1), compound (1-2), compound (1-7), compound (1-8), compound (1-11), Compound (1-12), compound (1-15), compound (1-22), compound (1-28), compound (1-30), compound (1-32), compound (1-33) or compound (1-36). Preferably, at least two of the first components are compound (1-1) and compound (1-2), compound (1-1) and compound (1-7), compound (1-8) and compound (1- 11), compound (1-8) and compound (1-12) or a combination of compound (1-33) and compound (1-36).

Desirable compound (2) is compound (2-1) to compound (2-13) described in item 3. Among these compounds, at least one of the second component is preferably compound (2-1), compound (2-2), and compound (2-3). Preferably, at least two of the second components are compound (2-1) and compound (2-2), compound (2-1) and compound (2-3), or compound (2-2) and compound (2- 3) combination.

Preferred compounds (3) are the compounds (3-1) to (3-25) described in item 7. Among these compounds, preferably at least one of the third component is compound (3-1), compound (3-2), compound (3-3), compound (3-6), compound (3-8), Compound (3-9), compound (3-10) or compound (3-14). Preferably, at least two of the third components are compound (3-1) and compound (3-6), compound (3-1) and compound (3-8), compound (3-1) and compound (3- 10), compound (3-1) and compound (3-14), compound (3-3) and compound (3-8), compound (3-3) and compound (3-10), compound (3-3) ) and compound (3-14), compound (3-6) and compound (3-8), compound (3-6) and compound (3-9), compound (3-6) and compound (3-10) or a combination of compound (3-6) and compound (3-14).

Preferred compounds (4) are the compounds (4-1) to (4-12) described in item 10. Among these compounds, preferably at least one of the fourth components is compound (4-2), compound (4-4), compound (4-5) or compound (4-6). Preferably, at least two of the fourth components are compound (4-2) and compound (4-4), compound (4-2) and compound (4-5), or compound (4-2) and compound (4) -6) combination.

Preferred compounds (5) are the compounds (5-1) to (5-29) described in item 14. Among these compounds, preferably at least one of the first additives is compound (5-1), compound (5-2), compound (5-24), compound (5-25), compound (5-26) , compound (5-27) or compound (5-29). Preferably, at least two of the first additives are compound (5-1) and compound (5-2), compound (5-1) and compound (5-19), compound (5-2) and compound (5) -24), compound (5-2) and compound (5-25), compound (5-2) and compound (5-26), compound (5-27) and compound (5-26) or compound (5- 18) and the 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 weight or less. A particularly preferred ratio is in the range of about 0.01% to about 2% by weight.

Antioxidants are added in order to prevent a drop 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 using the device 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 particularly preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferable examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole 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, and 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 the following. A particularly preferred ratio is in the range of about 100 ppm to about 10,000 ppm.

The matting agent is a compound that prevents the liquid crystal compound from decomposing by accepting the 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 effect, the preferred proportion of the matting agent 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 particularly 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 weight to about 10% by weight. 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 particularly 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. Instead of the compound (5), a polymerizable compound different from the compound (5) may be added to the composition. Preferable examples of such polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes), vinyl ketones and other compounds. Particularly preferred examples are derivatives of acrylate or methacrylate. The reactivity of the polymerizable compound and the pretilt angle of the liquid crystal molecules can be adjusted by changing the type of the compound (5) or by combining a polymerizable compound different from the compound (5) with the compound (5) in an appropriate ratio. By optimizing the pretilt angle, a short response time of the device can be achieved. Since the alignment of the liquid crystal molecules is stabilized, a large contrast ratio or a long lifetime can be achieved.

The polymerizable compound is polymerized by ultraviolet irradiation. The polymerization can also be carried out in the presence of a polymerization initiator such as a photopolymerization initiator. Appropriate conditions for carrying out the polymerization or suitable types and amounts of polymerization initiators are known to those skilled in the art and are 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 weight to about 5% by weight based on the weight of the polymerizable compound. A particularly preferred ratio is in the range of about 1% to about 3% by weight.

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

Polar compounds are organic compounds having polarity. Here, compounds having ionic bonds are not included. Atoms such as oxygen, sulfur, and nitrogen are electrically negative and tend to have partial negative charges. Carbon and hydrogen are neutral or have a tendency to have a partial positive charge. Polarity arises from the unequal distribution of partial charges among atoms of different species in a compound. For example, the polar compound has at least one of partial structures such as -OH, -COOH, -SH, -NH ₂ , >NH, and >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 (1-8) was synthesized by the method described in Japanese Patent Laid-Open No. 2016-47905. Compound (2-1) was synthesized by the method described in Japanese Patent Laid-Open No. 9-77692. Compound (3-8) was synthesized by the method described in JP-A No. 2-503441. Compound (4-4) was synthesized by the method described in Japanese Patent Laid-Open No. Sho 59-176221. Compound (5-19) was synthesized by the method described in Japanese Patent Laid-Open No. 7-101900. Antioxidants are commercially available. Compound (7-1) can be obtained from Sigma-Aldrich Corporation. Compound (7-2) and the like were 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 Syntheses" (John Wiley & Sons, Inc.), "Organic Syntheses" Reactions” (John Wiley & Sons, Inc.), “Comprehensive Organic Synthesis” (Pergamon Press), “Lectures on New Experimental Chemistry” ( Maruzen) etc. 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 constituent 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, OCB, IPS or FFS modes. 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. The composition can also be used in a nematic curvilinear aligned phase (NCAP) type element produced by microencapsulation, or a polymer in which a three-dimensional network polymer is formed in the composition Dispersed (polymer dispersed, PD) type components.

