JP2007031694A - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal composition having a wide temperature range of a nematic phase, a low viscosity, a suitable optical anisotropy, a large negative permittivity anisotropic property and a large specific resistance, and a liquid crystal display element containing this composition. <P>SOLUTION: The liquid crystal composition with a negative permittivity anisotropic property contains a first component, i.e., a liquid crystalline compound containing one fluorine atom of a specific structure and a second component, i.e., a liquid crystalline compound containing two or more fluorine atoms of a specific structure. The liquid crystal display element contains the liquid crystal composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a liquid crystal composition and a liquid crystal display device containing the composition.

The liquid crystal display element (in the present invention, the liquid crystal display element means a general term for a liquid crystal display panel and a liquid crystal display module) uses the optical anisotropy, dielectric anisotropy, etc. of the liquid crystal composition. However, the display modes of the liquid crystal display element include PC (phase change) mode, TN (twisted nematic) mode, STN (super twisted nematic) mode, BTN (Bistable twisted nematic) mode, ECB (electrically controlled birefringence) mode, Various modes such as an OCB (optically compensated bend) mode, an IPS (in-plane switching) mode, and a VA (vertical alignment) mode are known. Among these display modes, it is known that the ECB mode, the IPS mode, the VA mode, etc. can improve the narrowness of the viewing angle, which is a drawback of the conventional display modes such as the TN mode and the STN mode. A liquid crystal composition having negative dielectric anisotropy can be used for these display mode liquid crystal display elements. Conventionally, liquid crystal compounds having 2,3-difluorophenylene contained in the liquid crystal composition having negative dielectric anisotropy have been studied (for example, Patent Documents 1 and 2). Conventionally, liquid crystal compositions having negative dielectric anisotropy that can be used in these liquid crystal display elements have also been studied (for example, Patent Documents 4, 5, and 6).

  Patent Document 3 discloses a fluorine monosubstituted liquid crystalline compound and a liquid crystal composition containing these compounds. However, in Patent Document 3, only a liquid crystal composition having a positive dielectric anisotropy is examined, and a liquid crystal composition having a negative dielectric anisotropy is not studied at all. Patent Documents 4, 5 and 6 disclose liquid crystal compositions in which a liquid crystal compound having 2,3-difluorophenylene and a fluorine-free liquid crystal compound are combined. However, since these compositions contain a fluorine-free liquid crystalline compound having no negative dielectric anisotropy, there are cases where the dielectric anisotropy cannot be increased negatively. Patent Documents 4 and 6 disclose liquid crystal compositions in which a similar fluorine monosubstituted liquid crystalline compound is combined with the first component of the present invention. However, the compositions actually disclosed in Examples and the like have a small negative dielectric anisotropy, and the minimum temperature of the nematic phase is not clarified.

  In the present specification, the “liquid crystal compound” means a generic term for a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and a compound having no liquid crystal phase but useful as a liquid crystal composition. The content ratio of the component is calculated based on the total weight of the liquid crystal compound. In this case, the liquid crystalline compound is a compound represented by the following formula (A). This compound may be optically active.

In the formula (A), R _x and R _y are each independently hydrogen, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, acyloxy, acyloxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alkenyl, alkenyloxy, alkenyloxy Alkyl, alkoxyalkenyl, alkynyl, alkynyloxy, cyano, -NCS, fluorine, or chlorine. In these groups, the carbon number is 10 or less. In the group having 1 to 5 carbon atoms, arbitrary hydrogen may be replaced with fluorine or chlorine, and the total of the replaced fluorine and chlorine is 1 to 11. In the above formula (A), ring B is 1,4-cyclohexylene, 1,4-phenylene, pyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5- Diyl, pyrimidine-2,5-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, or naphthalene-2,6-diyl. In these rings B any hydrogen is
It may be replaced with fluorine or chlorine. The sum of fluorine and chlorine replaced in ring B is 1-4. Any one or two hydrogens in 1,4-phenylene may be replaced with cyano, methyl, difluoromethyl, or trifluoromethyl. In the formula (A), Y represents a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O.
_{-, - OCH 2 -, -} CF 2 O -, - OCF 2 -, - CH = CH -, - CF = CF -, - (
_{CH 2) 4 -, - (} CH 2) 3 -O -, - O- (CH 2) 3 -, - CH = CH- (CH 2) 2 -, - (CH 2) 2 -CH = CH-, _{- (CH 2) 2 CF 2} O -, - OCF 2 (CH 2) 2 -, - (CH 2) 2 COO -, - (CH 2) 2 OCO -, - COO (CH 2) 2 -, - OCO (CH ₂ ) ₂ —, —CH═CH—COO—, —CH═CH—OC
O—, —COO—CH═CH—, or —OCO—CH═CH—. In the above formula (A), n is 1, 2, 3, or 4.
Japanese Patent No. 2811342 Japanese Patent No. 1761492 JP 7-053432 A German Patent Application Publication No. 19607043 JP 2004-532344 A (Pamphlet of International Publication No. 02/99010) JP-A-10-176167

  Even liquid crystal display elements in display modes such as IPS mode and VA mode still have problems as display elements as compared with CRTs, and improvements in physical properties are desired. The liquid crystal display element displayed in the above-described IPS mode or VA mode mainly contains a liquid crystal composition having negative dielectric anisotropy. In order to further improve the physical properties, the liquid crystal composition is used. It is preferable that a thing has the characteristic shown by (1)-(5) below. (1) Wide nematic phase temperature range, (2) Low viscosity, (3) Appropriate optical anisotropy, (4) Large absolute value of dielectric anisotropy, (5) Ratio It is preferable that the resistance is large.

  The temperature range of the nematic phase is related to the temperature range in which the liquid crystal display element is used. A liquid crystal display element containing a liquid crystal composition having a wide nematic phase temperature range as shown in (1) is a liquid crystal display element. The temperature range to be used can be expanded. The liquid crystal display element containing a liquid crystal composition having a low viscosity as in (2) can shorten the response time. When the response time of the liquid crystal display element is short, it can be suitably used for moving image display. Further, when the liquid crystal composition is injected into the liquid crystal cell of the liquid crystal display element, the injection time can be shortened and workability can be improved. The liquid crystal display element containing a liquid crystal composition with appropriate optical anisotropy as in (3) can increase the contrast ratio. A liquid crystal display element containing a liquid crystal composition having a large absolute value of dielectric anisotropy as in (4) can lower the threshold voltage and lower the drive voltage. And power consumption can be reduced. The liquid crystal display element containing a liquid crystal composition having a large specific resistance as in (5) can increase the voltage holding ratio and the contrast ratio. Accordingly, a liquid crystal composition having a large specific resistance in the initial stage and a large specific resistance even after being used for a long time is preferable.

An object of the present invention is to provide a liquid crystal composition having a wide nematic phase temperature range, a low viscosity, an appropriate optical anisotropy, a large negative dielectric anisotropy and a large specific resistance. is there. Another object of the present invention is to provide a liquid crystal composition in which the plurality of characteristics are appropriately balanced. Still another object of the present invention is to provide a liquid crystal display device containing the composition.

  The inventors of the present invention have a liquid crystal composition containing a liquid crystal compound having a specific structure in which one hydrogen is replaced with fluorine and a liquid crystal compound having a specific structure containing two or more fluorine atoms, and the temperature range of the nematic phase is wide. The inventors have found that the viscosity is small, the optical anisotropy is appropriate, the negative dielectric anisotropy is large, and the specific resistance is large, and the present invention has been completed.

That is, the present invention has the following configurations [1] to [21].
[1]: A first component that is at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-3), and formula (2-1) to formula (2-3). And a second component which is at least one compound selected from the group of compounds represented by formula (1): a liquid crystal composition having negative dielectric anisotropy.

In formulas (1-1) to (1-3) and formulas (2-1) to (2-3),
R ¹¹ and R ¹² are independently alkyl, alkenyl, or alkoxy;
Ring A ¹¹ is independently 2-fluoro-1,4-phenylene or 3-fluoro-1,4-phenylene;
Ring A ¹² is independently 1,4-cyclohexylene or 1,4-phenylene;
Ring A ¹³ is independently 1,4-cyclohexylene, or 1,4-phenylene in which any hydrogen may be replaced by fluorine or chlorine;
Z ¹¹ and Z ¹² are each independently a single bond, —C ₂ H ₄ —, —CH ₂ O—, or —OCH ₂ —.

However, in the formula (1-2), a compound in which the ring A ¹¹ is 2-fluoro-1,4-phenylene, the ring A ¹² is 1,4-phenylene, Z ¹¹ and Z ¹² are a single bond, and the formula (1 -3), a compound in which ring A ¹¹ is 3-fluoro-1,4-phenylene, ring A ¹² is 1,4-phenylene, and Z ¹¹ and Z ¹² are single bonds is excluded.

  [2]: Formula (1-1-1), Formula (1-1-2), Formula (1-2-1), Formula (1-2-2), Formula (1-2-3), and A first component that is at least one compound selected from the group of compounds represented by formula (1-3-1), formula (2-1-1), formula (2-2-1), and formula ( A liquid crystal composition having negative dielectric anisotropy, comprising a second component that is at least one compound selected from the group of compounds represented by 2-3-1.

Formula (1-1-1), Formula (1-1-2), Formula (1-2-1), Formula (1-2-2), Formula (1-2-3), Formula (1-3) -1), formula (2-1-1), formula (2-2-1), and formula (2-3-1), R _a is independently alkyl or alkenyl; R _b is independently Alkyl, alkenyl, or alkoxy;
Ring A ²¹ is independently 2-fluoro-1,4-phenylene or 3-fluoro-1,4-phenylene;
Ring A ²² is independently 1,4-cyclohexylene, or 1,4-phenylene;
Ring A ²³ is independently 1,4-cyclohexylene, or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Z ²¹ is independently —CH ₂ O— or —OCH ₂ —.

