WO2019135350A1 - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

A liquid crystal composition which satisfies at least one of, or has a suitable balance of at least two of, the characteristics of having a high upper temperature limit, a low lower temperature limit, a low viscosity, a high optical anisotropy, a high dielectric anisotropy and a high elastic constant, and an AM element containing said composition are provided. This liquid crystal composition may contain a specific compound having a low viscosity as a first component, a specific compound having a low viscosity as a second component, a specific compound having a negative dielectric anisotropy as a third component, or a specific compound having a low viscosity as a fourth component.

Description

Liquid crystal composition and liquid crystal display device

The present invention relates to a liquid crystal composition, a liquid crystal display element containing the composition, and the like. In particular, the present invention relates to a liquid crystal composition having a negative dielectric anisotropy, and a liquid crystal display device containing the composition and having a mode such as IPS, VA, FFS, or FPA.

In liquid crystal display devices, classification based on the operation mode of liquid crystal molecules is as follows: phase change (PC), twisted nematic (TN), super twisted nematic (STN), electrically controlled birefringence (ECB), optically compensated bend (OCB), IPS These modes are modes such as (in-plane switching), VA (vertical alignment), FFS (fringe field switching), and FPA (field-induced photo-reactive alignment). The classification based on the driving system of elements is PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into thin film transistor (TFT), metal insulator metal (MIM), etc. The classification of TFT is amorphous silicon and polycrystal silicon. The latter are classified into high temperature type and low temperature type according to the manufacturing process. Source based classifications are reflective based on natural light, transmissive based on back light, and semi-transmissive based on both natural light and back light.

The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the properties of this composition, an AM element having good properties can be obtained. The associations in these properties are summarized in Table 1 below. The characteristics of the composition will be further described based on commercially available AM devices. The temperature range of the nematic phase is related to the usable temperature range of the device. The preferred upper temperature limit of the nematic phase is about 70 ° C. or higher, and the preferred lower temperature limit of the nematic phase is about -10 ° C. or lower. The viscosity of the composition is related to the response time of the device. Short response times are preferred for displaying motion pictures on the device. Even shorter response times of 1 millisecond are desirable. Thus, low viscosity in the composition is preferred. Smaller viscosities at lower temperatures are more preferred. The elastic constant of the composition is related to the contrast ratio of the device. In order to increase the contrast ratio in the device, a large elastic constant in the composition is more preferred.

The optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large or small optical anisotropy, ie a suitable optical anisotropy, is required. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate value of the product depends on the type of operating mode. This value is in the range of about 0.30 μm to about 0.40 μm in the VA mode device and in the range of about 0.20 μm to about 0.30 μm in the IPS mode or FFS mode device. In these cases, compositions with large optical anisotropy are preferred for small cell gap devices. The large dielectric anisotropy in the composition contributes to low threshold voltage, low power consumption and high contrast ratio in the device. Therefore, large dielectric anisotropy is preferred. The large resistivity in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a large specific resistance at the initial stage is preferred. After prolonged use, compositions having high specific resistance are preferred. The stability of the composition to ultraviolet light and heat is related to the lifetime of the device. When this stability is high, the lifetime of the device is long. Such characteristics are preferable for an AM element used for a liquid crystal monitor, a liquid crystal television or the like.

In a general-purpose liquid crystal display device, vertical alignment of liquid crystal molecules is achieved by a specific polyimide alignment film. In a polymer sustained alignment (PSA) type liquid crystal display device, a polymer is combined with an alignment film. First, a composition to which a small amount of a polymerizable compound is added is injected into the device. Next, the composition is irradiated with ultraviolet light while applying a voltage between the substrates of the device. The polymerizable compound polymerizes to form a polymer network in the composition. In this composition, the polymer can control the alignment of liquid crystal molecules, thereby reducing the response time of the device and improving the image sticking. Such an effect of the polymer can be expected to devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

On the other hand, in a liquid crystal display element having no alignment film, a liquid crystal composition containing a polymer and a polar compound is used. First, a composition to which a small amount of polymerizable compound and a small amount of polar compound are added is injected into the device. Here, the polar compound is adsorbed on the substrate surface of the device and arranged. The liquid crystal molecules are oriented according to this arrangement. Next, the composition is irradiated with ultraviolet light while applying a voltage between the substrates of the device. Here, the polymerizable compound is polymerized to stabilize the alignment of liquid crystal molecules. In this composition, it is possible to control the alignment of liquid crystal molecules by the polymer and the polar compound, so that the response time of the device is shortened and the image sticking is improved. Furthermore, in the element having no alignment film, the process of forming the alignment film is unnecessary. Since there is no alignment film, the interaction between the alignment film and the composition does not lower the electrical resistance of the device. Such an effect of the combination of a polymer and a polar compound can be expected for devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

In an AM device having a TN mode, a composition having positive dielectric anisotropy is used. In an AM device having a VA mode, a composition having negative dielectric anisotropy is used. In an AM device having an IPS mode or an FFS mode, a composition having positive or negative dielectric anisotropy is used. In a polymer-supported oriented AM element, a composition having positive or negative dielectric anisotropy is used. In an element having no alignment film, a composition having positive or negative dielectric anisotropy is used.

Chinese Patent Application Publication No. 104593009

Problems of the present invention include: high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, appropriate optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability to ultraviolet light, thermal It is to provide a liquid crystal composition satisfying at least one of the high stability, the large elastic constant, and the like. Another object is to provide a liquid crystal composition having a proper balance between at least two of these properties. Another object is to provide a liquid crystal display device containing such a composition. Another object is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long lifetime.

A compound 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, and the nematic phase and the negative dielectric constant anisotropy The present invention relates to a liquid crystal composition having a property, and a liquid crystal display device containing the composition. The present invention also relates to a liquid crystal composition having a nematic phase and negative dielectric anisotropy, and a liquid crystal display device containing the composition.

In the formula (2), R ¹ and R ^{2 each} represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, at least one hydrogen Is C 1-12 alkyl substituted with fluorine or chlorine, or C 2-12 alkenyl in which at least one hydrogen is substituted by fluorine or chlorine.

The advantages of the present invention are: high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, suitable optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability to ultraviolet light, thermal It is to provide a liquid crystal composition satisfying at least one of the high stability, the large elastic constant, and the like. Another advantage is to provide a liquid crystal composition having a suitable balance between at least two of these properties. Another advantage is to provide a liquid crystal display device containing such a composition. Another advantage is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long lifetime.