An example of a method of manufacturing a polymer-stabilized alignment-type device is described below. Assembling a component that includes two substrates, referred to as an array substrate and a color filter substrate. The substrate has an alignment film. At least one of the substrates has an electrode layer. The liquid crystal compound is mixed to prepare a liquid crystal composition. A polymerizable compound is added to this composition. Additives can be further added as needed. The composition is injected into the element. Light irradiation was performed in a state where a voltage was applied to the element. Ultraviolet rays are preferred. The polymerizable compound is polymerized by light irradiation. A polymer-containing composition is produced by this polymerization. The polymer-stabilized alignment-type element is fabricated in the sequence described above.

In this sequence, when a voltage is applied, the liquid crystal molecules are aligned by the action of the alignment film and the electric field. According to this alignment, the molecules of the polymerizable compound are also aligned. Since the polymerizable compound is polymerized by ultraviolet rays in this state, a polymer maintaining the alignment is produced. By the effect of the polymer, the response time of the element is shortened. Since the afterimage of the image is caused by the poor operation of the liquid crystal molecules, the afterimage is also improved by the effect of the polymer. In addition, the polymerizable compound in the composition may be polymerized in advance, and the composition may be disposed between the substrates of the liquid crystal display element. [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 at 500 MHz and 16 cumulative times. Tetramethylsilane was used as an internal standard. In the measurement of ¹⁹ F-NMR, CFCl ₃ was used as an internal standard, and the cumulative number of times was 24. In the description of NMR spectra, s means singlet, d means doublet, t means triplet, q means quartet, and quin means quintet (quintet), 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% by weight), 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 method described below. 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 (weight ratio) of the liquid crystal compound. When the capillary column described above is used, the correction coefficient of each liquid crystal compound can be regarded as 1. Therefore, the ratio (% by weight) of the liquid crystal compound can be calculated from the area ratio of the peaks.

Measurement sample: When measuring the properties of the composition and the element, the composition was 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 weight) with the mother liquid crystal (85% by weight). 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. At 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% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% by weight 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 proportions of the constituent compounds are expressed in % by weight.

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. method. Thin film transistors (TFTs) were not mounted on the TN elements used for the measurement.

(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. In some embodiments, the upper limit temperature of the nematic phase is simply referred to as the "upper limit temperature".

(2) Lower limit temperature of nematic phase (TC; ° _C ): put the sample with nematic phase into a glass bottle, and put it in a glass bottle at 0 °C, -10 °C, -20 °C, -30 °C and -40 °C After storing in a refrigerator for 10 days, the liquid crystal phase was observed. For example, when the sample maintains the state of the nematic phase at -20°C and changes to the crystalline or smectic phase at -30°C, the T _C is recorded as <-20°C. In some examples, the lower limit temperature of the nematic phase is simply referred to as the "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 VA element with a gap (cell gap) between two glass substrates of 20 μm. A voltage was applied to the element in steps 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 in assay (6).

(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.): The value of the dielectric anisotropy was calculated according to 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 washed 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⊥): The polyimide solution was coated on the fully washed glass substrate. After firing the glass substrate, the obtained alignment film was subjected to a rubbing treatment. 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.

(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 normally black mode VA element in which the distance between two glass substrates (cell gap) 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 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 10%.

(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 (5 V, 60 microseconds). Using a high-speed voltmeter, the decayed voltage was measured for 16.7 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 80°C; %): The voltage holding ratio was measured in the same procedure as described above, except that the measurement was performed at 80°C instead of 25°C. The obtained value is represented by VHR-2.

(10) Voltage holding ratio (VHR-3; measured at 25° 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 light was irradiated for 20 minutes. The light source is an ultra-high pressure mercury lamp USH-500D (manufactured by Ushio Motor), and the distance between the element and the light source is 20 cm. In the measurement of VHR-3, the decayed voltage was measured during 16.7 milliseconds. Compositions with large VHR-3 have large UV stability. VHR-3 is preferably 90% or more, particularly preferably 95% or more.

(11) Voltage holding ratio (VHR-4; measured at 25°C; %): After the TN element injected with the sample was heated 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 16.7 milliseconds. Compositions with large VHR-4 have large thermal stability.

(12) Response time (τ(25); 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 FFS element in which the distance between two glass substrates (cell gap) was 3.2 μm and the rubbing direction was antiparallel. The element is sealed with a UV-curable adhesive. At 25°C, a voltage (60 Hz, rectangular wave) was applied to the element while increasing from 0 V to 20 V in steps 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 voltage when the transmittance is 95% is expressed by V95 (V) and used as the applied voltage when measuring the response time. Next, a rectangular wave (60 Hz, V95, 0.5 seconds) was applied to the element. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. When the light amount 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.

(13) Response time (τ(-20); measured at -20°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 FFS element in which the distance between two glass substrates (cell gap) was 3.2 μm and the rubbing direction was antiparallel. The element is sealed with a UV-curable adhesive. A rectangular wave (60 Hz, V95, 2 seconds) was applied to the element. Here, V95 was measured by the same method as described above. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. When the light amount 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.

(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) Elastic constant (K11: splay elastic constant, K33: bend elastic constant; measured at 25°C; pN): EC manufactured by TOYO Corporation was used in the measurement -1 type elastic constant tester. A sample was placed in a vertical alignment element with a gap (cell gap) between two glass substrates of 20 μm. An electric charge of 20 volts to 0 volts was applied to this element, and the electrostatic 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), the measured electrostatic capacitance (C) was fitted to the value of the applied voltage (V), and according to the equation (2.100) to obtain the value of the elastic constant.