[3]: In the above formula (1-1-1), formula (1-1-2), formula (1-2-1), formula (1-2-2), and (1-2-3) A first component that is at least one compound selected from the group of compounds represented by formula (2-1-1), formula (2-2-1), and formula (2-3-1)
The liquid crystal composition according to item [2], comprising a second component which is at least one compound selected from the group of compounds represented by formula (1).

  [4]: Items [1] to [3] in which the content ratio of the first component is 10 to 80 wt% and the content ratio of the second component is 20 to 90 wt% based on the total weight of the liquid crystal compound ] The liquid crystal composition of any one of.

  [5] Any of the items [1] to [3], further comprising a third component which is at least one compound selected from the group of compounds represented by formulas (3-1) to (3-3) 2. A liquid crystal composition according to item 1.

In formulas (3-1) to (3-3), R _a is independently alkyl or alkenyl; R _b is independently alkyl, alkenyl, or alkoxy; R _c is alkyl, alkenyl, A plurality of rings A ²² are each independently 1,4-cyclohexylene or 1,4-phenylene; ring A ²³ is 1,4-cyclohexylene or any hydrogen; Is 1,4-phenylene which may be replaced by fluorine; Z ²² is independently a single bond, —CH ₂ O—, —OCH ₂ —, or —COO—.

  [6]: Based on the total weight of the liquid crystal compound, the content ratio of the first component is 5 to 75% by weight, the content ratio of the second component is 20 to 80% by weight, and the content ratio of the third component Item 5. The liquid crystal composition according to item [5], wherein is 5 to 45% by weight.

  [7]: Formula (1-1-1-1), Formula (1-1-1-2), Formula (1-1-2-1), Formula (1-1-2-2), Formula ( 1-2-1-1), Formula (1-2-1-2), Formula (1-2-2-1), Formula (1-2-3-1), and Formula (1-2-3) -2), a first component which is at least one compound selected from the group of compounds represented by formula (2-1-1-1), formula (2-2-1-1), formula (2- 2-1-2), selected from the compound group represented by formula (2-2-1-3), formula (2-2-1-4), and formula (2-2-1-5) A liquid crystal composition having negative dielectric anisotropy, comprising a second component which is at least one compound.

Formula (1-1-1-1), Formula (1-1-1-2), Formula (1-1-2-1), Formula (1-1-2-2), Formula (1-2) 1-1), Formula (1-2-1-2), Formula (1-2-2-1), Formula (1-2-3-1), Formula (1-2-3-2), Formula (2-1-1-1), Formula (2-2-1-1), Formula (2-2-1-2), Formula (2-2-1-3), Formula (2-2-1) -4), and formula (2-2-1-5), R _a is independently alkyl or alkenyl; R _b is independently alkyl, alkenyl, or alkoxy.

  [8]: In the above formula (1-1-1-1), formula (1-1-2-1), formula (1-2-1-1), and formula (1-2-3-1) A first component which is at least one compound selected from the group of compounds represented, the formula (2-1-1-1), and the formula (2-2-1-1) to the formula (2-2-2) The liquid crystal composition according to item [7], comprising a second component which is at least one compound selected from the group of compounds represented by 1-5).

  [9]: Formula (1-1-1-1), Formula (1-1-1-2), Formula (1-2-1-1), Formula (1-2-1-2), and A first component which is at least one compound selected from the group of compounds represented by formula (1-2-2-1), the above formula (2-1-1-1), and formula (2-2-2) 1-1) The liquid crystal composition according to item [7], comprising a second component that is at least one compound selected from the group of compounds represented by formula (2-2-1-5).

  [10]: In the above formula (1-1-1-1), formula (1-1-2-1), formula (1-2-1-1), and formula (1-2-3-1) A first component that is at least one compound selected from the group of compounds represented by formula (2-1-1-1), formula (2-2-1-1), and formula (2-2-2) Item 2. The liquid crystal composition according to item [7], comprising a second component that is at least one compound selected from the group of compounds represented by 1-2).

  [11]: In the above formula (1-1-2-1), formula (1-1-2-2), formula (1-2-3-1), and formula (1-2-3-2) A first component that is at least one compound selected from the group of compounds represented by formula (2-1-1-1), formula (2-2-1-1), and formula (2-2-2) Item 2. The liquid crystal composition according to item [7], comprising a second component that is at least one compound selected from the group of compounds represented by 1-2).

  [12]: a first component that is at least one compound selected from the group of compounds represented by formula (1-1-2-1) and formula (1-2-3-1); A second compound which is at least one compound selected from the group of compounds represented by (2-1-1-1), formula (2-2-1-1), and formula (2-2-1-2) Item 7. The liquid crystal composition according to item [7] containing the component.

  [13]: Items [7] to [12] in which the content ratio of the first component is 30 to 75% by weight and the content ratio of the second component is 25 to 70% by weight based on the total weight of the liquid crystal compound. ] The liquid crystal composition of any one of.

  [14]: In formula (3-1-1), formula (3-1-2), formula (3-2-1), formula (3-3-1), and formula (3-3-2) Item 6. The liquid crystal composition according to any one of items [7] to [12], further containing a third component which is at least one compound selected from the group of compounds represented.

In Formula (3-1-1), Formula (3-1-2), Formula (3-2-1), Formula (3-3-1), and Formula (3-3-2), R _a is _Rb is independently alkyl, alkenyl, or alkoxy; _Rc is independently alkyl, alkenyl, alkoxy, or alkoxymethyl.

  [15]: At least one selected from the group of compounds represented by the above formula (3-1-1), formula (3-1-2), and formula (3-2-1) as the third component The liquid crystal composition according to item [14], which is a compound.

[16] The liquid crystal composition according to item [14], wherein the third component is at least one compound selected from the group of compounds represented by formula (3-2-1).
[17]: Based on the total weight of the liquid crystal compound, the content ratio of the first component is 10 to 65 wt%, the content ratio of the second component is 25 to 60 wt%, and the content ratio of the third component Item 24. The liquid crystal composition according to any one of items [14] to [16], wherein the ratio is 5 to 35% by weight.

  [18]: The liquid crystal compound component is the above formula (1-1-1), formula (1-1-2), formula (1-2-1), formula (1-2-2), formula (1) -2-3) and a first component that is at least one compound selected from the group of compounds represented by formula (1-3-1), the above formula (2-1-1), and formula (2- 2-1) and a second component which is at least one compound selected from the group of compounds represented by formula (2-3-1), and the above formula (3-1) to formula (3-3) A liquid crystal composition having negative dielectric anisotropy, comprising only a third component which is at least one compound selected from the group of compounds represented.

  [19]: The liquid crystal compound component is the above formula (1-1-1), formula (1-1-2), formula (1-2-1), formula (1-2-2), formula (1) -2-3) and a first component that is at least one compound selected from the group of compounds represented by formula (1-3-1), the above formula (2-1-1), and formula (2- 2-1), and a liquid crystal composition having negative dielectric anisotropy, comprising only a second component that is at least one compound selected from the group of compounds represented by formula (2-3-1) .

[20] The liquid crystal composition according to any one of items [1] to [19], wherein the value of dielectric anisotropy is in the range of −6.5 to −2.0.
[21]: The liquid crystal composition according to any one of items [1] to [20], wherein the value of optical anisotropy is in the range of 0.080 to 0.120.

[22] A liquid crystal display device comprising the liquid crystal composition according to any one of items [1] to [21].
[23] The liquid crystal display element according to item [22], which is displayed in a VA mode or an IPS mode and driven by an active matrix method.

  The liquid crystal composition of the present invention has a wide nematic phase temperature range, a low viscosity, suitable optical anisotropy, a large negative dielectric anisotropy, and a large specific resistance. Moreover, the said composition is excellent also in the balance of these characteristics. In particular, the liquid crystal composition of the present invention can have an optical anisotropy in the range of 0.080 to 0.120 and a dielectric anisotropy in the range of -6.5 to -2.0. The liquid crystal display element of the present invention contains the above liquid crystal composition and has a high voltage holding ratio. Further, this liquid crystal display element can be suitably used as a liquid crystal display element (hereinafter also referred to as “AM element”) that is displayed in a VA mode, an IPS mode, or the like and is driven by an active matrix (AM) method.

  The liquid crystal composition of the present invention includes a first component that is a liquid crystal compound having a specific structure in which one hydrogen is replaced by fluorine, a second component that is a liquid crystal compound having a specific structure containing two or more fluorine atoms, and And a third component which is a liquid crystal compound having a specific structure.

Hereinafter, for each component, the structure of the compound used for the component, the characteristics and effects of the component, specific examples and preferred embodiments will be described.
[First component]
The first component of the liquid crystal composition of the present invention is at least one liquid crystal compound containing one fluorine represented by the following formulas (1-1) to (1-3).

In the above formulas (1-1) to (1-3), R ¹¹ , R ¹² , ring A ¹¹ , rings A ¹² , Z ¹¹ , and Z ¹² are independently defined as follows.
R ¹¹ and R ¹² are independently alkyl, alkenyl, or alkoxy.

  Among the alkyls, alkyls having 1 to 20 carbon atoms are preferable, alkyls having 1 to 10 carbon atoms are more preferable, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl are more preferable, ethyl, Propyl, butyl, pentyl, and heptyl are particularly preferred.

  Among the alkenyls, alkenyl having 2 to 20 carbon atoms is preferable, alkenyl having 2 to 10 carbon atoms is more preferable, 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, and 5-hexenyl are more preferable, vinyl, 1-propenyl, 3-butenyl, And 3-pentenyl are particularly preferred.