The usage of the terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "composition" and "element", respectively. "Liquid crystal display element" is a generic term for liquid crystal display panels and liquid crystal display modules. The “liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase or a smectic phase and has no liquid crystal phase, but for the purpose of adjusting properties such as temperature range of the nematic phase, viscosity and dielectric anisotropy. It is a general term for compounds mixed in a composition. This compound has, for example, a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecule (liquid crystal molecule) is rod like. The "polymerizable compound" is a compound to be added for the purpose of forming a polymer in the composition. Liquid crystal compounds having alkenyl are not classified as polymerizable compounds in that sense.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as optically active compounds and polymerizable compounds are added to the liquid crystal composition as needed. The proportion of the liquid crystal compound is represented by mass percentage (mass%) based on the mass of the liquid crystal composition not including the additive even when the additive is added. The proportion of the additive is represented by mass percentage (mass%) based on the mass of the liquid crystal composition containing no additive. That is, the proportions of the liquid crystal compound and the additive are calculated based on the total mass of the liquid crystal compound. Parts per million (ppm) by mass may be used. The proportions of the polymerization initiator and the polymerization inhibitor are exceptionally expressed based on the weight of the polymerizable compound.

The “upper limit temperature of the nematic phase” may be abbreviated as the “upper limit temperature”. The “lower limit temperature of the nematic phase” may be abbreviated as the “lower limit temperature”. The expression "increase the dielectric anisotropy" means that in the case of a composition having a positive dielectric anisotropy, the value increases positively, and a composition having a negative dielectric anisotropy. In the case of goods, it means that the value increases negatively. The "high voltage holding ratio" means that the device has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit at the initial stage, and after a long period of use it shows a large voltage not only at room temperature but also at a temperature close to the upper limit. It means having a retention rate. The characteristics of the composition or the device may be examined by a time-dependent change test.

Formula (1z) is taken as an example. At least one compound selected from the compounds represented by formula (1z) may be abbreviated as “compound (1z)”.

The “compound (1z)” means one compound represented by the formula (1z), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas. The expression "at least one compound selected from compounds represented by the formula (1z) and the formula (2z)" means at least one compound selected from the group of the compound (1z) and the compound (2z) .

In formula (1z), the expression “Ra and Rb is alkyl, alkoxy or alkenyl” means that Ra and Rb are independently selected from the group of alkyl, alkoxy and alkenyl. That is, the group represented by Ra and the group represented by Rb may be the same or different. This rule is also applied when the symbol of Ra is used for a plurality of compounds. This rule also applies when multiple Ras are used in one compound.

In the formula (1z), symbols of α and β surrounded by a hexagon correspond to the ring α and the ring β, respectively, and represent a ring such as a 6-membered ring or a fused ring. When the index 'x' is 2, two rings α are present. The two groups represented by the two rings α may be identical or different. This rule applies to any two rings α when the index 'x' is greater than two. The oblique lines crossing one side of the ring β indicate that any hydrogen on the ring β may be replaced with a substituent (—Sp—P). The index 'y' indicates the number of substituted substituents. There is no such substitution when the index 'y' is zero. When the index 'y' is 2 or more, a plurality of substituents (-Sp-P) are present on the ring β. The rule "may be identical or different" applies also if the compounds have identical substituents.

The expression "at least one 'A'" means that the number of 'A' is arbitrary. In the expression “at least one 'A' may be replaced by 'B'”, when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is two Even in the case of three or more, their positions can be selected without limitation. The expression "at least one -CH _2- may be replaced by -O-" may be used. In this case, -CH ₂ -CH ₂ -CH ₂ -may be converted to -O-CH ₂ -O- by replacing non-adjacent -CH ₂ -with -O-. However, adjacent -CH _2- is not replaced by -O-. This replacement is because -OO-CH _2- (peroxide) is formed.

The alkyl of the liquid crystal compound is linear or branched and does not contain cyclic alkyl. Linear alkyls are preferred over branched alkyls. The same is true for end groups such as alkoxy and alkenyl. The configuration of 1,4-cyclohexylene is preferably trans rather than cis in order to increase the maximum temperature. Because 2-fluoro-1,4-phenylene is left-right asymmetrical, there are left (L) and right (R) orientations.

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

The present invention includes the following items.

Item 1. A compound 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, and the nematic phase and the negative dielectric constant anisotropy Liquid crystal composition having conductivity.

In the formula (2), R ¹ and R ^{2 each} represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, at least one hydrogen Is C 1-12 alkyl substituted with fluorine or chlorine, or C 2-12 alkenyl in which at least one hydrogen is substituted by fluorine or chlorine.

Item 2. Item 2. The liquid crystal composition according to item 1, wherein the proportion of the first component is in the range of 3% by mass to 30% by mass, and the proportion of the second component is in the range of 15% by mass to 45% by mass.

Item 3. Item 3. The liquid crystal composition according to item 1 or 2, containing at least one compound selected from the compounds represented by formula (3) as a third component.

In the formula (3), R ³ and R ⁴ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or at least Ring A and ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-, wherein C 1-12 alkyl in which one hydrogen is replaced by fluorine or chlorine; Diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2, in which at least one hydrogen is replaced by fluorine or chlorine, 6-diyl, chroman-2,6-diyl, or chroma in which at least one hydrogen is replaced by fluorine or chlorine Ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1 , 4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7- Diyl, 4,6-difluorodibenzofuran-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2,5-diyl; Z ¹ and Z ² are a single bond, ethylene, carbonyloxy A is 1, 2 or 3; b is 0 or 1; and the sum of a and b is 3 or less.

Item 4. 4. The liquid crystal composition according to any one of items 1 to 3, containing at least one compound selected from the compounds represented by formulas (3-1) to (3-35) as a third component.

In formulas (3-1) to (3-35), R ³ and R ^{4 each} represent hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, 2 to 12 alkenyloxy, or C 1 to C 12 alkyl in which at least one hydrogen is replaced by fluorine or chlorine.

Item 5. 5. The liquid crystal composition according to item 3 or 4, wherein the proportion of the third component is in the range of 30% by mass to 65% by mass.

Item 6. 6. The liquid crystal composition according to any one of items 1 to 5, containing at least one compound selected from compounds represented by formula (4) as a fourth component.

In Formula (4), R ⁵ and R ^{6 each} represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon in which at least one hydrogen is replaced by fluorine or chlorine. And alkyl having a number of 1 to 12 or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; ring D and ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ³ is a single bond, ethylene or carbonyloxy; c is 1, 2, or 3 Ring D is different from ring E when c is 1.

Item 7. 7. The liquid crystal composition according to any one of items 1 to 6, containing at least one compound selected from the compounds represented by formulas (4-1) to (4-11) as a fourth component.