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 weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additives. Finally, the characteristic values of the composition are summarized.

[Comparative Example 1] Example 16 of International Publication No. 2012/86437 was selected as Comparative Example 1. This is because this composition contains the compound (1-24) as the first component of the present invention, and has the smallest viscosity (η). 3-Pnr(F6)-O2 (1-24) 3% 2-HH-5 (-) 3% 3-HH-4 (-) 15% 3-HH-5 (-) 4% 3-H2B(2F ,3F)-O2 (3-2) 27% 3-HHB(2F,3Cl)-O2 (3-11) 5% 3-HBB(2F,3F)-O2 (3-14) 12% 5-HBB( 2F,3F)-O2 (3-14) 9% 3-HB-O2 (4-1) 12% 3-HHB-1 (4-4) 3% 3-HHB-3 (4-4) 4% 3 -HHB-O1 (4-4) 3% NI=74.8℃; η=22.8 mPa·s; Δn=0.094; Δε=-4.4.

[Example 1] A composition prepared by replacing the second component of the present invention with 2-HH-5, 3-HH-4 and 3-HH-5 in the composition of Comparative Example 1. 3-Pnr(F6)-O2 (1-24) 3% V-HH-V (2-1) 3% V-HH-V1 (2-2) 19% 3-H2B(2F,3F)-O2 ( 3-2) 27% 3-HHB(2F,3Cl)-O2 (3-11) 5% 3-HBB(2F,3F)-O2 (3-14) 12% 5-HBB(2F,3F)-O2 (3-14) 9% 3-HB-O2 (4-1) 12% 3-HHB-1 (4-4) 3% 3-HHB-3 (4-4) 4% 3-HHB-O1 (4 -4) 3% NI=70.2℃; η=19.0 mPa·s; Δn=0.099; Δε=-4.4.

[Example 2] 5-HFLF4-3 (1-8) 5% V-HH-V (2-1) 10% V-HH-V1 (2-2) 25% 3-HB (2F, 3F)- O2 (3-1) 6% 5-HB(2F,3F)-O2 (3-1) 5% 3-BB(2F,3F)-O2 (3-6) 6% 3-HHB(2F,3F) -O2 (3-8) 8% 5-HHB(2F,3F)-O2 (3-8) 4% 3-HBB(2F,3F)-O2 (3-14) 7% 4-HBB(2F,3F) )-O2 (3-14) 8% 5-HBB(2F,3F)-O2 (3-14) 3% 3-HB-O2 (4-1) 6% 1-BB-3 (4-2) 4 % 3-HHB-1 (4-4) 3% NI=71.1℃; Tc＜-20℃; η=14.1 mPa·s; Δn=0.104; Δε=-2.8; γ1=47.3 mPa·s; K11=12.7 pN; K33=12.7 pN.

[Example 3] 5-HFLF4-3 (1-8) 5% V-HH-V (2-1) 10% V-HH-V1 (2-2) 25% 2-H1OB (2F, 3F)- O2 (3-3) 7% 3-H1OB(2F,3F)-O2 (3-3) 7% 3-HHB(2F,3F)-O2 (3-8) 4% 3-HBB(2F,3F) -O2 (3-14) 7% 4-HBB(2F,3F)-O2 (3-14) 4% 5-HBB(2F,3F)-O2 (3-14) 9% 3-dhBB(2F,3F) )-O2 (3-16) 4% 3-HB-O2 (4-1) 8% 3-HBB-2 (4-5) 10% NI=78.2℃; Tc＜-20℃; η=15.2 mPa· s; Δn=0.108; Δε=-2.9; γ1=52.1 mPa·s; K11=13.7 pN; K33=13.2 pN.

[Example 4] 5-HFLF4-3 (1-8) 4% V-HH-V (2-1) 24% 3-HB(2F, 3F)-O2 (3-1) 13% 5-HB( 2F,3F)-O2 (3-1) 3% V-HHB(2F,3F)-O1 (3-8) 4% V-HHB(2F,3F)-O2 (3-8) 10% 2-HHB (2F,3F)-O2 (3-8) 3% 3-HHB(2F,3F)-O2 (3-8) 4% 5-HHB(2F,3F)-O2 (3-8) 2% 3- HDhB(2F,3F)-O2 (3-13) 10% 3-dhBB(2F,3F)-O2 (3-16) 4% 1-BB-3 (4-2) 3% 3-HBB-2 ( 4-5) 5% V-HBB-2 (4-5) 11% NI=82.2℃; η=19.0 mPa·s; Δn=0.106; Δε=-3.5; γ1=64.2 mPa·s; K11=13.5 pN ; K33=13.1 pN; V95=4.64 V; τ(25)=4 4.9 ms; τ(-20) = 845.6 ms.

[Example 5] 5-HFLF4-3 (1-8) 4% V-HH-V1 (2-2) 28% 3-HB(2F, 3F)-O2 (3-1) 13% 5-HB( 2F,3F)-O2 (3-1) 5% V-HHB(2F,3F)-O1 (3-8) 4% V-HHB(2F,3F)-O2 (3-8) 10% 2-HHB (2F,3F)-O2 (3-8) 3% 3-HHB(2F,3F)-O2 (3-8) 4% 3-HDhB(2F,3F)-O2 (3-13) 10% 3- dhBB(2F,3F)-O2 (3-16) 6% 1-BB-3 (4-2) 3% 3-HBB-2 (4-5) 2% V-HBB-2 (4-5) 8 % NI=83.4℃; Tc＜-20℃; η=19.0 mPa·s; Δn=0.104; Δε=-3.6; γ1=64.2 mPa·s; V95=4.53 V; τ(25)=44.3 ms; τ( -20) = 844.6 ms.