When R ¹¹ or R ¹² is the above alkenyl, the preferred configuration of —CH═CH— in these alkenyls depends on the position of the double bond. R ¹¹ or R ¹² is an odd number of carbon positions where a double bond such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl, or 5-hexenyl begins. In some cases, the trans configuration is preferred. When R ¹¹ or R ¹² is an even number in the position number of the carbon at which a double bond such as 2-propenyl, 2-butenyl, 2-pentenyl, 4-pentenyl, 2-hexenyl, 4-hexenyl and the like begins, is a cis configuration Is preferred.

  Among the above alkoxys, alkoxy having 1 to 20 carbon atoms is preferable, alkoxy having 1 to 10 carbon atoms is more preferable, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and heptyloxy are further preferable, and methoxy , Ethoxy, and butoxy are particularly preferred.

Ring A ¹¹ is independently 2-fluoro-1,4-phenylene or 3-fluoro-1,4-phenylene, and Ring A ¹² is independently 1,4-cyclohexylene or 1,4-phenylene. . Z ¹¹ and Z ¹² are each independently a single bond, —C ₂ H ₄ —, —CH ₂ O—, or —OCH ₂ —. In addition, when the ring contained in the compounds represented by the above formulas (1-1) to (1-3) is 1,4-cyclohexylene, the steric configuration is preferably a trans configuration. .

However, in the formula (1-2), a compound in which the ring A ¹¹ is 2-fluoro-1,4-phenylene, the ring A ¹² is 1,4-phenylene, Z ¹¹ and Z ¹² are a single bond, and the formula (1 -3), a compound in which ring A ¹¹ is 3-fluoro-1,4-phenylene, ring A ¹² is 1,4-phenylene, and Z ¹¹ and Z ¹² are single bonds is excluded.

  The compounds represented by the above formulas (1-1) to (1-3) contain only one fluorine, and the fluorine-containing group is 2-fluoro-1,4-phenylene or 3-fluoro- It is characterized by being 1,4-phenylene. When the liquid crystal compound as the first component has such a structure, in the liquid crystal composition according to the present invention, the negative dielectric anisotropy can be increased and the minimum temperature of the nematic phase can be decreased. it can.

  Among the compounds represented by these formulas (1-1) to (1-3), the following formula (1-1-1), formula (1-1-2), formula (1-2-1) to Compounds represented by formula (1-2-3) and formula (1-3-1) are preferred.

The above formula (1-1-1), formula (1-1-2), formula (1-2-1), formula (1-2-2), formula (1-2-3), and formula (1) In 3-1), each of R _a , R _b , ring A ²¹ , ring A ²² , and Z ²¹ is independently defined as follows.

R _a is alkyl or alkenyl. Preferred embodiments of alkyl and alkenyl are the same as those for R ¹¹ . R _b is alkyl, alkenyl, or alkoxy. Alkyl, alkenyl, and preferred features of the alkoxy is the same as in the case of R ^11.

Ring A ²¹ is 2-fluoro-1,4-phenylene or 3-fluoro-1,4-phenylene. Ring A ²² is 1,4-cyclohexylene or 1,4-phenylene.

Z ²¹ is —CH ₂ O— or —OCH ₂ —.
When the liquid crystalline compound as the first component is a compound represented by the above formula, the dielectric anisotropy of the liquid crystal composition can be further increased negatively, and the minimum temperature of the nematic phase can be reduced. Can be lowered.

  Among these compounds, the liquid crystalline compounds represented by the above formulas (1-1-1) and (1-1-2) have a higher upper limit temperature of the nematic phase compared to general liquid crystalline compounds. Although there is no medium, the viscosity is medium, the optical anisotropy is medium, the negative dielectric anisotropy is medium, and the specific resistance is large.

  Among these compounds, the liquid crystalline compounds represented by the above formulas (1-2-1) and (1-2-2) have a higher maximum temperature of the nematic phase as compared with general liquid crystalline compounds, The viscosity is medium, the optical anisotropy is medium to large, the negative dielectric anisotropy is medium, and the specific resistance is large.

  Among these compounds, the liquid crystalline compound represented by the above formula (1-2-3) has a higher upper limit temperature of the nematic phase and a medium to large viscosity as compared with a general liquid crystalline compound. The anisotropy is medium, the negative dielectric anisotropy is medium, and the specific resistance is large.

  Among these compounds, the liquid crystalline compound represented by the above formula (1-3-1) has a higher upper limit temperature of the nematic phase and a medium to large viscosity as compared with a general liquid crystalline compound. The anisotropy is moderate to large, the negative dielectric anisotropy is medium, and the specific resistance is large.

  It is represented by the above formula (1-1-1), formula (1-1-2), formula (1-2-1) to formula (1-2-3), and formula (1-3-1). Among the compounds, compounds represented by formula (1-1-1), formula (1-1-2), and formula (1-2-1) to formula (1-2-3) are preferable.

  When the liquid crystalline compound as the first component is a compound represented by the above formula, the temperature range of the nematic phase can be adjusted widely, and the dielectric anisotropy of the liquid crystal composition should be negatively increased. Can do.

  Moreover, it is represented by the above formula (1-1-1), formula (1-1-2), formula (1-2-1) to formula (1-2-3), and formula (1-3-1). Among the compounds to be prepared, the following formula (1-1-1-1), formula (1-1-1-2), formula (1-1-2-1), formula (1-1-2-2) , Formula (1-2-1-1), Formula (1-2-1-2), Formula (1-2-2-1), Formula (1-2-3-1), and Formula (1- The compound represented by 2-3-2) is more preferable.

Formula (1-1-1-1), Formula (1-1-1-2), Formula (1-1-2-1), Formula (1-1-2-2), Formula (1-2) -1-1), formula (1-2-1-2), formula (1-2-2-1), formula (1-2-3-1), and formula (1-2-3-2) In the formula, R _a is independently alkyl or alkenyl, and preferred embodiments of these alkyl and alkenyl are the same as those for R ¹¹ . R _b is independently alkyl, alkenyl, or alkoxy, and preferred embodiments of these alkyl, alkenyl, and alkoxy are the same as those for R ¹¹ .

  When the liquid crystalline compound as the first component is a compound represented by the above formula, the dielectric anisotropy of the liquid crystal composition can be negatively increased. Further, the temperature range of the nematic phase can be easily changed by changing the content ratio of the first component with respect to the total weight of the liquid crystal compound.

Among these compounds, the above formula (1-1-1-1), formula (1-1-2-1), formula (1-2)
-1-1) and a liquid crystal compound represented by formula (1-2-3-1) are preferable, and in the above formula (1-1-2-1) and formula (1-2-3-1) The liquid crystalline compound represented is more preferable. When the first component is the above compound, in particular, the dielectric anisotropy of the liquid crystal composition can be increased more negatively.

  Among these compounds, the above formula (1-1-1-1), formula (1-1-1-2), formula (1-2-1-1), formula (1-2-1-2), and In the case of the liquid crystal compound represented by the formula (1-2-2-1), the viscosity of the liquid crystal composition can be further reduced.

These liquid crystalline compounds may be used alone or in combination as a first component.
[Second component]
The second component of the liquid crystal composition of the present invention is at least one liquid crystal compound represented by the following formulas (2-1) to (2-3).

In the above formulas (2-1) to (2-3), R ¹¹ , R ¹² , and ring A ¹² are represented by formulas (1-1) to (1-3) that are the first component. The same as in the case of the compound. In the above formulas (2-1) to (2-3), the ring A ¹³ is 1,4-cyclohexylene, or 1,4-phenylene in which arbitrary hydrogen may be replaced by fluorine or chlorine.

  The compounds represented by the above formulas (2-1) to (2-3) contain two or more fluorine atoms, and have at least one 2,3-difluoro-1,4-phenylene as the fluorine-containing group. There is a special feature. When the liquid crystal compound as the second component has such a structure, in the liquid crystal composition according to the present invention, the dielectric anisotropy of the liquid crystal composition can be negatively increased.

  Among the compounds represented by these formulas (2-1) to (2-3), the following formulas (2-1-1), (2-2-1), and (2-3-1) The compound represented by these is preferable.

In the above formula (2-1-1), formula (2-2-1), and formula (2-3-1), R _a ,
R _b and ring A ²² are the above-mentioned first component of formula (1-1-1), formula (1-1-2), formula (1-2)
-1) to the formula (1-2-3) and the compounds represented by the formula (1-3-1). In the above formula (2-1-1), formula (2-2-1), and formula (2-3-1), ring A ²³ is 1,4-cyclohexylene, or any hydrogen is replaced by fluorine 1,4-phenylene.

When the liquid crystalline compound as the second component is a compound represented by the above formula, the dielectric anisotropy of the liquid crystal composition can be negatively increased.
Among these compounds, the liquid crystalline compound represented by the above formula (2-1-1) has a medium viscosity although the upper limit temperature of the nematic phase is not necessarily high as compared with a general liquid crystalline compound. The optical anisotropy is moderate to relatively large, the negative dielectric anisotropy is moderate to relatively large, and the specific resistance is large.

  Among these compounds, the liquid crystalline compound represented by the above formula (2-2-1) has an upper limit temperature of a nematic phase that is moderate to high and a viscosity that is moderate to large compared to a general liquid crystalline compound. The optical anisotropy is moderate to large, the negative dielectric anisotropy is large, and the specific resistance is large.

  Among these compounds, the liquid crystalline compound represented by the above formula (2-3-1) has a medium to high upper limit temperature of the nematic phase and a medium to large viscosity compared to a general liquid crystalline compound. The optical anisotropy is moderate to large, the negative dielectric anisotropy is large, and the specific resistance is large.

  Among the compounds represented by the above formula (2-1-1), formula (2-2-1), and formula (2-3-1), the following formula (2-1-1-1), formula ( 2-2-1), formula (2-2-1-2), formula (2-2-1-3), formula (2-2-1-4), and formula (2-2-1) The compound represented by -5) is preferred.