In formulas (4-1) to (4-11), R ⁵ and R ^{6 each} represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, at least one hydrogen Is C 1-12 alkyl substituted with fluorine or chlorine, or C 2-12 alkenyl in which at least one hydrogen is substituted by fluorine or chlorine.

Item 8. Item 8. The liquid crystal composition according to item 6 or 7, wherein the proportion of the fourth component is in the range of 3% by mass to 35% by mass.

Item 9. 9. A liquid crystal display device containing the liquid crystal composition according to any one of items 1 to 8.

Item 10. 10. The liquid crystal display element according to item 9, wherein an operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and a driving method of the liquid crystal display element is an active matrix method.

Item 11. 9. Use of the liquid crystal composition according to any one of items 1 to 8 in a liquid crystal display device.

The present invention also includes the following items. (A) As an additive, at least one of an additive such as an optically active compound, an antioxidant, an ultraviolet light absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound The above composition containing. (B) AM element containing the above composition. (C) Polymer supported orientation (PSA) type AM element containing the above composition. (D) An AM element of polymer supported orientation (PSA) type containing the composition described above and in which the polymerizable compound in the composition is polymerized. (E) A device containing the composition described above and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA. (F) A transmission type device containing the above composition. (G) Use of the above composition as a composition having a nematic phase. (H) Use of an optically active composition obtained by adding an optically active compound to the above composition.

The composition of the present invention will be described in the following order. First, the composition of the composition will be described. Second, the main properties of the component compounds and the main effects of the compounds on the composition and the device are explained. Third, the combination of the component compounds in the composition, the preferred ratio, and the basis thereof will be described. Fourth, the preferred embodiments of the component compounds are described. Fifth, preferred component compounds are shown. Sixth, additives that may be added to the composition will be described. Seventh, the synthesis methods of the component compounds will be described. Finally, the application of the composition is described.

First, the composition of the composition will be described. This composition contains a plurality of liquid crystal compounds. The composition may contain an additive. The additive is an optically active compound, an antioxidant, an ultraviolet light absorber, a quencher, a pigment, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, a polar compound and the like. This composition is classified into the composition A and the composition B from the viewpoint of the liquid crystal compound. Composition A further contains other liquid crystal compounds, additives and the like in addition to the liquid crystal compounds selected from compound (1), compound (2), compound (3) and compound (4) It is also good. The “other liquid crystal compound” is a liquid crystal compound different from the compound (1), the compound (2), the compound (3), and the compound (4). Such compounds are mixed into the composition for the purpose of further adjusting the properties.

The composition B substantially consists only of the liquid crystal compound selected from the compound (1), the compound (2), the compound (3), and the compound (4). The term "substantially" means that composition B may contain an additive, but does not contain any other liquid crystal compound. Composition B has a smaller number of components than composition A. Composition B is preferable to composition A in terms of cost reduction. Composition A is preferable to composition B from the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds.

Second, the main properties of the component compounds and the main effects of the compounds on the composition are explained. The main properties of the component compounds are summarized in Table 2 based on the effects of the present invention. In the symbols of Table 2, L means large or high, M medium, and S small or low. The symbols L, M, S are classifications based on qualitative comparisons among the component compounds, and the symbol 0 (zero) means smaller than S (small).

The main effects of the component compounds on the properties of the composition are as follows. Compound (1) and compound (2) lower the lower limit temperature and lower the viscosity. Compound (3) lowers the lower limit temperature and raises the dielectric anisotropy. Compound (4) lowers the lower temperature limit and raises the upper temperature limit.

Third, the combination of the component compounds in the composition, the preferable ratio and the basis thereof will be described. Preferred combinations of the components in the composition are compound (1) + compound (2), compound (1) + compound (2) + compound (3), and compound (1) + compound (2) + compound (3) + Compound (4). A further preferred combination is compound (1) + compound (2) + compound (3) + compound (4).

The preferred proportion of the compound (1) is about 3% by mass or more to reduce the viscosity, and about 30% by mass or less to reduce the lower limit temperature. A further preferred ratio is in the range of about 3% by weight to about 25% by weight. An especially desirable ratio is in the range of about 3% by mass to about 20% by mass.

The preferred proportion of the compound (2) is about 15% by mass or more to reduce the viscosity, and about 45% by mass or less to reduce the lower limit temperature. A further preferred ratio is in the range of about 20% by weight to about 40% by weight. An especially desirable ratio is in the range of about 25% by mass to about 35% by mass.

The preferred proportion of the compound (3) is about 30% by mass or more for increasing the dielectric anisotropy, or about 65% by mass or less for decreasing the viscosity. A further preferred ratio is in the range of about 35% by weight to about 60% by weight. An especially desirable ratio is in the range of about 40% by weight to about 55% by weight.

The preferred proportion of the compound (4) is about 3% by mass or more to reduce the viscosity, and about 35% by mass or less to reduce the lower limit temperature. A further preferred ratio is in the range of about 5% by weight to about 30% by weight. An especially desirable ratio is in the range of about 8% by mass to about 25% by mass.

Fourth, the preferred embodiments of the component compounds are described.
In the formulas (2), (3) and (4), R ¹ and R ^{2 each} represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, 2 to 12 alkenyloxy, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Desirable R ¹ or R ² is alkenyl having 2 to 12 carbons to lower the viscosity, and alkyl having 1 to 12 carbons to increase the stability to ultraviolet light and heat. R ³ and R ⁴ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or at least one hydrogen is fluorine or It is a C1-C12 alkyl substituted by chlorine. Desirable R ³ or R ⁴ is alkenyl having 2 to 12 carbon atoms to lower the viscosity, alkyl having 1 to 12 carbons to increase the stability to ultraviolet light and heat, and to increase dielectric anisotropy C 1 to C 12 alkoxy for the purpose of R ⁵ and R ^{6 each} represents an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, an alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Or at least one hydrogen is an alkenyl having 2 to 12 carbons replaced with fluorine or chlorine. Desirable R ⁵ or R ⁶ is alkenyl having 2 to 12 carbons to lower the viscosity, and alkyl having 1 to 12 carbons to increase the stability to ultraviolet light and heat.

Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More preferred alkyl is methyl, ethyl, propyl, butyl or pentyl to lower the viscosity.

Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. More preferred alkoxy is methoxy or ethoxy to lower the viscosity.

Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl. More preferred alkenyl is vinyl, 1-propenyl, 3-butenyl or 3-pentenyl to reduce viscosity. The preferred configuration of —CH = CH— in these alkenyls depends on the position of the double bond. In alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl, trans is preferred to reduce viscosity. Cis is preferred for alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl.