[Example 6] 5-HFLF4-3 (1-8) 3% 5-HFLF4-4 (1-8) 1% 5-HFLF4-2V (1-8) 1% 3-HPnr(F6)-O2 ( 1-25) 2% 3-H1OPnr(F6)-O2 (1-28) 2% 5-H1OPnr(F6)-O2 (1-28) 2% V-HH-V (2-1) 15% V- HH-V1 (2-2) 25% V-HH-2V1 (2-4) 8% 3-DhB(2F,3F)-O2 (3-4) 3% 3-BB(2F,3F)-O2 ( 3-6) 4% 5-BB(2F,3F)-O2 (3-6) 4% 3-HH2B(2F,3F)-O2 (3-9) 10% 3-HDhB(2F,3F)-O2 (3-13) 4% 3-dhBB(2F,3F)-O2 (3-16) 9% V-HHB-1 (4-4) 2% V-HBB-2 (4-5) 5% NI=74.2℃; η=17.5 mPa·s; Δn=0.100; Δε=-3.3.

[Example 7] 5-HFLF4-3 (1-8) 4% 5-HFLF4-4 (1-8) 1% 5-HFLF4-2V (1-8) 1% 3-DhFLF4-5 (1-11 ) 1% 5-H2FLF4-3 (1-12) 1% 3-HK(F4)-H (1-33) 1% 4-HK(F4)-H (1-33) 1% 5-HK(F4 )-H (1-33) 1% V-HH-V (2-1) 9% V-HH-V1 (2-2) 19% V-HH-2V (2-3) 6% 1V-HH- 2V1 (2-7) 5% 3-HB(2F,3F)-O2 (3-1) 7% V2-BB(2F,3F)-O2 (3-6) 5% V-HHB(2F,3F) -O2 (3-8) 5% 2-HHB(2F,3F)-O2 (3-8) 3% 3-HHB(2F,3F)-O2 (3-8) 4% 3-HHB(2F,3Cl)-O2 (3-11) 3% 3-HBB(2F,3F)- O2 (3-14) 7% 3-HBB(2F,3Cl)-O2 (3-15) 3% 3-dhBB(2F,3F)-O2 (3-16) 3% 3-HBB-2 (4- 5) 5% 3-HH-V (-) 5% NI=78.6℃; Tc＜-20℃; η=17.0 mPa·s; Δn=0.100; Δε=-2.7.

[Example 8] 5-H1OFL (1F, 8F, 9F)-O2 (1-7) 3% 3-H1OFL (1F, 8F, 9F, 9F)-O2 (1-7) 1% 4-H1OFL (1F) ,8F,9F,9F)-O2 (1-7) 1% 5-H1OFL(1F,8F,9F,9F)-O2 (1-7) 1% 3-HK(F4)-H (1-33) 1% 4-HK(F4)-H (1-33) 1% 5-HK(F4)-H (1-33) 1% V-HH-V (2-1) 10% V-HH-V1 ( 2-2) 15% V-HH-2V1 (2-4) 5% V2-HH-2V1 (2-9) 6% V-HB(2F,3F)-O2 (3-1) 7% V2-BB (2F,3F)-O2 (3-6) 10% V-HHB(2F,3F)-O2 (3-8) 7% V2-HHB(2F,3F)-O2 (3-8) 4% 3- HH2B(2F,3F)-O2 (3-9) 9% 3-HchB(2F,3F)-O2 (3-12) 3% V-HBB(2F,3F)-O2 (3-14) 6% V-HBB(2F,3F)-O4 (3-14) ) 5% 3-HHB-1 (4-4) 4% NI=83.0℃; Tc＜-20℃; η=15.9 mPa·s; Δn=0.106; Δε=-3.2.

[Example 9] 3-HPnr(F6)-O2 (1-25) 2% 3-H1OPnr(F6)-O2 (1-28) 2% 3-H1OXt(3F, 4F, 5F)-O2 (1- 32) 2% 4-H1OXt(3F,4F,5F)-O2 (1-32) 2% 5-H1OXt(3F,4F,5F)-O2 (1-32) 2% V-HH-V (2- 1) 17% V-HH-V1 (2-2) 14% V-HH-2V (2-3) 2% 1V-HH-V1 (2-5) 2% 1V2-HH-2V1 (2-10) 2% VFF-HH-VFF (2-13) 2% 3-DhB(2F,3F)-O2 (3-4) 5% 2-HH1OB(2F,3F)-O2 (3-10) 2% 3- HDhB(2F,3F)-O2 (3-13) 5% 2-HBB(2F,3F)-O2 (3-14) 4% 3-HBB(2F,3F)-O2 (3-14) 8% V-HH2BB(2F,3F)-O2 (3-24) 3% 3-HB-O2 (4-1) 5% 1-BB-5 (4-2) 4% 3-HHB-3 (4 -4) 5% V-HHB-1 (4-4) 4% V-HBB-2 (4-5) 3% 3-HHEBH-3 (4-10) 3% NI=84.5℃; η=17.5 mPa ·s;Δn=0.101;Δε=-3.2.