The above formula (2-1-1-1), formula (2-2-1-1), formula (2-2-1-2), formula (2-2-1-3), formula (2-2) In the formula (1-1-4) and the formula (2-2-1-5), R _a is independently alkyl or alkenyl. With regard to preferred embodiments of these alkyls and alkenyls, ) To R ^{11 in} the compound represented by formula (1-3). R _b is independently alkyl, alkenyl, or alkoxy, and preferred embodiments of these alkyl, alkenyl, and alkoxy are the same as those for R ¹¹ above.

  When the liquid crystalline compound as the second component is a compound represented by the above formula, the dielectric anisotropy of the liquid crystal composition can be increased negatively. Moreover, optical anisotropy can be easily changed by changing the content rate of the 2nd component with respect to the liquid crystal compound total weight.

  Among these compounds, compounds represented by the above formula (2-1-1-1), formula (2-2-1-1), and formula (2-2-1-2) are preferable. When the second component is the above compound, the upper limit temperature of the nematic phase of the liquid crystal composition can be increased, and the dielectric anisotropy can be increased negatively. Moreover, optical anisotropy can be easily changed by changing the content rate of the 2nd component with respect to the liquid crystal compound total weight. Compared to other second components, compounds represented by formula (2-2-1-3), formula (2-2-1-4), formula (2-2-1-5) and the like. The viscosity can be further reduced.

These liquid crystalline compounds may be used alone or in combination as the second component.
[Third component]
The liquid crystal composition of the present invention further contains a third component, which is at least one liquid crystal compound represented by the following formulas (3-1) to (3-3), if necessary.

In the above formulas (3-1) to (3-3), R _a is independently alkyl or alkenyl. With regard to preferred embodiments of these alkyls and alkenyls, the first component formula (1-1) to The same as in the case of R ^{11 in} the compound represented by the formula (1-3). R _b is independently alkyl, alkenyl, or alkoxy, and preferred embodiments of these alkyl, alkenyl, and alkoxy are the same as those for R ¹¹ above.

In the above formulas (3-1) to (3-3), R _c is alkyl, alkenyl, alkoxy, or alkoxymethyl. Preferred embodiments of these alkyl, alkenyl and alkoxy are the same as those for R ¹¹ above. Among these alkoxymethyl, alkoxymethyl having 2 to 20 carbon atoms is preferable, alkoxymethyl having 2 to 10 carbon atoms is more preferable, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, and pentyloxymethyl are further preferable, and methoxy Methyl is particularly preferred.

In the above formulas (3-1) to (3-3), Z ²² is a single bond, —CH ₂ O—, —OCH ₂ —, or —COO—.
In the above formulas (3-1) to (3-3), the plurality of rings A ²² are each independently 1,4-cyclohexylene or 1,4-phenylene, and the ring A ²³ is 1,4- Cyclohexylene or 1,4-phenylene in which any hydrogen may be replaced by fluorine.

  When the liquid crystalline compound as the third component has such a structure, the viscosity of the liquid crystal composition according to the present invention can be reduced. Further, by changing the content ratio of the third component with respect to the total weight of the liquid crystal compound, the upper limit temperature of the nematic phase can be easily changed, and the optical anisotropy can be easily changed.

  Among these compounds, the liquid crystal compound represented by the above formula (3-1) has a lower viscosity and lower optical anisotropy than the general liquid crystal compound, although the upper limit temperature of the nematic phase is not so high. Is small to medium, has a very small negative dielectric anisotropy, and has a large specific resistance.

  Among these compounds, the liquid crystalline compound represented by the above formula (3-2) has a moderate upper limit temperature of the nematic phase, a low viscosity, and an optical anisotropy as compared with a general liquid crystalline compound. It is moderate, has a very low negative dielectric anisotropy, and is characterized by a large specific resistance.

  Among these compounds, the liquid crystalline compound represented by the above formula (3-3) has an extremely high upper limit temperature of the nematic phase, a medium viscosity, and an optical anisotropy as compared with a general liquid crystalline compound. Is moderate to large, has a small negative dielectric anisotropy, and has a large specific resistance.

  Among the compounds represented by the above formula (3-1) to formula (3-3), the following formula (3-1-1), formula (3-1-2), formula (3-2-1), Compounds represented by formula (3-3-1) and formula (3-3-2) are preferable.

R _a , R _b , and R _c are the same as in the case of the compounds represented by the above (3-1) to formula (3-3).
When the liquid crystal compound as the third component is a compound represented by the above formula, the viscosity of the liquid crystal composition can be further reduced.

  Among these compounds, compounds represented by the above formula (3-1-1), formula (3-1-2), and formula (3-2-1) are preferable, and in the above formula (3-2-1) The compounds represented are more preferred. When the third component is the above compound, the viscosity of the liquid crystal composition can be further reduced.

These liquid crystalline compounds may be used alone or in combination as a third component.
[Synthesis Method of Liquid Crystalline Compound]
Hereinafter, a method for synthesizing a liquid crystal compound used in the liquid crystal composition according to the present invention will be exemplified.

  Formula (2-1) represented by the above formula (2-1-1-1), and compounds represented by formula (2-2-1-1) to formula (2-2-1-5) and The compound represented by the formula (2-2) can be synthesized based on the method described in Japanese Patent No. 2811342.

Further, the compound represented by the formula (3-1) represented by the compound represented by the above formula (3-1-1) or the like is disclosed in JP-A-59-70624 or JP-A-60-16940. It can synthesize | combine based on the method described in gazette.

For compounds that cannot be synthesized only from the above documents, Organic Synthesis (John Wiley & Sons, Inc), Organic Reactions (Organic Reactions, John Wiley & Sons, Inc), Comprehensive Organic Synthesis can be performed based on methods described in synthesis (Comprehensive Organic Synthesis, Pergamon Press), new experimental chemistry course (Maruzen), and the like.

[Liquid crystal composition (1)]
Hereinafter, the combination of each component of a composition and the preferable ratio of each component are demonstrated.
The liquid crystal composition of the present invention is characterized by combining the first component and the second component (hereinafter also referred to as “liquid crystal composition (1)”).

  By combining these two components, the dielectric anisotropy of the composition can be increased negatively, and the lower limit temperature of the nematic phase can be decreased. Compared to a liquid crystal composition in which the liquid crystal compound is composed of only the second component and the third component, the liquid crystal composition in which the third component is replaced with the first component while the content ratio of the second component remains the same, the dielectric constant Anisotropy can be increased negatively. In addition, a liquid crystal composition in which the liquid crystal compound is composed only of the second component and the third component may not be able to negatively increase the dielectric anisotropy of the composition while keeping the minimum temperature of the nematic phase low.

  The content ratio of the first component and the second component of the liquid crystal composition (1) according to the present invention is not particularly limited, but the first component is based on the total weight of the liquid crystal compound in the liquid crystal composition (1). The content of the component is 10 to 80% by weight, the content of the second component is preferably 20 to 90% by weight, the content of the first component is 30 to 75% by weight, The content ratio is more preferably 25 to 70% by weight.

  When the content ratio of the first component and the second component is in the above range, the temperature range of the nematic phase of the liquid crystal composition is widened to an appropriate optical anisotropy, and an appropriate range of dielectric anisotropy is achieved. Having a small viscosity and a large specific resistance.

[Liquid crystal composition (2)]
In the liquid crystal composition according to the present invention, a combination of the third component in addition to the first component and the second component is also preferable (hereinafter also referred to as “liquid crystal composition (2)”). By using such a combination, the dielectric anisotropy of the composition can be negatively increased, and the temperature range of the nematic phase can be widened. The content ratio of the first component, the second component, and the third component of the liquid crystal composition (2) according to the present invention is not particularly limited, but the content ratio of the first component is based on the total weight of the liquid crystal compound. Is preferably in the range of 5 to 75% by weight, the content of the second component is in the range of 20 to 80% by weight, and the content of the third component is preferably in the range of 5 to 45% by weight. Is more preferably in the range of 10 to 65% by weight, the content of the second component in the range of 25 to 60% by weight, and the content of the third component in the range of 5 to 35% by weight.

  When the content ratios of the first component, the second component, and the third component of the liquid crystal composition (2) are in the above ranges, the temperature range of the nematic phase of the liquid crystal composition is expanded and appropriate optical anisotropy is achieved. And having an appropriate range of dielectric anisotropy, decreasing the viscosity, and further increasing the specific resistance.

[Mode of liquid crystal composition, etc.]
In the liquid crystal composition according to the present invention, in addition to the first component, the second component, and the liquid crystalline compound that is a third component added as necessary, for example, for the purpose of adjusting the characteristics of the liquid crystal composition, Other liquid crystal compounds may be added and used. Further, for example, from the viewpoint of cost, in the liquid crystal composition of the present invention, the liquid crystal compound other than the liquid crystal compound which is the first component, the second component, and the third component to be added as necessary is not added. Sometimes used.

Moreover, you may add additives, such as an optically active compound, a pigment | dye, an antifoamer, a ultraviolet absorber, antioxidant, to the liquid-crystal composition based on this invention.
When an optically active compound is added to the liquid crystal composition according to the present invention, a helical structure can be induced in the liquid crystal to give a twist angle.

When a dye is added to the liquid crystal composition according to the present invention, the liquid crystal composition can be applied to a liquid crystal display element that is displayed in a GH (Guest host) mode.
When an antifoaming agent is added to the liquid crystal composition according to the present invention, it is possible to suppress foaming from the liquid crystal composition during transportation of the liquid crystal composition or during the manufacturing process of the liquid crystal display element. Become.