Preferred examples of the alkyl in which at least one hydrogen is replaced by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl Or 8-fluorooctyl. Further preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl or 5-fluoropentyl to increase the dielectric anisotropy.

Preferred examples of the alkenyl in which at least one hydrogen is replaced by fluorine or chlorine are: 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro -4-pentenyl or 6,6-difluoro-5-hexenyl. Further preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl for decreasing the viscosity.

Ring A and ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is replaced by fluorine or chlorine 1 , 4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen is fluorine or chlorine And preferred ring A or ring C is 1,4-cyclohexylene to lower the viscosity or to raise the upper temperature limit, and to lower the lower temperature limit. 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine to increase dielectric anisotropy 1, It is 4-phenylene. Ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,4, 5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl (FLF4), 4,6- Difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2), or 1,1,6,7-tetrafluoroindane-2,5-diyl (InF4) It is. Preferred ring B is 2,3-difluoro-1,4-phenylene to increase dielectric anisotropy.

Ring D and ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene. Preferred ring D or ring E is 1,4-cyclohexylene to lower the viscosity or to raise the upper limit temperature, and 1,4-phenylene to increase the optical anisotropy.

Z ¹ and Z ² are a single bond, ethylene, carbonyloxy or methyleneoxy. Preferred Z ¹ or Z ² is a single bond to lower the viscosity, and methyleneoxy to increase the dielectric anisotropy. Z ³ is a single bond, ethylene or carbonyloxy. Preferred Z ³ is a single bond to lower the viscosity.

A is 1, 2 or 3; b is 0 or 1; and the sum of a and b is 3 or less. Preferred a is 1 to lower the viscosity and 2 to raise the upper temperature limit. Preferred b is 0 to lower the viscosity and 1 to raise the upper temperature limit. c is 1, 2 or 3; Preferred c is 1 to lower the viscosity and 2 to raise the upper temperature limit.

Fifth, preferred component compounds are shown. The preferred compound (3) is the compound (3-1) to the compound (3-33) described in Item 4. In these compounds, at least one of the third components is a compound (3-1), a compound (3-3), a compound (3-6), a compound (3-8), a compound (3-10), a compound (3 3-13), Compound (3-14) or Compound (3-16) is preferred. Compound (3-3) and Compound (3-8), Compound (3-3) and Compound (3-10), Compound (3-3) and Compound (3-14), Compound (3-3) and Compound (3-18), compound (3-6) and compound (3-8), compound (3-6) and compound (3-10), compound (3-6) and compound (3-16), compound (3 It is preferable that it is a combination of compound 3-6) and compound (3-18), or compound (3-10) and compound (3-14).

The preferred compound (4) is the compound (4-1) described in Item 7 to the compound (4-11). In these compounds, at least one of the fourth components is a compound (4-1), a compound (4-2), a compound (4-3), a compound (4-4), a compound (4-5), a compound (4) It is preferable that it is 4-9) or the compound (4-11). It is preferable that at least two of the fourth components be a combination of the compound (4-3) and the compound (4-4), the compound (4-2) and the compound (4-3).

Sixth, additives that may be added to the composition will be described. Such additives include optically active compounds, antioxidants, ultraviolet light absorbers, quenchers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules to give a twist angle. Examples of such compounds are compound (6-1) to compound (6-5). The preferred proportion of the optically active compound is about 5% by mass or less. A further preferred ratio is in the range of about 0.01% by weight to about 2% by weight.

In order to prevent the decrease in specific resistance due to heating in the atmosphere, or after using the device for a long time, in order to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature, Is added to the Preferred examples of the antioxidant include compounds (7-1) to (7-3).

Since the compound (7-2) has low volatility, it is effective to maintain 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. The preferred proportion of the antioxidant is about 50 ppm or more to obtain its effect, and is about 600 ppm or less so as not to lower the upper temperature limit or to raise the lower temperature limit. A further preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferred examples of the UV absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Also preferred are light stabilizers such as sterically hindered amines. Preferred examples of the light stabilizer include compound (8-1) to compound (8-16). The preferred proportion of these absorbents and stabilizers is about 50 ppm or more in order to obtain the effect, and is about 10000 ppm or less so as not to lower the upper temperature limit or to raise the lower temperature limit. A further preferred ratio is in the range of about 100 ppm to about 10000 ppm.

A quencher is a compound which receives the light energy absorbed by the liquid crystal compound and converts it into heat energy to prevent the decomposition of the liquid crystal compound. Preferred examples of the quencher are compound (9-1) to compound (9-7). The preferred proportion of these quenchers is about 50 ppm or more to obtain the effect, and about 20000 ppm or less to lower the lower limit temperature. A further preferred ratio is in the range of about 100 ppm to about 10000 ppm.

In order to conform to a guest host (GH) mode device, a dichroic dye such as an azo dye or an anthraquinone dye is added to the composition. The preferred proportion of dye is in the range of about 0.01% by weight to about 10% by weight. In order to prevent foaming, an antifoam agent such as dimethyl silicone oil, methylphenyl silicone oil or the like is added to the composition. The preferable proportion of the antifoaming agent is about 1 ppm or more in order to obtain the effect, and is about 1000 ppm or less in order to prevent display defects. A further preferred ratio is in the range of about 1 ppm to about 500 ppm.

Polar compounds are organic compounds with polarity. Here, compounds having an ionic bond are not included. Atoms such as oxygen, sulfur and nitrogen are more electronegative and tend to have a partial negative charge. Carbon and hydrogen tend to be neutral or have a partial positive charge. Polarity results from the inhomogeneous distribution of partial charges among different types of atoms in the compound. For example, the polar compound has at least one of partial structures such as -OH, -COOH, -SH, -NH ₂ ,>NH,> N-.

Seventh, the synthesis methods of the component compounds will be described. These compounds can be synthesized by known methods. The synthesis method is illustrated. The compound (1) is synthesized by the method described in JP-A-5-140003. The compound (2) is synthesized by the method described in JP-A-59-176221. The compound (3-8) is synthesized by the method described in JP-A-2-503441. The compound (4-3) is synthesized by the method described in JP-A-59-176221. Antioxidants are commercially available. Compound (6-1) can be obtained from Aldrich (Sigma-Aldrich Corporation). The compound (6-2) and the like are synthesized by the method described in US Pat. No. 3,660,505.