[Example 10] 5-HFLF4-3 (1-8) 4% V-HH-V (2-1) 16% V-HH-V1 (2-2) 5% V-HB (2F, 3F)- O2 (3-1) 11% 3-HB(2F,3F)-O2 (3-1) 10% V-HHB(2F,3F)-O1 (3-8) 4% V-HHB(2F,3F) -O2 (3-8) 6% 2-HHB(2F,3F)-O2 (3-8) 3% 3-HHB(2F,3F)-O2 (3-8) 5% V-HBB(2F,3F) )-O2 (3-14) 6% 3-HBB(2F,3F)-O2 (3-14) 7% 1-BB-3 (4-2) 3% 3-HHB-1 (4-4) 5 % V-HBB-2 (4-5) 12% 2-HH-3 (-) 3% NI=75.0℃; Tc＜- 20℃; η=18.4 mPa·s; Δn=0.107; Δε=-3.1.

[Example 11] 5-HFLF4-3 (1-8) 3% 5-HFLF4-4 (1-8) 1% 5-HFLF4-2V (1-8) 1% 3-DhFLF4-5 (1-11 ) 1% 5-H2FLF4-3 (1-12) 1% 3-H1OPnr(F6)-O2 (1-28) 1% 5-H1OPnr(F6)-O2 (1-28) 1% V-HH-V (2-1) 15% V-HH-V1 (2-2) 17% 1V-HH-2V (2-6) 2% 3-HB(2F,3F)-O2 (3-1) 13% 5- HB(2F,3F)-O2 (3-1) 2% V-HHB(2F,3F)-O2 (3-8) 10% 3-HHB(2F,3F)-O2 (3-8) 4% 5 -HHB(2F,3F)-O2 (3-8) 5% 3-HB(2F,3F)B-1 (3-17) 3% 3-HB(2F,3F)B-2 (3-17) 3% 2-BB(2F,3F)B-3 (3-19) 4% 2-BB(2F,3F )B-4 (3-19) 5% 3-HBB-2 (4-5) 5% 3-HH-V1 (-) 3% NI=75.0℃; Tc＜-20℃; η=18.1 mPa·s ;Δn=0.106;Δε=-3.1.

[Example 12] 5-H1OFL (1F, 8F, 9F)-O2 (1-7) 1% 5-HFLF4-3 (1-8) 3% 5-HFLF4-4 (1-8) 1% 5- H2FLF4-3 (1-12) 1% 3-HPnr(F6)-O2 (1-25) 2% 3-H1OPnr(F6)-O2 (1-28) 2% 5-H1OPnr(F6)-O2 (1 -28) 2% V-HH-V (2-1) 15% V-HH-V1 (2-2) 12% V-HH-2V (2-3) 7% V2-HH-2V1 (2-9 ) 4% 3-H2B(2F,3F)-O2 (3-2) 3% 5-H2B(2F,3F)-O2 (3-2) 3% 2O-B(2F)B(2F,3F)- O2 (3-7) 2% 2O-B(2F)B(2F,3F)-O4 (3-7) 2% 3-HchB(2F,3F)-O2 (3-1 2) 3% V-HchB(2F,3F)-O2 (3-12) 3% 2-HBB(2F,3F)-O2 (3-14) 3% 3-HBB(2F,3F)-O2 (3 -14) 5% 5-HB-O2 (4-1) 5% 3-HHB-O1 (4-4) 3% 1V2-HHB-1 (4-4) 3% 3-HBB-2 (4-5 ) 4% V-HBB-2 (4-5) 5% 3-HH-4 (-) 3% 3-HH-5 (-) 3% NI=79.5℃; Tc＜-20℃; η=17.3 mPa ·s;Δn=0.102;Δε=-3.0.

[Example 13] 5-H1OFL (1F, 8F, 9F)-O2 (1-7) 3% 3-H1OFL (1F, 8F, 9F, 9F)-O2 (1-7) 1% 4-H1OFL (1F) ,8F,9F,9F)-O2 (1-7) 1% 5-H1OFL(1F,8F,9F,9F)-O2 (1-7) 1% 5-H1OPnr(F6)-O2 (1-28) 2% 3-H1OXt(3F,4F,5F)-O2 (1-32) 1% 3-HK(F4)-H (1-33) 1% V-HH-V (2-1) 10% V- HH-V1 (2-2) 23% V2-HH-2V (2-8) 4% V-HB(2F,3F)-O4 (3-1) 4% 2-BB(2F,3F)-O2 ( 3-6) 5% 3-BB(2F,3F)-O2 (3-6) 9% V2-BB(2F,3F)-O2 (3-6) 8% V-HHB(2F,3F)-O4 (3-8) 5% 2-HHB(2F,3F)-O2 (3-8) 3% 3-HHB(2F,3F)-O2 (3-8) 5% 3-HB(2F)B(2F,3F)-O2 (3-18) 3% V-H2BBB(2F,3F)-O2 (3 -25) 3% V2-HHB-1 (4-4) 5% 1O1-HBBH-4 (-) 3% NI=72.5℃; η=18.4 mPa·s; Δn=0.111; Δε=-3.5.

[Example 14] 5-HFLF4-3 (1-8) 4% 3-HK(F4)-H (1-33) 1% 4-HK(F4)-H (1-33) 1% 5-HK (F4)-H (1-33) 1% V-HH-V (2-1) 15% V-HH-V1 (2-2) 20% 3-H2B(2F,3F)-O2 (3-2 ) 10% 5-H2B(2F,3F)-O2 (3-2) 10% 3-chB(2F,3F)-O2 (3-5) 2% 3-HH1OB(2F,3F)-O2 (3- 10) 5% 2-HHB(2F,3Cl)-O2 (3-11) 2% 4-HHB(2F,3Cl)-O2 (3-11) 2% 5-HHB(2F,3Cl)-O2 (3 -11) 2% 3-HBB(2F,3F)-O2 (3-14) 5% 5-HBB(2F,3F)-O2 (3-14) 5% 3-BB(2F)B(2F,3F )-O2 (3-2 0) 2% 3-BB(F)B(2F,3F)-O2 (3-21) 2% 3-HH2BB(2F,3F)-O2 (3-24) 2% V2-BB-1 (4- 2) 2% 2-BB(F)B-3 (4-6) 2% V2-BB2B-1 (4-8) 3% 5-HBB(F)B-2 (4-12) 2% NI= 72.7℃; Tc＜-20℃; η=15.8 mPa·s; Δn=0.105; Δε=-3.0.