  When an ultraviolet absorber or an antioxidant is added to the liquid crystal composition according to the present invention, it becomes possible to prevent deterioration of the liquid crystal composition and the liquid crystal display device containing the liquid crystal composition. For example, the antioxidant can suppress a decrease in specific resistance when the liquid crystal composition is heated.

Examples of the ultraviolet absorber include benzophenone ultraviolet absorbers, benzoate ultraviolet absorbers, and triazole ultraviolet absorbers.
A specific example of the benzophenone ultraviolet absorber is 2-hydroxy-4-octoxybenzophenone.

Specific examples of the benzoate UV absorber include 2,4-di-t-butylphenyl-3,5-
Di-t-butyl-4-hydroxybenzoate.
Specific examples of the triazole ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydroxyphthalimide-methyl)- 5-methylphenyl] benzotriazole, and 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole.

Examples of the antioxidant include phenol-based antioxidants and organic sulfur-based antioxidants.
Specific examples of the phenolic antioxidant include 3,5-di-tert-butyl-4-hydroxytoluene, 2,2′-methylenebis (6-tert-butyl-4-methylphenol), 4,4′-butylidenebis ( 6-t-butyl-3-methylphenol), 2,6-di-t-butyl-4- (2-octadecyloxycarbonyl) ethylphenol, and pentaerythritol tetrakis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate]
It is.

Specific examples of the organic sulfur antioxidant include dilauryl-3,3′-thiopropionate, dimyristyl-3,3′-thiopropionate, distearyl-3,3′-thiopropionate, pentaerythritol. Tetrakis (3-lauryl thiopropionate) and 2-mercaptobenzimidazole.

The above-mentioned additives typified by ultraviolet absorbers, antioxidants and the like can be used by adding an amount in a range that does not impair the object of the present invention and can achieve the object of adding the additive. For example, when the ultraviolet absorber is added, the addition ratio is usually in the range of 100 ppm to 1000000 ppm, preferably 100 to 100, based on the total weight of the liquid crystal compound.
An amount in the range of 00 ppm, more preferably an amount in the range of 1000-10000 ppm. For example, when the above antioxidant is added, the addition ratio is usually in the range of 10 ppm to 500 ppm, preferably in the range of 30 to 300 ppm, more preferably, based on the total weight of the liquid crystal compound. An amount in the range of 40-200 ppm.

  The liquid crystal composition according to the present invention includes impurities such as synthesis raw materials, by-products, reaction solvents, and synthesis catalysts mixed in the synthesis process of each compound constituting the liquid crystal composition, the liquid crystal composition preparation process, and the like. In some cases.

[Method for producing liquid crystal composition]
In the liquid crystal composition according to the present invention, for example, when each compound as a component is a liquid, by mixing and shaking each compound, and when containing a solid, each compound is mixed, It can be prepared by shaking each other by heating and then shaking. The liquid crystal composition according to the present invention can be prepared by other known methods.

[Characteristics of liquid crystal composition]
The liquid crystal composition according to the present invention usually has an optical anisotropy in the range of 0.080 to 0.120. In the liquid crystal composition according to the present invention, the optical anisotropy can be set in the range of 0.050 to 0.180 and in the range of 0.050 to 0.200 by appropriately adjusting the composition and the like.

  In the liquid crystal composition according to the present invention, the dielectric anisotropy is usually in the range of -6.5 to -2.0, preferably the dielectric anisotropy in the range of -5.0 to -2.5. A liquid crystal composition having properties can be obtained. The liquid crystal composition in the above numerical range can be suitably used as a liquid crystal display element displayed in the IPS mode and the VA mode.

In the liquid crystal composition according to the present invention, a liquid crystal composition having both the optical anisotropy in the above numerical range and the dielectric anisotropy in the above numerical range can be usually obtained.
Further, in order to maximize the contrast ratio of the liquid crystal display element displayed in the VA mode and the IPS mode, the product value of the optical anisotropy (Δn) of the liquid crystal composition and the cell gap (d) of the liquid crystal display element. Design so that (Δn · d) is a constant value. In the VA mode, this value (Δn · d) is preferably in the range of 0.30 to 0.35 μm, for example, and in the IPS mode, it is preferably in the range of 0.20 to 0.30 μm, for example. Since the cell gap (d) is usually 3 to 6 μm, the optical anisotropy of the liquid crystal composition is preferably in the range of 0.05 to 0.11, for example, in order to maximize the contrast ratio. . When the cell gap (d) is 3 μm or less, the optical anisotropy of the liquid crystal composition is preferably larger than the range of 0.10 to 0.11.

[Liquid crystal display element]
The liquid crystal composition according to the present invention can be used for a liquid crystal display element. The liquid crystal display element according to the present invention may be driven by any of AM mode and passive matrix (PM) mode, and any of PC mode, TN mode, STN mode, OCB mode, VA mode, IPS mode, etc. It may be displayed in the display mode. The liquid crystal display element driven by the AM method and the PM method can be applied to any liquid crystal display such as a reflective type, a transmissive type, and a transflective type.

The liquid crystal composition according to the present invention includes a DS (dynamic scattering) mode element using a liquid crystal composition to which a conductive agent is added, and an NCAP (nematic curvilinear aligned phase) element manufactured by microencapsulating the liquid crystal composition. It can also be used for PD (polymer dispersed) elements in which a three-dimensional network polymer is formed in a liquid crystal composition, for example, PN (polymer network) elements.

  Since the liquid crystal composition according to the present invention has the above-described characteristics, it is particularly suitable for an AM liquid crystal display element that displays in a display mode using negative dielectric anisotropy, for example, a VA mode, an IPS mode, or the like. In particular, it can be suitably used for an AM liquid crystal display element that displays in the VA mode.

In a liquid crystal display element that displays in TN mode, VA mode, or the like, the direction of the electric field is perpendicular to the liquid crystal layer. On the other hand, in the liquid crystal display element that displays in the IPS mode or the like, the direction of the electric field is parallel to the liquid crystal layer. The structure of the liquid crystal display element that displays in the VA mode is reported in K. Ohmuro, S. Kataoka, T. Sasaki and Y. Koike, SID '97 Digest of Technical Papers, 28, 845 (1997). The structure of the liquid crystal display element to be displayed is reported in International Publication No. 91/10936 pamphlet (family: US55768867).

〔Example〕
Hereinafter, the liquid crystal composition obtained by the present invention will be described in detail with reference to examples. The liquid crystalline compounds used in the examples are represented by symbols based on the definitions in Table 1 below. In Table 1, the configuration of 1,4-cyclohexylene is a trans configuration. The ratio (percentage) of each compound is a weight percentage (% by weight) based on the total weight of the liquid crystal compound unless otherwise specified. The characteristic values of the liquid crystal composition obtained at the end of each example are shown.

  In addition, the number described in the portion of the liquid crystal compound used in each example corresponds to the formula number indicating the liquid crystal compound used for the first to third components of the present invention described above. When it is simply described as “-” without description, it means that this compound is another liquid crystal compound that does not correspond to these components.

  The notation method by the symbol of a compound is shown below.

  The characteristic values were measured according to the following method. Many of these measurement methods are the methods described in the Standard of Electric Industries Association of Japan EIAJ / ED-2521A or a modified method thereof.

(1) Maximum temperature of nematic phase (NI; ° C)
A sample was placed on a hot plate of a melting point measurement apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when a part of the sample changed from a nematic phase to an isotropic liquid. Hereinafter, the upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”.

(2) Minimum temperature of nematic phase (Tc; ° C)
A sample having a nematic phase was put in a glass bottle and stored in a freezer at 0 ° C., −10 ° C., −20 ° C., −30 ° C., and −40 ° C. for 10 days, and then the liquid crystal phase was observed. For example, when the sample remained in a nematic phase at −20 ° C. and changed to a crystal or smectic phase at −30 ° C., Tc was described as ≦ −20 ° C. Hereinafter, the lower limit temperature of the nematic phase may be abbreviated as “lower limit temperature”.

(3) Optical anisotropy (Δn; measured at 25 ° C.)
Measurement was performed using an Abbe refractometer with a polarizing plate attached to the eyepiece using light having a wavelength of 589 nm. First, after rubbing the surface of the main prism in one direction, the sample was dropped on the main prism. Then, the refractive index (n‖) when the polarization direction was parallel to the rubbing direction and the refractive index (n⊥) when the polarization direction was perpendicular to the rubbing direction were measured. The value of optical anisotropy (Δn) is
(Δn) = (n∥) − (n∥)
It was calculated from the formula of

(4) Viscosity (η; measured at 20 ° C .; mPa · s)
An E-type viscometer was used for the measurement.
(5) Dielectric anisotropy (Δε; measured at 25 ° C.)
An ethanol (20 ml) solution of octadecyltriethoxysilane (0.16 ml) was applied to a well-cleaned glass substrate. The glass substrate was rotated with a spinner and then heated at 150 ° C. for 1 hour. A VA device having an interval (cell gap) of 20 μm was assembled from two glass substrates.

  In the same manner, a polyimide alignment film was prepared on a glass substrate. After the alignment film of the obtained glass substrate was rubbed, a TN device in which the distance between the two glass substrates was 9 μm and the twist angle was 80 degrees was assembled.

A sample (liquid crystal composition) was put into the obtained VA device, 0.5 V (1 kHz, sine wave) was applied, and the dielectric constant (ε‖) in the major axis direction of liquid crystal molecules was measured.
A sample (liquid crystal composition) was put into the obtained TN device, 0.5 V (1 kHz, sine wave) was applied, and the dielectric constant (ε に お け る) in the minor axis direction of the liquid crystal molecules was measured.