Compounds that did not describe the method of synthesis were organic syntheses (John Wiley & Sons, Inc.), Organic Reactions (John Wiley & Sons, Inc.), complementary organic syntheses ( It can be synthesized by the method described in the book of Comprehensive Organic Synthesis, Pergamon Press), New Experimental Chemistry Lecture (Maruzen) and the like. The compositions are prepared from the compounds thus obtained by known methods. For example, the component compounds are mixed and dissolved together by heating.

Finally, the application of the composition is described. Most compositions have a lower temperature limit of about -10.degree. C. or lower, an upper temperature limit of about 70.degree. 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 may be prepared by controlling the proportions of the component compounds, or by mixing other liquid crystal compounds. Furthermore, compositions having optical anisotropy in the range of about 0.10 to about 0.30 may be prepared by trial and error. Devices containing this composition have a large voltage holding ratio. This composition is suitable for an AM device. This composition is particularly suitable for transmissive AM devices. This composition can be used as a composition having a nematic phase or as an optically active composition by adding an optically active compound.

This composition can be used for an AM device. Furthermore, the use to PM element is also possible. This composition can be used for AM devices and PM devices having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA. The use for an AM device having a TN, OCB, IPS mode or FFS mode is particularly preferred. In an AM device having an IPS mode or an FFS mode, when no voltage is applied, the alignment of liquid crystal molecules may be parallel to or perpendicular to the glass substrate. These elements may be reflective, transmissive or semi-transmissive. Its use for transmission type devices is preferred. The use for amorphous silicon-TFT elements or polycrystalline silicon-TFT elements is also possible. The composition can be used for an element of NCAP (nematic curvilinear aligned phase) type prepared by microencapsulation or a element of PD (polymer dispersed) type in which a three-dimensional network polymer is formed in the composition.

The invention will be further described by way of examples. The invention is not limited by these examples. The present invention comprises a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes a mixture of at least two of the compositions of the Examples. The compound synthesized was identified by a method such as NMR analysis. The properties of the compounds, compositions and devices were measured by the methods described below.

NMR analysis: For measurement, DRX-500 manufactured by Bruker Biospin Ltd. was used. ^In the measurement of ¹ H-NMR, the sample was dissolved in a deuterated solvent such as CDCl _3, and the measurement was performed at room temperature under conditions of 500 MHz and 16 integrations. Tetramethylsilane was used as an internal standard. ^{In the 19} F-NMR measurement, CFCl ₃ was used as an internal standard, and the integration was performed 24 times. In the description of nuclear magnetic resonance spectrum, s is singlet, d is doublet, t is triplet, q is quartet, quin is quintet, sex is sextet, m is multiplet, br is broad.

Gas Chromatographic Analysis: A GC-14B gas chromatograph made by Shimadzu Corporation was used for measurement. The carrier gas is helium (2 mL / min). The sample vaporization chamber was set at 280 ° C. and the detector (FID) was set at 300 ° C. For separation of the component compounds, capillary columns DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm; fixed liquid phase is dimethylpolysiloxane; nonpolar) manufactured by Agilent Technologies Inc. were used. The column was kept at 200 ° C. for 2 minutes and then heated to 280 ° C. at a rate of 5 ° C./minute. The sample was prepared in an acetone solution (0.1% by mass), and 1 μL thereof was injected into the sample vaporization chamber. The recorder is Model C-R5A Chromatopac manufactured by Shimadzu Corporation, or its equivalent. The obtained gas chromatogram showed the retention time of the peak corresponding to the component compound and the area of the peak.

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

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

Measurement sample: When measuring the characteristics of the composition and the device, the composition was used as it was as a sample. When measuring the properties of the compound, a sample for measurement was prepared by mixing this compound (15% by mass) with the mother liquid crystal (85% by mass). The characteristic values of the compound were calculated by extrapolation from the values obtained by the measurement. (Extrapolated value) = {(measured value of sample) −0.85 × (measured value of mother liquid crystal)} / 0.15. When a smectic phase (or crystal) precipitates at 25 ° C. in this proportion, the proportion of the compound and the base liquid crystal is 10 mass%: 90 mass%, 5 mass%: 95 mass%, 1 mass%: 99 mass% in this order. changed. The values of the upper limit temperature, the optical anisotropy, the viscosity, and the dielectric anisotropy of the compound were determined by this extrapolation method.

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

Measurement method: The measurement of the characteristics was performed by the following method. Many of these are modified methods or methods described in the JEITA standard (JEITA ED-2521B), which is deliberately established by the Japan Electronics and Information Technology Industries Association (hereinafter referred to as JEITA). It was a method. A thin film transistor (TFT) was not attached to the TN device 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 apparatus equipped with a polarization microscope and heated at a rate of 1 ° C./min. The temperature was measured when part of the sample changed from the nematic phase to the isotropic liquid. The upper limit temperature of the nematic phase may be abbreviated as "upper limit temperature".

(2) Lower limit temperature of nematic phase (T _C ; ° C.): A sample having a nematic phase is placed in a glass bottle and kept for 10 days in a freezer at 0 ° C., -10 ° C., -20 ° C., -30 ° C. and -40 ° C. After storage, the liquid crystal phase was observed. For example, the sample remained in the -20 ° C. in a nematic phase, when changed to -30 ° C. At crystals or a smectic phase was described as <-20 ° C. The T _C. The lower limit temperature of the nematic phase may be abbreviated as "lower limit temperature".

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

(4) Viscosity (rotational viscosity; γ1; measured at 25 ° C .; mPa · s): For measurement, a rotational viscosity measurement system LCM-2 type manufactured by Toyo Technica Co., Ltd. was used. The sample was injected into a VA device in which the distance between two glass substrates (cell gap) was 10 μm. A rectangular wave (55 V, 1 ms) was applied to this element. The peak current and peak time of transient current generated by this application were measured. The values of rotational viscosity were obtained using these measured values and dielectric anisotropy. The dielectric anisotropy was measured by the method described in the measurement (6).

(5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25 ° C.): Measurement was performed using an Abbe refractometer with a polarizing plate attached to the ocular, using light of wavelength 589 nm. After rubbing the surface of the main prism in one direction, a sample was dropped on the main prism. The refractive index n∥ was measured when the polarization direction was parallel to the rubbing direction. The refractive index n⊥ was measured when the polarization direction was perpendicular to the rubbing direction. The value of optical anisotropy was calculated from the formula of Δn = n∥−n⊥.