[Example 15] 5-HFLF4-4 (1-8) 1% 3-HPnr(F6)-O2 (1-25) 4% 3-H1OPnr(F6)-O2 (1-28) 2% 5-H1OPnr (F6)-O2 (1-28) 2% 3-H1OXt(3F,4F,5F)-O2 (1-32) 1% V-HH-V (2-1) 12% V-HH-V1 (2 -2) 15% V-HH-2V (2-3) 8% V-HH-2V1 (2-4) 8% 2-BB(2F,3F)-O2 (3-6) 6% 3-BB( 2F,3F)-O2 (3-6) 6% 3-HH2B(2F,3F)-O2 (3-9) 5% 3-HDhB(2F,3F)-O2 (3-13) 8% 5-HBB (2F,3Cl)-O2 (3-15) 3% 3-H2BBB(2F,3F)-O2 (3-25) 2% 7-HB-1 (4-1 ) 3% 1V2-BB-1 (4-2) 2% 3-HHB-3 (4-4) 3% 5-B(F)BB-2 (4-7) 3% 3-HHEBH-3 (4 -10) 2% 1V2-HH-1 (-) 2% 1V2-HH-3 (-) 2% NI=72.2℃; Tc＜-20℃; η=17.7 mPa·s; Δn=0.101; Δε=- 3.2.

[Example 16] 5-H1OFL (1F, 8F, 9F)-O2 (1-7) 2% 3-H1OFL (1F, 8F, 9F, 9F)-O2 (1-7) 1% 4-H1OFL (1F) ,8F,9F,9F)-O2 (1-7) 1% 5-H1OFL(1F,8F,9F,9F)-O2 (1-7) 1% 5-HFLF4-3 (1-8) 3% 3 -HK(F4)-H (1-33) 1% 4-HK(F4)-H (1-33) 1% 5-HK(F4)-H (1-33) 1% V-HH-V ( 2-1) 17% V-HH-V1 (2-2) 10% 3-HB(2F,3F)-O2 (3-1) 11% 5-HB(2F,3F)-O2 (3-1) 7% 3-BB(2F,3F)-O2 (3-6) 5% V-HHB(2F,3F)-O1 (3-8) 3% V-HHB(2F,3F)-O2 (3-8) ) 3% V-HHB(2F,3F)-O4 (3-8) 3% 2-BB(2F,3F)B-3 (3-19) 5% 2-BB(2F,3F)B-4 (3-19) 5% 3-HHEH-3 (4-3) 3% V-HBB-2 (4-5) 5% 1-BB(F)B-2V (4-6) 3% 3-HHEBH-4 (4-10) 2% 5-HB(F)BH-5 ( 4-11) 3% 4-HH-V (-) 2% 5-HH-V (-) 2% NI=72.1℃; η=18.2 mPa·s; Δn=0.110; Δε=-3.0.

[Example 17] 3-H1OPnr(F6)-O2 (1-28) 5% 5-H1OPnr(F6)-O2 (1-28) 5% 3-HK(F4)-H (1-33) 1% 4-HK(F4)-H (1-33) 1% 5-HK(F4)-H (1-33) 1% V-HH-V (2-1) 15% V-HH-V1 (2- 2) 20% V-HH-2V (2-3) 5% V-HH-2V1 (2-4) 5% V-HB(2F,3F)-O2 (3-1) 5% V-HB(2F ,3F)-O4 (3-1) 5% 3-HBB(2F,3F)-O2 (3-14) 5% 5-HBB(2F,3F)-O2 (3-14) 5% 3-HBB- 2 (4-5) 7% 5-B(F)BB-2 (4-7) 3% 5-B(F)BB-3 (4-7) 3% 3-HB(F)HH-5 (4-9) 2% 2-HH-3 (-) 5% 3-HBBH-5 (-) 2% NI=74.0℃; Tc＜ -20℃; η=17.3 mPa·s; Δn=0.100; Δε=-3.3.

[Example 18] 2O-dbt(4F, 6F)-O4 (1-15) 4% 2O-dbt(4F, 6F)-O5 (1-15) 4% V-HH-V (2-1) 21 % 3-HB(2F,3F)-O2 (3-1) 7% 5-HB(2F,3F)-O2 (3-1) 7% 2-HHB(2F,3F)-O2 (3-8) 6% 3-HHB(2F,3F)-O2 (3-8) 3% 4-HHB(2F,3F)-O2 (3-8) 5% 3-HchB(2F,3F)-O2 (3-12) ) 5% 5-HchB(2F,3F)-O2 (3-12) 5% 3-HBB(2F,3F)-O2 (3-14) 8% 2-BB(2F)B(2F,3F)- O4 (3-20) 2% 3-BB(F)B(2F,3F)-O2 (3-21) 2% 3-HH-V (-) 21% NI=74.2℃; Tc＜-20℃; η=14.0 mPa･s; Δn=0.096; Δε=-3.5.