The value of dielectric anisotropy was calculated from the equation (Δε) = (ε‖) − (ε⊥).
A composition having a negative value is a composition having a negative dielectric anisotropy.
(6) Voltage holding ratio (VHR; measured at 25 ° C. and 100 ° C .;%)
A sample was put in a cell having a polyimide alignment film and a distance (cell gap) between two glass substrates of 6 μm to produce a TN device. At 25 ° C., the TN device was charged by applying a pulse voltage (5 V, 60 microseconds). The waveform of the voltage applied to the TN device was observed with a cathode ray oscilloscope, and the area between the voltage curve and the horizontal axis in a unit cycle (16.7 milliseconds) was determined. The area was similarly determined from the waveform of the voltage applied after removing the TN element. The value of voltage holding ratio (%) is
(Voltage holding ratio) = (Area value when TN element is present) / (Area value when TN element is not present) × 100
It was calculated from the formula of

The voltage holding ratio thus obtained is indicated as “VHR-1”. Next, this TN device was heated at 100 ° C. for 250 hours. After returning the TN device to 25 ° C., the voltage holding ratio was measured by the same method as described above. The voltage holding ratio obtained after this heating test was shown as “VHR-2”. This heating test is an accelerated test and is a test corresponding to a long-term durability test of the TN device.

(7) Gas chromatographic analysis The measuring apparatus used was a GC-14B gas chromatograph manufactured by Shimadzu Corporation or an equivalent measuring instrument. The column used was a capillary column CBP1-M25-025 (length 25 m, inner diameter 0.22 mm, film thickness 0.25 μm; fixed liquid phase was dimethylpolysiloxane; nonpolar) manufactured by Shimadzu Corporation. Helium was used as the carrier gas, and the flow rate was adjusted to 2 ml / min. The column was held at 200 ° C. for 2 minutes and then heated to 280 ° C. at a rate of 5 ° C./min. The temperature of the sample vaporizing chamber was set to 280 ° C., and the temperature of the detector (FID) portion was set to 300 ° C.

The sample was dissolved in acetone to prepare a 0.1 wt% solution, and 1 μl of the obtained solution was injected into the sample vaporizing chamber.
As a recorder, C-R5A type Chromatopac manufactured by Shimadzu Corporation or an equivalent thereof was used. The obtained gas chromatogram shows the peak retention time and peak area value corresponding to the component compounds.

As a sample dilution solvent, for example, chloroform or hexane may be used. In addition, as a column, capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc., H manufactured by Agilent Technologies Inc.
P-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm), Rtx-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Restek Corporation, manufactured by SGE International Pty. Ltd. BP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) or the like may be used. In order to prevent compound peaks from overlapping, 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.

  The area ratio of peaks in the gas chromatogram corresponds to the ratio of component compounds. In general, the weight% of the component compound of the sample is not completely the same as the area% of each peak of the sample. However, in the present invention, when the above-described column is used, the correction factor is substantially 1. Therefore, the weight% of the component compound in the sample substantially corresponds to the area% of each peak in the sample. This is because there is no significant difference in the correction coefficients of the liquid crystal compounds of the respective components. In order to more accurately determine the composition ratio of the liquid crystal compound in the liquid crystal composition by gas chromatogram, an internal standard method using gas chromatogram is used. The liquid crystal compound component (test component) weighed in a certain amount accurately and the reference liquid crystal compound (reference material) are simultaneously measured by gas chromatography, and the area ratio between the peak of the obtained test component and the peak of the reference material Is calculated in advance. When correction is performed using the relative intensity of the peak area of each component with respect to the reference substance, the composition ratio of the liquid crystal compound in the liquid crystal composition can be determined more accurately from gas chromatography analysis.

[Comparative Example 1]
The following compositions containing the second component and the third component of the present invention were prepared, and each characteristic value was measured by the method described above.
3-HB (2F, 3F) -O2 (2-1-1-1) 14%
5-HB (2F, 3F) -O2 (2-1-1-1) 14%
3-HHB (2F, 3F) -O2 (2-2-1-1) 11%
5-HHB (2F, 3F) -O2 (2-2-1-1) 11%
2-HHB (2F, 3F) -1 (2-2-1-1) 10%
3-HHB (2F, 3F) -1 (2-2-1-1) 10%
3-HH-4 (3-1-1) 7%
3-HH-5 (3-1-1) 7%
3-HB-O1 (3-1-2) 8%
5-HB-3 (3-1-2) 8%
NI = 68.9 ° C .; Tc ≦ −10 ° C .; Δn = 0.081; Δε = −3.3;
VHR-1 = 99.3%.

The following compositions were prepared and each characteristic value was measured by the method described above.
3-HB (2F) -O2 (1-1-1-1) 8%
3-HB (3F) -O2 (1-1-1-2) 8%
3-HHB (2F) -O2 (1-2-1-1) 7%
3-HHB (3F) -O2 (1-2-1-2) 7%
3-HB (2F, 3F) -O2 (2-1-1-1) 14%
5-HB (2F, 3F) -O2 (2-1-1-1) 14%
3-HHB (2F, 3F) -O2 (2-2-1-1) 11%
5-HHB (2F, 3F) -O2 (2-2-1-1) 11%
2-HHB (2F, 3F) -1 (2-2-1-1) 10%
3-HHB (2F, 3F) -1 (2-2-1-1) 10%
NI = 84.3 ° C .; Tc ≦ −10 ° C .; Δn = 0.096; Δε = −4.3;
η = 38.8 mPa · s; VHR-1 = 99.3%.
In the composition of Comparative Example 1, the third component halogen-free liquid crystalline compound was replaced with the first component fluorine 1-substituted compound. Compared to Comparative Example 1, the lower limit temperature of the composition of Example 1 is the same, but the upper limit temperature is high, Δε is negatively large, and has a large voltage holding ratio. By combining the first component and the second component, the temperature range of the nematic phase could be widened and Δε could be increased negatively.

The following compositions were prepared and each characteristic value was measured by the method described above.
3-HB (2F) -3 (1-1-1-1) 8%
3-HB (2F) -O2 (1-1-1-1) 8%
3-HHB (2F) -O2 (1-2-1-1) 6%
3-HHB (2F) -1 (1-2-1-1) 6%
3-HHB (3F) -O2 (1-2-1-2) 7%
3-HHB (3F) -1 (1-2-1-2) 8%
3-H1OB (2F) -O2 (1-1-2-1) 6%
3-H1OB (3F) -3 (1-1-2-2) 6%
3-H1OB (3F) -O2 (1-1-2-2) 6%
3-H1OB (2F) H-3 (1-3-1) 7%
3-H1OB (2F) H-O2 (1-3-1) 7%
3-HB (2F, 3F) -O2 (2-1-1-1) 5%
3-HB (2F, 3F) -O4 (2-1-1-1) 5%
5O-HHB (2F, 3F) -1 (2-2-1-1) 5%
3-HB (2F) B (2F, 3F) -O2 (2-2-1-3) 5%
3-HB (3F) B (2F, 3F) -O2 (2-2-1-4) 5%
NI = 71.2 ° C .; Tc ≦ −20 ° C .; Δn = 0.087; Δε = −3.3;
η = 28.4 mPa · s.
Compared to Comparative Example 1, the composition of Example 2 had a higher maximum temperature and a lower minimum temperature of ≦ −20 ° C., and was able to widen the temperature range of the nematic phase.

The following compositions were prepared and each characteristic value was measured by the method described above.
3-HB (3F) -3 (1-1-1-2) 10%
3-HB (3F) -O2 (1-1-1-2) 10%
3-H1OB (2F) H-3 (1-3-1) 7%
3-H1OB (2F) H-O2 (1-3-1) 8%
3-H1OB (2F) B-3 (1-3-1) 8%
3-H1OB (2F) B-O2 (1-3-1) 7%
3-HH1OB (2F) -O2 (1-2-3-1) 5%
3-HH1OB (2F) -1 (1-2-3-1) 5%
5-HB (2F, 3F) -O2 (2-1-1-1) 5%
5-HB (2F, 3F) -O4 (2-1-1-1) 5%
3-HHB (2F, 3F) -1 (2-2-1-1) 5%
3-HHB (2F, 3F) -2 (2-2-1-1) 5%
3-HHB (2F, 3F) -O2 (2-2-1-1) 7%
5-HHB (2F, 3F) -O2 (2-2-1-1) 8%
5-HBB (2F, 3F) -O2 (2-2-1-2) 5%
NI = 98.1 ° C .; Tc ≦ −20 ° C .; Δn = 0.108; Δε = −3.4;
η = 32.5 mPa · s.
Compared with Comparative Example 1, the composition of Example 3 had a higher maximum temperature and a lower minimum temperature of ≦ −20 ° C., and was able to widen the temperature range of the nematic phase.

The following compositions were prepared and each characteristic value was measured by the method described above.
3-HHB (2F) -O2 (1-2-1-1) 5%
3-HHB (3F) -1 (1-2-1-2) 5%
3-HHB (3F) -O2 (1-2-1-2) 5%
3-HH1OB (2F) -1 (1-2-3-1) 7%
3-HH1OB (2F) -O2 (1-2-3-1) 7%
2O-HHB (2F, 3F) -1 (2-2-1-1) 7%
3-HHB (2F, 3F) -O2 (2-2-1-1) 7%
5-HHB (2F, 3F) -O2 (2-2-1-1) 6%
5O-HHB (2F, 3F) -1 (2-2-1-1) 7%
3-HBB (2F, 3F) -O2 (2-2-1-2) 8%
5-HBB (2F, 3F) -O2 (2-2-1-2) 8%
3-HB-O2 (3-1-2) 7%
5-HB-O2 (3-1-2) 7%
5-HB-3 (3-1-2) 7%
7-HB-1 (3-1-2) 7%
NI = 102.8 ° C .; Tc ≦ −20 ° C .; Δn = 0.098; Δε = −3.1;
η = 27.7 mPa · s; VHR-1 = 99.2%.
Compared to Comparative Example 1, the composition of Example 4 had a higher maximum temperature and a lower minimum temperature of ≦ −20 ° C., and was able to widen the temperature range of the nematic phase. This composition also has a large voltage holding ratio.