(6) Dielectric anisotropy (Δε; measured at 25 ° C.): The value of dielectric anisotropy was calculated from the equation of Δε = εε−ε⊥. The dielectric constants (ε∥ and ε⊥) were measured as follows.
1) Measurement of dielectric constant (ε∥): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a well-cleaned glass substrate. The glass substrate was rotated by a spinner and then heated at 150 ° C. for 1 hour. A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 4 μm, and this device was sealed with an adhesive cured with ultraviolet light. Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant (ε∥) in the major axis direction of liquid crystal molecules was measured.
2) Measurement of dielectric constant (ε⊥): A polyimide solution was applied to a well-cleaned glass substrate. After firing the glass substrate, the obtained alignment film was rubbed. The sample was placed in a TN device in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant (⊥) in the minor axis direction of liquid crystal molecules was measured.

(7) Threshold voltage (Vth; measured at 25 ° C .; V): An LCD-5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. A sample is placed in a normally black mode VA device in which the distance between two glass substrates (cell gap) is 4 μm and the rubbing direction is antiparallel, and an adhesive for curing this device with ultraviolet light is used. Used and sealed. The voltage (60 Hz, rectangular wave) applied to this element was gradually increased by 0.02 V from 0 V to 20 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The threshold voltage was represented by the voltage at 10% transmittance.

(8) Voltage holding ratio (VHR-1; measured at 25 ° C .;%): The TN device used for measurement had a polyimide alignment film, and the distance between two glass substrates (cell gap) was 5 μm. . The element was sealed with an adhesive that cures with ultraviolet light after the sample was placed. A pulse voltage (60 microseconds at 5 V) was applied to the TN device to charge it. The decaying voltage was measured with a high-speed voltmeter for 16.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined. The area B was the area when it did not decay. The voltage holding ratio was expressed as a percentage of the area A to the area B.

(9) Voltage holding ratio (VHR-2; measured at 80 ° C .;%): The voltage holding ratio was measured by the same procedure as described above except that measurement was performed at 80 ° C. instead of 25 ° C. The obtained value was expressed as VHR-2.

(10) Voltage holding ratio (VHR-3; measured at 25 ° C .;%): After irradiation with ultraviolet light, the voltage holding ratio was measured to evaluate the stability to ultraviolet light. The TN device used for the measurement had a polyimide alignment film, and the cell gap was 5 μm. A sample was injected into the device and irradiated with light for 20 minutes. The light source was an ultra-high pressure mercury lamp USH-500D (manufactured by Ushio Inc.), and the distance between the element and the light source was 20 cm. In the measurement of VHR-3, the decaying voltage was measured for 16.7 milliseconds. Compositions having large VHR-3 have high stability to ultraviolet light. 90% or more is preferable and 95% or more of VHR-3 is more preferable.

(11) Voltage holding ratio (VHR-4; measured at 25 ° C .;%): The TN device injected with the sample is heated in a thermostatic chamber at 80 ° C. for 500 hours, and then the voltage holding ratio is measured and stability to heat Was evaluated. In the measurement of VHR-4, the decaying voltage was measured for 16.7 milliseconds. Compositions having large VHR-4 have high thermal stability.

(12) Response time (τ; measured at 25 ° C .; ms): For measurement, LCD Evaluation System Model LCD-5100 made by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. The low pass filter (Low-pass filter) was set to 5 kHz. The 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 antiparallel. The device was sealed using an adhesive that cures with ultraviolet light. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to this element. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. It was considered that the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The response time is represented by the time (fall time; milliseconds) taken to change from 90% transmittance to 10% transmittance.

(13) Elastic constant (K11: splay elastic constant, K33: bend elastic constant; measured at 25 ° C .; pN): To measure, use an EC-1 type elastic constant measuring instrument manufactured by Toyo Corporation. Using. The sample was placed in a vertical alignment cell in which the distance between two glass substrates (cell gap) was 20 μm. A charge of 20 volts to 0 volts was applied to the cell, and the capacitance and the applied voltage were measured. Fitting the measured capacitance (C) and applied voltage (V) values using the formula (2.98) and formula (2.101) on page 75 of “Liquid Crystal Device Handbook” (Nippon Kogyo Shimbun Ltd.) And the value of the elastic constant was obtained from equation (2.100).

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

The compounds in the examples are represented by symbols based on the definition of Table 3 below. In Table 3, the configuration for 1,4-cyclohexylene is trans. The numbers in parentheses after the symbols correspond to the compound numbers. The symbol (-) means other liquid crystal compounds. The proportion (percentage) of the liquid crystal compound is a mass percentage (mass%) based on the mass of the liquid crystal composition. Finally, the characteristic values of the composition were summarized.

As a comparative example, Example 7 was selected from the compositions disclosed in Chinese Patent Application Publication No. 104593009. This composition contains the compound (1) and has negative dielectric anisotropy.

Comparative Example 1
Cpr-2HB (2F, 3F) -O2 (-) 12%
Cpr-HHB (2F, 3F) -O2 (-) 8%
Cpr-2HH1OB (2F, 3F) -O2 (-) 8%
2-HH1OB (2F, 3F) -O2 (3-10) 12%
1-HB-4 (4-1) 15%
2-BB-1 (1) 10%
1-BBB-2 (4) 10%
4-BB (2F, 3F) B-O2 (3-19) 6%
2-BB (2F, 3F) B (2F, 3F)-O2
(3) 5%
Cpr-1 BB (2F, 3F) B-4 (-) 7%
3-HB (2F, 3F) -4 (3-1) 7%
NI = 105.5 ° C .; Δn = 0.1735; Δε = −5.5; γ1 = 110.9 mPa · s.

Example 1
2-BB-1 (1) 14%
3-HH-2 (2) 25%
3-H1OB (2F, 3F) -O2 (3-3) 8%
3-HHB (2F, 3F) -O2 (3-8) 11%
2-HH1OB (2F, 3F) -O2 (3-10) 6%
3-HH1OB (2F, 3F) -O2 (3-10) 20%
3-HB (2F) B (2F, 3F) -O2 (3-18) 4%
3-HHB-1 (4-3) 8%
3-BB-1 (-) 4%
NI = 73.7 ° C .; Tc <−20 ° C .; Δn = 0.097; Δε = −3.1; γ1 = 93.0 mPa · s; K33 = 13.8 pN.

Example 2
2-BB-1 (1) 10%
3-HH-2 (2) 28%
3-HB (2F, 3F) -O2 (3-1) 10%
2-HH1OB (2F, 3F) -O2 (3-10) 14%
3-HH1OB (2F, 3F) -O2 (3-10) 16%
3-HBB-2 (4-4) 19%
3-BB-1 (-) 3%
Tc <−20 ° C .; Δn = 0.100; Δε = −2.4; γ1 = 91.4 mPa · s; K33 = 11.9 pN.