[Example 19] 2O-dbt(4F, 6F)-O4 (1-15) 4% 2O-dbt(4F, 6F)-O5 (1-15) 4% V-HH-V1 (2-2) 21 % 3-HB(2F,3F)-O2 (3-1) 7% 5-HB(2F,3F)-O2 (3-1) 7% 2-HHB(2F,3F)-O2 (3-8) 6% 3-HHB(2F,3F)-O2 (3-8) 3% 4-HHB(2F,3F)-O2 (3-8) 5% 3-HchB(2F,3F)-O2 (3-12) ) 5% 5-HchB(2F,3F)-O2 (3-12) 5% 3-HBB(2F,3F)-O2 (3-14) 8% 2-BB(2F)B(2F,3F)- O4 (3-20) 2% 3-BB(F)B(2F,3F)-O2 (3-21) 2% 3-HH-V (-) 21% NI=83.3℃; Tc＜-20℃; η=16.0 mPa･s; Δn=0.102; Δε=-3.5.

[Example 20] 2O-dbt(4F, 6F)-O4 (1-15) 4% 2O-dbt(4F, 6F)-O5 (1-15) 4% V-HH-V (2-1) 21 % V-HH-V1 (2-2) 21% 3-HB(2F,3F)-O2 (3-1) 7% 5-HB(2F,3F)-O2 (3-1) 7% 2-HHB (2F,3F)-O2 (3-8) 6% 3-HHB(2F,3F)-O2 (3-8) 3% 4-HHB(2F,3F)-O2 (3-8) 5% 3- HchB(2F,3F)-O2 (3-12) 5% 5-HchB(2F,3F)-O2 (3-12) 5% 3-HBB(2F,3F)-O2 (3-14) 8% 2 -BB(2F)B(2F,3F)-O4 (3-20) 2% 3-BB(F)B(2F,3F)-O2 (3-21) 2% NI=76.1℃; Tc＜-20 ℃; η=14.7 mPa･s; Δn=0.101; Δε=-3.5.

The viscosity of the composition of Comparative Example 1 was 22.8 mPa·s. On the other hand, the viscosity of the composition of Example 1 was 19.0 mPa·s. The viscosity of the compositions of Examples 2 to 20 was in the range of 14.0 mPa·s to 19.0 mPa·s. As described above, the compositions of Examples had smaller viscosity than those of Comparative Examples. Therefore, it can be 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

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Claims (20)

A liquid crystal composition comprising at least one compound selected from the compounds represented by the formula (1) as the first component and at least one compound selected from the compounds represented by the formula (2) as the second component, the At least one compound in the second component is a compound represented by formula (2-2), and the liquid crystal composition has negative dielectric anisotropy,

In formula (1) and formula (2), R ¹ and R ² are independently hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon Alkenyloxy with 2 to 12 carbons, or alkyl with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; R ³ and R ⁴ are independently alkenyl with 2 to 12 carbons, 2 to 12 carbons Alkenyloxy of 12, or alkenyl of carbon number 2 to 12 in which at least one hydrogen is substituted by fluorine or chlorine; Ring A and Ring C are independently 1,4-cyclohexylene, 1,4-cyclohexene base, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine; ring B is perylene-2,7-diyl , dibenzothiophene-3,7-diyl, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, dibenzopyran-2,6-diyl or Dihydroindene-2,5-diyl, in these rings, at least one hydrogen can be substituted by fluorine or chlorine; Z ¹ and Z ² are independently a single bond, ethylidene, carbonyloxy or methyleneoxy ; a is 0, 1, 2 or 3, b is 0 or 1, and the sum of a and b is 3 or less. The liquid crystal composition according to claim 1, wherein the first component is at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-38),

In formula (1-1) to formula (1-38), R ¹ and R ² are independently hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkoxy having 2 to 12 carbons alkenyl, 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; X ¹ and X ² are independently hydrogen or fluorine. The liquid crystal composition according to claim 1, wherein the second component is selected from the group consisting of compounds represented by formula (2-1) and formula (2-3) to formula (2-13) at least one compound of

The liquid crystal composition according to claim 1, wherein the ratio of the first component is in the range of 3% by weight to 20% by weight. The liquid crystal composition according to claim 1, wherein the ratio of the second component is in the range of 10% by weight to 70% by weight. The liquid crystal composition according to item 1 of the claimed scope, comprising at least one compound selected from the compounds represented by the formula (3) as the third component,

In formula (3), R ⁵ and R ⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyl having 2 to 12 carbons Oxy group, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; Ring D and Ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydro Pyran-2,5-diyl, 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is substituted with fluorine or chlorine; ring E is 2,3-difluoro-1,4- phenylene, 2-chloro-3-fluoro-1,4-phenylene or 2,3-difluoro-5-methyl-1,4-phenylene; Z ³ and Z ⁴ are independently single bonds , ethylidene, carbonyloxy or methyleneoxy; c is 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 6, wherein the third component is at least one compound selected from the group of compounds represented by formula (3-1) to formula (3-25),

In formula (3-1) to formula (3-25), R ⁵ and R ⁶ 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. , an alkenyloxy group having 2 to 12 carbons, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine. The liquid crystal composition according to claim 6, wherein the ratio of the third component is in the range of 10% by weight to 70% by weight. The liquid crystal composition according to claim 1, comprising at least one compound selected from the group consisting of compounds represented by formula (4) as the fourth component,