The following compositions were prepared and each characteristic value was measured by the method described above.
3-HB (2F) -O2 (1-1-1-1) 7%
3-HHB (3F) -1 (1-2-1-2) 6%
3-H1OB (3F) -3 (1-1-2-2) 7%
3-H1OB (3F) -O2 (1-1-2-2) 6%
3-H1OB (2F) H-3 (1-3-1) 6%
3-H1OB (2F) B-3 (1-3-1) 5%
3-H1OB (2F) B-O2 (1-3-1) 5%
3-HH1OB (2F) -O2 (1-2-3-1) 5%
3-HH1OB (2F) -1 (1-2-3-1) 5%
3-HHB (2F, 3F) -O1 (2-2-1-1) 5%
3-HHB (2F, 3F) -O2 (2-2-1-1) 7%
5-HHB (2F, 3F) -O2 (2-2-1-1) 8%
5-HBB (2F, 3F) -O2 (2-2-1-2) 8%
3-HH-4 (3-1-1) 7%
3-HB-O2 (3-1-2) 6%
5-HB-3 (3-1-2) 7%
NI = 90.5 ° C .; Tc ≦ −20 ° C .; Δn = 0.098; Δε = −2.7;
η = 27.5 mPa · s.
Compared to Comparative Example 1, the composition of Example 5 had a higher maximum temperature and a lower minimum temperature of ≦ −20 ° C., and could widen the temperature range of the nematic phase.

The following compositions were prepared and each characteristic value was measured by the method described above.
3-HB (3F) -3 (1-1-1-2) 8%
3-HB (3F) -O2 (1-1-1-2) 8%
3-HHB (3F) -O2 (1-2-1-2) 5%
3-HHB (3F) -1 (1-2-1-2) 5%
3-H1OB (2F) -3 (1-1-2-1) 7%
3-H1OB (2F) H-3 (1-3-1) 7%
3-H1OB (2F) H-O2 (1-3-1) 7%
3-HH1OB (2F) -O2 (1-2-3-1) 5%
3-HH1OB (2F) -1 (1-2-3-1) 5%
3-HB1OB (2F) -O2 (1-2-3) 5%
3-HB (2F, 3F) -O2 (2-1-1-1) 8%
3-HB (2F, 3F) -O4 (2-1-1-1) 8%
3-HB (2F) B (2F, 3F) -O2 (2-2-1-3) 7%
3-HB (3F) B (2F, 3F) -O2 (2-2-1-4) 7%
1O1-HBBH-3 (3-3-1) 5%
1O1-HBBH-5 (3-3-1) 3%
NI = 85.3 ° C .; Tc ≦ −20 ° C .; Δn = 0.100; Δε = −3.5;
η = 32.4 mPa · s.
Compared with Comparative Example 1, the composition of Example 6 had a higher maximum temperature and a lower minimum temperature of ≦ −20 ° C., and was able to widen the temperature range of the nematic phase.

The following compositions were prepared and each characteristic value was measured by the method described above.
3-HB (2F) -O2 (1-1-1-1) 5%
3-HHB (3F) -O2 (1-2-1-2) 3%
3-HBB (3F) -O2 (1-2-2-1) 5%
3-H1OB (3F) -3 (1-1-2-2) 6%
3-H1OB (2F) H-O2 (1-3-1) 5%
3-H1OB (2F) B-O2 (1-3-1) 6%
3-HB1OB (2F) -O2 (1-2-3) 5%
3-HB1OB (2F) -1 (1-2-3) 5%
3-HB (2F, 3F) -O2 (2-1-1-1) 5%
3-HB (2F, 3F) -O4 (2-1-1-1) 6%
2O-HHB (2F, 3F) -1 (2-2-1-1) 3%
3-HBB (2F, 3F) -O2 (2-2-1-2) 7%
5-HBB (2F, 3F) -O2 (2-2-1-2) 7%
3-HB (3F) B (2F, 3F) -O2 (2-2-1-4) 7%
3-HH-4 (3-1-1) 8%
5-HB-3 (3-1-2) 7%
3-HHB-3 (3-2-1) 5%
3-HHB-O1 (3-2-1) 5%
NI = 91.0 ° C .; Tc ≦ −20 ° C .; Δn = 0.108; Δε = −3.4;
η = 28.1 mP · s.
Compared to Comparative Example 1, the composition of Example 7 had a higher maximum temperature and a lower minimum temperature of ≦ −20 ° C., and was able to widen the temperature range of the nematic phase.

The following compositions were prepared and each characteristic value was measured by the method described above.
3-HB (2F) -3 (1-1-1-1) 10%
3-HB (2F) -O2 (1-1-1-1) 10%
3-HHB (2F) -O2 (1-2-1-1) 7%
3-HB (2F, 3F) -O2 (2-1-1-1) 10%
3-HB (2F, 3F) -O4 (2-1-1-1) 10%
3-HB (2F) B (2F, 3F) -O2 (2-2-1-3) 8%
3-HB (3F) B (2F, 3F) -O2 (2-2-1-4) 7%
3-HB (2F, 3F) B (2F, 3F) -O2 (2-2-1-5) 7%
3-HB-O2 (3-1-2) 8%
5-HB-O2 (3-1-2) 8%
5-HBB (3F) B-2 (3-3-2) 5%
5-HBB (3F) B-O2 (3-3-2) 5%
5-HBB (3F) B-3 (3-3-2) 5%
NI = 80.3 ° C .; Tc ≦ −20 ° C .; Δn = 0.116; Δε = −4.3;
η = 34.1 mPa · s.
Compared to Comparative Example 1, the composition of Example 8 has a higher maximum temperature, a lower minimum temperature of ≦ −20 ° C., and a large Δε.

The following compositions were prepared and each characteristic value was measured by the method described above.
3-HB1OB (2F) -O2 (1-2-3) 6%
3-HB1OB (2F) -1 (1-2-3) 6%
3-HB (2F, 3F) -O2 (2-1-1-1) 11%
3-HB (2F, 3F) -O4 (2-1-1-1) 10%
5-HB (2F, 3F) -O2 (2-1-1-1) 10%
5-HB (2F, 3F) -O4 (2-1-1-1) 9%
3-HB (2F) B (2F, 3F) -O2 (2-2-1-3) 7%
3-HB (3F) B (2F, 3F) -O2 (2-2-1-4) 7%
3-HB (2F, 3F) B (2F, 3F) -O2 (2-2-1-5) 6%
V-HHB-1 (3-2-1) 8%
V2-HHB-1 (3-2-1) 8%
1O1-HBBH-4 (3-3-1) 5%
1O1-HBBH-5 (3-3-1) 4%
5-HBB (3F) B-2 (3-3-2) 3%
NI = 91.8 ° C .; Tc ≦ −20 ° C .; Δn = 0.110; Δε = −4.1;
η = 36.7 mPa · s.
Compared to Comparative Example 1, the composition of Example 9 has a higher maximum temperature, a lower limit temperature of ≦ −20 ° C., and a large Δε.

The following compositions were prepared and each characteristic value was measured by the method described above.
3-HB (3F) -3 (1-1-1-2) 10%
3-HB (3F) -O2 (1-1-1-2) 8%
3-HHB (2F) -1 (1-2-1-1) 5%
3-HHB (3F) -O2 (1-2-1-2) 5%
3-HHB (3F) -1 (1-2-1-2) 5%
3-HB (2F, 3F) -O2 (2-1-1-1) 5%
3-HB (2F, 3F) -O4 (2-1-1-1) 5%
3-HHB (2F, 3F) -O2 (2-2-1-1) 5%
5-HHB (2F, 3F) -O2 (2-2-1-1) 3%
3-HB (2F) B (2F, 3F) -O2 (2-2-1-3) 8%
3-HB (3F) B (2F, 3F) -O2 (2-2-1-4) 8%
2-HH-5 (3-1-1) 5%
3-HH-4 (3-1-1) 12%
3-HHB-3 (3-2-1) 5%
3-HHB-O1 (3-2-1) 3%
5-HBB (3F) B-2 (3-3-2) 3%
5-HBB (3F) B-O2 (3-3-2) 5%
NI = 94.3 ° C .; Tc ≦ −20 ° C .; Δn = 0.096; Δε = −3.4;
η = 31.5 mPa · s.
Compared with Comparative Example 1, the composition of Example 10 had a higher maximum temperature and a lower minimum temperature of ≦ −20 ° C., and could widen the temperature range of the nematic phase.

The following compositions were prepared and each characteristic value was measured by the method described above.
3-HB (2F) -O2 (1-1-1-1) 13%
3-HB (3F) -O2 (1-1-1-2) 13%
3-HHB (2F) -O2 (1-2-1-1) 7%
5-HHB (2F) -O2 (1-2-1-1) 7%
3-HHB (3F) -O2 (1-2-1-2) 7%
5-HHB (3F) -O2 (1-2-1-2) 7%
3-HB (2F, 3F) -O2 (2-1-1-1) 13%
5-HB (2F, 3F) -O2 (2-1-1-1) 13%
3-HHB (2F, 3F) -O2 (2-2-1-1) 4%
2-HHB (2F, 3F) -1 (2-2-1-1) 8%
3-HHB (2F, 3F) -1 (2-2-1-1) 8%
NI = 71.2 ° C .; Tc ≦ −20 ° C .; Δn = 0.091; Δε = −3.1;
η = 23.0 mPa · s
Compared with Comparative Example 1, the composition of Example 11 had a higher maximum temperature and a lower minimum temperature of ≦ −20 ° C., and was able to widen the temperature range of the nematic phase.