[Example 3]
2-BB-1 (1) 8%
3-HH-V (2) 7%
3-HH-2 (2) 15%
2-H1OB (2F, 3F)-O2 (3-3) 3%
3-H1OB (2F, 3F) -O2 (3-3) 3%
V2-BB (2F, 3F) -O2 (3-6) 5%
2-HHB (2F, 3F) -O2 (3-8) 3%
3-HHB (2F, 3F) -O2 (3-8) 4%
5-HHB (2F, 3F) -O2 (3-8) 3%
V-HHB (2F, 3F) -O1 (3-8) 3%
V-HHB (2F, 3F) -O2 (3-8) 3%
V-HHB (2F, 3F) -O4 (3-8) 2%
3-HH2B (2F, 3F) -O2 (3-9) 4%
5-HH2B (2F, 3F) -O2 (3-9) 4%
2-HBB (2F, 3F) -O2 (3-14) 3%
3-HBB (2F, 3F) -O2 (3-14) 3%
3-H1OCro (7F, 8F) -5 (3-26) 3%
V-HHB-1 (4-3) 4%
V2-HHB-1 (4-3) 4%
5-B (F) BB-2 (4-6) 3%
3-BB-1 (-) 3%
5-BB-1 (-) 3%
1V2-BB-1 (-) 3%
1O1-HBBH-5 (-) 4%
Tc <−20 ° C .; Δn = 0.111; Δε = −2.3; γ1 = 92.5 mPa · s.

Example 4
2-BB-1 (1) 3%
3-HH-V (2) 10%
3-HH-V1 (2) 3%
3-HH-2 (2) 10%
5-HH-V (2) 3%
1V2-HH-2V1 (2) 3%
V-HB (2F, 3F) -O2 (3-1) 3%
V-ch B (2F, 3F)-O2 (3-5) 3%
2-BB (2F, 3F)-O2 (3-6) 3%
3-BB (2F, 3F)-O2 (3-6) 3%
2O-BB (2F, 3F)-O2 (3-6) 3%
2O-B (2F) B (2F, 3F) -O2 (3-7) 3%
V-HH1OB (2F, 3F) -O2 (3-10) 3%
3-HchB (2F, 3F) -O2 (3-12) 5%
5-HchB (2F, 3F) -O2 (3-12) 5%
V2-HchB (2F, 3F) -O2 (3-12) 4%
3-dhBB (2F, 3F) -O2 (3-16) 5%
2-B2BB (2F, 3F) -O2 (3-22) 3%
2-BB2B (2F, 3F)-3 (3-23) 3%
3-HH1OCro (7F, 8F) -5 (3-27) 3%
3-HHB-3 (4-3) 3%
V2-BB2B-1 (4-7) 3%
3-HHEBH-3 (4-9) 3%
3-BB-1 (-) 4%
V2-BB-1 (-) 6%
NI = 74.0 ° C .; Tc <−20 ° C .; Δn = 0.117; Δε = −2.5; γ1 = 91.4 mPa · s.

[Example 5]
2-BB-1 (1) 8%
V-HH-V (2) 8%
V-HH-V1 (2) 8%
3-HH-V (2) 8%
1V2-HH-3 (2) 4%
5-HB (2F, 3F) -O2 (3-1) 5%
3-DhB (2F, 3F)-O2 (3-4) 5%
3-chB (2F, 3F)-O2 (3-5) 5%
V-HHB (2F, 3F) -O2 (3-8) 3%
V-HHB (2F, 3F) -O4 (3-8) 3%
V-HH1OB (2F, 3F) -O2 (3-10) 5%
3-HDhB (2F, 3F) -O2 (3-13) 3%
4-HBB (2F, 3F) -O2 (3-14) 3%
5-HBB (2F, 3F) -O2 (3-14) 3%
3-BB (2F) B (2F, 3F)-O2 (3-20) 3%
5-BB (2F) B (2F, 3F)-O2 (3-20) 3%
V-HH2BB (2F, 3F) -O2 (3-24) 3%
3-HB-O2 (4-1) 3%
V-HHB-1 (4-3) 3%
3-HBB-2 (4-4) 3%
V-HBB-2 (4-4) 3%
3-HB (F) HH-2 (4-8) 3%
5-HB (F) BH-2 (4-10) 5%
NI = 85.2 ° C .; Tc <−20 ° C .; Δn = 0.118; Δε = −2.5; γ1 = 92.8 mPa · s.

[Example 6]
2-BB-1 (1) 7%
3-HH-V1 (2) 8%
3-HH-2 (2) 20%
3-H2B (2F, 3F)-O2 (3-2) 5%
5-H2B (2F, 3F)-O2 (3-2) 5%
3-HH1OB (2F, 3F) -O2 (3-10) 8%
3-HHB (2F, 3Cl) -O2 (3-11) 3%
5-HHB (2F, 3Cl) -O2 (3-11) 3%
3-HchB (2F, 3F) -O2 (3-12) 3%
5-HchB (2F, 3F) -O2 (3-12) 3%
V-HBB (2F, 3F) -O2 (3-14) 3%
3-HBB (2F, 3Cl) -O2 (3-15) 4%
5-HBB (2F, 3Cl) -O2 (3-15) 3%
5-HB-3 (4-1) 4%
3-HHB-1 (4-3) 3%
V-HBB-3 (4-4) 3%
1-BB (F) B-2V (4-5) 3%
2-BB (F) B-2 V (4-5) 3%
3-BB (F) B-2V (4-5) 3%
V2-BB-1 (-) 3%
1V2-BB-1 (-) 3%
NI = 83.6 ° C .; Tc <−20 ° C .; Δn = 0.118; Δε = −1.8; γ1 = 91.7 mPa · s.

[Example 7]
2-BB-1 (1) 3%
3-HH-V (2) 31%
3-HH-VFF (2) 4%
3-HB (2F, 3F) -O2 (3-1) 5%
5-HB (2F, 3F) -O2 (3-1) 5%
3-BB (2F, 3F)-O2 (3-6) 10%
3-HHB (2F, 3F) -O2 (3-8) 5%
V-HHB (2F, 3F) -O2 (3-8) 3%
3-HH2B (2F, 3F) -O2 (3-9) 8%
2-HBB (2F, 3F) -O2 (3-14) 3%
3-HBB (2F, 3F) -O2 (3-14) 6%
4-HBB (2F, 3F) -O2 (3-14) 3%
2-BB (2F, 3F) B-3 (3-19) 3%
2-BB (2F, 3F) B-4 (3-19) 3%
3-HHEH-3 (4-2) 4%
5-HBB (F) B-2 (4-11) 2%
5-HBB (F) B-3 (4-11) 2%
Tc <−20 ° C .; Δn = 0.107; Δε = −2.4; γ1 = 90.0 mPa · s.