In formula (4), R ⁷ and R ⁸ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, at least one hydrogen is substituted with fluorine or chlorine The alkyl group with 1 to 12 carbon atoms, or the alkenyl group with 2 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; Ring G and Ring I are independently 1,4-cyclohexylene, 1,4-cyclohexylene phenyl, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ⁵ is a single bond, ethylene or carbonyloxy; e is 1, 2 or 3; when e is 1, ring I is 1,4-phenylene. The liquid crystal composition according to item 9 of the patent application scope, wherein the fourth component is at least one compound selected from the group of compounds represented by formula (4-1) to formula (4-12),

In formula (4-1) to formula (4-12), R ⁷ and R ⁸ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons , an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, 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 9, wherein the ratio of the fourth component is in the range of 2% by weight to 50% by weight. The liquid crystal composition according to claim 6, comprising at least one compound selected from the group consisting of compounds represented by formula (4) as the fourth component,

In formula (4), R ⁷ and R ⁸ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, at least one hydrogen is substituted with fluorine or chlorine The alkyl group with 1 to 12 carbon atoms, or the alkenyl group with 2 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; Ring G and Ring I are independently 1,4-cyclohexylene, 1,4-cyclohexylene phenyl, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ⁵ is a single bond, ethylene or carbonyloxy; e is 1, 2 or 3; when e is 1, ring I is 1,4-phenylene. The liquid crystal composition according to claim 1, comprising at least one compound selected from the polymerizable compounds represented by the formula (5) as a first additive,

In formula (5), ring J and ring L are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxyl Alkyl-2-yl, pyrimidin-2-yl or pyridin-2-yl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons , or at least one hydrogen is substituted by an alkyl group having 1 to 12 carbon atoms substituted by fluorine or chlorine; ring K 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 base, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, carbon Alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or alkyl with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; Z ⁶ and Z ⁷ are independently a single bond or carbon The alkylene group of numbers 1 to 10, in the alkylene group, at least one -CH ₂ - may be substituted by -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ -CH ₂ - Can be substituted by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ )-, among these groups, 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 alkylene group having 1 to 10 carbon atoms, the In the alkyl group, at least one -CH ₂ - can be substituted by -O-, -COO-, -OCO- or -OCOO-, and at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C -Substituted, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; f is 0, 1 or 2; g, h and i are independently 0, 1, 2, 3 or 4, and g, h and i The sum is 1 or more. The liquid crystal composition according to claim 13, wherein in the formula (5), P ¹ , P ² and P ³ are independently represented by formulas (P-1) to (P-5) A group in the group of polymerizable groups,

In formula (P-1) to formula (P-5), M ¹ , M ² and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or carbon wherein at least one hydrogen is substituted with fluorine or chlorine 1 to 5 alkyl groups. The liquid crystal composition according to claim 13, wherein the first additive is at least one compound selected from the group of polymerizable compounds represented by formula (5-1) to formula (5-29). ,

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) base in;

Wherein, M ¹ , M ² and M ³ are independently hydrogen, fluorine, an alkyl group with 1 to 5 carbon atoms, or an alkyl group with 1 to 5 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; Sp ¹ , Sp ² and Sp ³ is independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be substituted by -O-, -COO-, -OCO- or -OCOO- , at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C-, and in these groups, at least one hydrogen can be substituted by fluorine or chlorine. According to the liquid crystal composition of claim 15, the ratio of the first additive is in the range of 0.03% by weight to 10% by weight. The liquid crystal composition according to item 6 of the claimed scope, comprising at least one compound selected from the polymerizable compounds represented by the formula (5) as the first additive,

In formula (5), ring J and ring L are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxyl Alkyl-2-yl, pyrimidin-2-yl or pyridin-2-yl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons , or at least one hydrogen is substituted by an alkyl group having 1 to 12 carbon atoms substituted by fluorine or chlorine; ring K 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 base, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, carbon Alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or alkyl with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; Z ⁶ and Z ⁷ are independently a single bond or carbon The alkylene group of numbers 1 to 10, in the alkylene group, at least one -CH ₂ - may be substituted by -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ -CH ₂ - Can be substituted by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ )-, among these groups, 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 alkylene group having 1 to 10 carbon atoms, the In the alkyl group, at least one -CH ₂ - can be substituted by -O-, -COO-, -OCO- or -OCOO-, and at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C -Substituted, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; f is 0, 1 or 2; g, h and i are independently 0, 1, 2, 3 or 4, and g, h and i The sum is 1 or more. The liquid crystal composition according to claim 12, comprising at least one compound selected from the polymerizable compounds represented by the formula (5) as a first additive,

In formula (5), ring J and ring L are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxyl Alkyl-2-yl, pyrimidin-2-yl or pyridin-2-yl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons , or at least one hydrogen is substituted by an alkyl group having 1 to 12 carbon atoms substituted by fluorine or chlorine; ring K 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 base, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, carbon Alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or alkyl with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; Z ⁶ and Z ⁷ are independently a single bond or carbon The alkylene group of numbers 1 to 10, in the alkylene group, at least one -CH ₂ - may be substituted by -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ -CH ₂ - Can be substituted by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ )-, among these groups, 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 alkylene group having 1 to 10 carbon atoms, the In the alkyl group, at least one -CH ₂ - can be substituted by -O-, -COO-, -OCO- or -OCOO-, and at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C -Substituted, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; f is 0, 1 or 2; g, h and i are independently 0, 1, 2, 3 or 4, and g, h and i The sum is 1 or more. A liquid crystal display element containing the liquid crystal composition according to claim 1. Use of a liquid crystal composition, such as the liquid crystal composition described in item 1 of the patent application scope, used in a liquid crystal display element.