[Example 8]
2-BB-1 (1) 4%
V-HH-V (2) 14%
V-HH-V1 (2) 5%
3-HH-2 (2) 6%
3-HH-4 (2) 3%
2-HH-5 (2) 3%
2-H1OB (2F, 3F)-O2 (3-3) 6%
2-HH1OB (2F, 3F) -O2 (3-10) 13%
3-HB (2F, 3F) B-O2 (3-17) 8%
3-HB (2F) B (2F, 3F) -O2 (3-18) 4%
3-BB (F) B (2F, 3F) -O2 (3-21) 3%
2-B2BB (2F, 3F) -O2 (3-22) 3%
3-H2BBB (2F, 3F) -O2 (3-25) 3%
5-HFLF 4-3 (3-28) 3%
3-HB-O2 (4-1) 3%
5-HB-O2 (4-1) 3%
7-HB-1 (4-1) 4%
3-HHB-O1 (4-3) 3%
5-B (F) BB-3 (4-6) 3%
3-HHEBH-3 (4-9) 3%
V2-BB-1 (-) 3%
NI = 73.0 ° C .; Tc <−20 ° C .; Δn = 0.107; Δε = −2.9; γ1 = 91.9 mPa · s.

[Example 9]
2-BB-1 (1) 6%
V-HH-V (2) 2%
V-HH-V1 (2) 2%
3-HH-2 (2) 10%
3-HH-O1 (2) 4%
5-HH-O1 (2) 4%
V-HB (2F, 3F) -O2 (3-1) 3%
3-HB (2F, 3F) -O2 (3-1) 3%
2-H1OB (2F, 3F)-O2 (3-3) 5%
3-H1OB (2F, 3F) -O2 (3-3) 5%
3-BB (2F, 3F)-O2 (3-6) 5%
5-BB (2F, 3F)-O2 (3-6) 5%
3-HHB (2F, 3F) -O2 (3-8) 4%
3-HH1OB (2F, 3F) -O2 (3-10) 12%
3-HHEH-3 (4-2) 3%
3-HHEH-5 (4-2) 3%
3-HHB-O1 (4-3) 3%
2-BB (F) B-3 (4-5) 3%
2-BB (F) B-5 (4-5) 3%
3-HHEBH-3 (4-9) 3%
3-HHEBH-4 (4-9) 3%
3-HHEBH-5 (4-9) 3%
V2-BB-1 (-) 3%
1V2-BB-1 (-) 3%
Tc <−20 ° C .; Δn = 0.104; Δε = −2.8; γ1 = 92.1 mPa · s.

The rotational viscosity of the composition of Comparative Example 1 was 110.9 mPa · s. On the other hand, the rotational viscosity of the composition of Example 1 was 93.0 mPa · s. Thus, the composition of Example 1 had lower viscosity as compared to the composition of Comparative Example. Therefore, it is concluded that the liquid crystal composition of the present invention has excellent properties.

The liquid crystal composition of the present invention can be used for a liquid crystal monitor, a liquid crystal television and the like.

Claims (11)

1. A compound 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, and the nematic phase and the negative dielectric constant anisotropy Liquid crystal composition having conductivity.
   

   

   
   In the formula (2), R ¹ and R ^{2 each} represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, at least one hydrogen Is C 1-12 alkyl substituted with fluorine or chlorine, or C 2-12 alkenyl in which at least one hydrogen is substituted by fluorine or chlorine.
2. The liquid crystal composition according to claim 1, wherein the proportion of the first component is in the range of 3% by mass to 30% by mass, and the proportion of the second component is in the range of 15% by mass to 45% by mass.
3. The liquid crystal composition according to claim 1, containing at least one compound selected from the compounds represented by Formula (3) as a third component.
   

   

   
   In the formula (3), R ³ and R ⁴ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or at least Ring A and ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-, wherein C 1-12 alkyl in which one hydrogen is replaced by fluorine or chlorine; Diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2, in which at least one hydrogen is replaced by fluorine or chlorine, 6-diyl, chroman-2,6-diyl, or chroma in which at least one hydrogen is replaced by fluorine or chlorine Ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1 , 4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7- Diyl, 4,6-difluorodibenzofuran-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2,5-diyl; Z ¹ and Z ² are a single bond, ethylene, carbonyloxy A is 1, 2 or 3; b is 0 or 1; and the sum of a and b is 3 or less.
4. The liquid crystal composition according to any one of claims 1 to 3, containing at least one compound selected from the compounds represented by formulas (3-1) to (3-35) as a third component. .
   

   

   
   

   

   
   

   

   
   In formulas (3-1) to (3-35), R ³ and R ^{4 each} represent hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, 2 to 12 alkenyloxy, or C 1 to C 12 alkyl in which at least one hydrogen is replaced by fluorine or chlorine.
5. The liquid crystal composition according to claim 3 or 4, wherein the proportion of the third component is in the range of 30% by mass to 65% by mass.
6. The liquid crystal composition according to any one of claims 1 to 5, containing at least one compound selected from the compounds represented by formula (4) as a fourth component.
   

   

   
   In Formula (4), R ⁵ and R ^{6 each} represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon in which at least one hydrogen is replaced by fluorine or chlorine. And alkyl having a number of 1 to 12 or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; ring D and ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ³ is a single bond, ethylene or carbonyloxy; c is 1, 2, or 3 Ring D is different from ring E when c is 1.
7. The liquid crystal composition according to any one of claims 1 to 6, containing at least one compound selected from the compounds represented by formulas (4-1) to (4-11) as a fourth component. .
   

   

   
   In formulas (4-1) to (4-11), R ⁵ and R ^{6 each} represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, at least one hydrogen Is C 1-12 alkyl substituted with fluorine or chlorine, or C 2-12 alkenyl in which at least one hydrogen is substituted by fluorine or chlorine.
8. The liquid crystal composition according to claim 6 or 7, wherein the proportion of the fourth component is in the range of 3% by mass to 35% by mass.
9. A liquid crystal display device comprising the liquid crystal composition according to any one of claims 1 to 8.
10. 10. The liquid crystal display element according to claim 9, wherein an operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and a driving method of the liquid crystal display element is an active matrix method.
11. Use of the liquid crystal composition according to any one of claims 1 to 8 in a liquid crystal display device.