The following compositions were prepared and each characteristic value was measured by the method described above.
3-HB (2F) -O2 (1-1-1-1) 5%
5-HB (3F) -O1 (1-1-1-2) 5%
3-HHB (3F) -O2 (1-2-1-2) 4%
3-HBB (3F) -O2 (1-2-2-1) 4%
3-H1OB (3F) -3 (1-1-2-2) 7%
3-H1OB (2F) H-O2 (1-3-1) 5%
3-H1OB (2F) B-O2 (1-3-1) 5%
3-HB1OB (2F) -1 (1-2-3) 5%
3-HB (2F, 3F) -O2 (2-1-1-1) 5%
3-HB (2F, 3F) -O4 (2-1-1-1) 6%
3-HBB (2F, 3F) -O2 (2-2-1-2) 7%
5-HBB (2F, 3F) -O2 (2-2-1-2) 7%
3-HH-4 (3-1-1) 9%
3-HB-5 (3-1-2) 6%
3-HHB-3 (3-2-1) 6%
3-HHB-O1 (3-2-1) 4%
5-HHB (3F) -F-5%
4-HBB (3F) -F-5%
NI = 84.7 ° C .; Tc ≦ −20 ° C .; Δn = 0.101; Δε = −2.4;
η = 29.3 mP · s.
Compared with Comparative Example 1, the composition of Example 12 had a higher maximum temperature and a lower minimum temperature of ≦ −20 ° C., and was able to widen the temperature range of the nematic phase.

To the composition of Example 4, 140 ppm 3,5-di-tert-butyl-4-hydroxytoluene was added as an antioxidant. The characteristics of the obtained composition were as follows.
NI = 102.8 ° C .; Tc ≦ −20 ° C .; Δn = 0.098; Δε = −3.1;
η = 27.7 mPa · s; VHR-1 = 99.2%.

Claims (23)

A first component that is at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-3), and a formula (2-1) to formula (2-3) A liquid crystal composition having negative dielectric anisotropy, comprising a second component which is at least one compound selected from the group of compounds described above.

(In Formula (1-1)-Formula (1-3) and Formula (2-1)-Formula (2-3),
R ¹¹ and R ¹² are independently alkyl, alkenyl, or alkoxy;
Ring A ¹¹ is independently 2-fluoro-1,4-phenylene or 3-fluoro-1,4-phenylene;
Ring A ¹² is independently 1,4-cyclohexylene or 1,4-phenylene;
Ring A ¹³ is independently 1,4-cyclohexylene, or 1,4-phenylene in which any hydrogen may be replaced by fluorine or chlorine;
Z ¹¹ and Z ¹² are each independently a single bond, —C ₂ H ₄ —, —CH ₂ O—, or —OCH ₂ —.
However, in the formula (1-2), a compound in which the ring A ¹¹ is 2-fluoro-1,4-phenylene, the ring A ¹² is 1,4-phenylene, Z ¹¹ and Z ¹² are a single bond, and the formula (1 -3), a compound in which ring A ¹¹ is 3-fluoro-1,4-phenylene, ring A ¹² is 1,4-phenylene, and Z ¹¹ and Z ¹² are single bonds is excluded. ) Formula (1-1-1), Formula (1-1-2), Formula (1-2-1), Formula (1-2-2), Formula (1)
-2-3) and a first component that is at least one compound selected from the group of compounds represented by formula (1-3-1), formula (2-1-1), formula (2-2) -1), and the 2nd component which is at least 1 compound selected from the compound group represented by Formula (2-3-1), The liquid crystal composition which has negative dielectric constant anisotropy.

(Formula (1-1-1), Formula (1-1-2), Formula (1-2-1), Formula (1-2-2), Formula (1-2-3), Formula (1- 3-1), formula (2-1-1), formula (2-2-1), and formula (2-3-1), R _a is independently alkyl or alkenyl; R _b is Independently alkyl, alkenyl, or alkoxy;
Ring A ²¹ is independently 2-fluoro-1,4-phenylene or 3-fluoro-1,4-phenylene;
Ring A ²² is independently 1,4-cyclohexylene, or 1,4-phenylene;
Ring A ²³ is independently 1,4-cyclohexylene, or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Z ²¹ is independently —CH ₂ O— or —OCH ₂ —. )   It is represented by the above formula (1-1-1), formula (1-1-2), formula (1-2-1), formula (1-2-2), and formula (1-2-3). A first component which is at least one compound selected from the compound group, and a compound represented by the above formula (2-1-1), formula (2-2-1), and formula (2-3-1) The liquid crystal composition according to claim 2, comprising a second component that is at least one compound selected from the group.   The content ratio of the first component is 10 to 80% by weight and the content ratio of the second component is 20 to 90% by weight based on the total weight of the liquid crystal compound. The liquid crystal composition described. The liquid crystal according to any one of claims 1 to 3, further comprising a third component which is at least one compound selected from the group of compounds represented by formula (3-1) to formula (3-3). Composition.

(In Formula (3-1) to Formula (3-3), R _a is independently alkyl or alkenyl; R _b is independently alkyl, alkenyl, or alkoxy; R _c is alkyl, alkenyl; A plurality of rings A ²² are each independently 1,4-cyclohexylene or 1,4-phenylene; ring A ²³ is 1,4-cyclohexylene, or any of Hydrogen is 1,4-phenylene optionally substituted by fluorine; Z ²² is independently a single bond, —CH ₂ O—, —OCH ₂ —, or —COO—.)   Based on the total weight of the liquid crystal compound, the content of the first component is 5 to 75% by weight, the content of the second component is 20 to 80% by weight, and the content of the third component is 5 to 45%. The liquid crystal composition according to claim 5, wherein the liquid crystal composition is wt%. Formula (1-1-1-1), Formula (1-1-1-2), Formula (1-1-2-1), Formula (1-1-2-2), Formula (1-2) 1-1), formula (1-2-1-2), formula (1-2-2-1), formula (1-2-3-1), and formula (1-2-3-2) A first component that is at least one compound selected from the group of compounds represented by formula (2-1-1-1), formula (2-2-1-1), formula (2-2-1 2) at least one compound selected from the group of compounds represented by formula (2-2-1-3), formula (2-2-1-4), and formula (2-2-1-5) A liquid crystal composition having negative dielectric anisotropy, comprising a second component which is:

(Formula (1-1-1-1), Formula (1-1-1-2), Formula (1-1-2-1), Formula (1-1-2-2), Formula (1-2) -1-1), formula (1-2-1-2), formula (1-2-2-1), formula (1-2-3-1), formula (1-2-3-2), Formula (2-1-1-1), Formula (2-2-1-1-1), Formula (2-2-1-2), Formula (2-2-1-3), Formula (2-2-2) 1-4), and in formula (2-2-1-5), R _a is independently alkyl or alkenyl; R _b is independently alkyl, alkenyl, or alkoxy.   Compounds represented by the above formula (1-1-1-1), formula (1-1-2-1), formula (1-2-1-1), and formula (1-2-3-1) A first component which is at least one compound selected from the group, the above formula (2-1-1-1), and the formula (2-2-1-1) to the formula (2-2-1-5) The liquid crystal composition according to claim 7, further comprising a second component that is at least one compound selected from the group of compounds represented by:   The above formula (1-1-1-1), formula (1-1-1-2), formula (1-2-1-1), formula (1-2-1-2), and formula (1- A first component which is at least one compound selected from the compound group represented by 2-2-1), the above formula (2-1-1-1), and formula (2-2-1-1) The liquid crystal composition according to claim 7, comprising: a second component that is at least one compound selected from the group of compounds represented by formula (2-2-1-5).   Compounds represented by the above formula (1-1-1-1), formula (1-1-2-1), formula (1-2-1-1), and formula (1-2-3-1) A first component which is at least one compound selected from the group, and the above formula (2-1-1-1), formula (2-2-1-1), and formula (2-2-1-2) The liquid crystal composition according to claim 7, further comprising a second component that is at least one compound selected from the group of compounds represented by:   Compounds represented by the above formula (1-1-2-1), formula (1-1-2-2), formula (1-2-3-1), and formula (1-2-3-2) A first component which is at least one compound selected from the group, and the above formula (2-1-1-1), formula (2-2-1-1), and formula (2-2-1-2) The liquid crystal composition according to claim 7, further comprising a second component that is at least one compound selected from the group of compounds represented by:   A first component that is at least one compound selected from the group of compounds represented by formula (1-1-2-1) and formula (1-2-3-1), and formula (2-1) -1-1), a second component which is at least one compound selected from the group of compounds represented by formula (2-2-1-1) and formula (2-2-1-2) The liquid crystal composition according to claim 7.   The content ratio of the first component is 30 to 75% by weight, and the content ratio of the second component is 25 to 70% by weight, based on the total weight of the liquid crystal compound. The liquid crystal composition described. Compounds represented by formula (3-1-1), formula (3-1-2), formula (3-2-1), formula (3-3-1), and formula (3-3-2) The liquid crystal composition according to any one of claims 7 to 12, further comprising a third component which is at least one compound selected from the group.

(In Formula (3-1-1), Formula (3-1-2), Formula (3-2-1), Formula (3-3-1), and Formula (3-3-2), R _a Are independently alkyl or alkenyl; R _b is independently alkyl, alkenyl, or alkoxy; R _c is independently alkyl, alkenyl, alkoxy, or alkoxymethyl.)   The third component is at least one compound selected from the group of compounds represented by formula (3-1-1), formula (3-1-2), and formula (3-2-1). Item 15. A liquid crystal composition according to item 14.   The liquid crystal composition according to claim 14, wherein the third component is at least one compound selected from the group of compounds represented by formula (3-2-1). Based on the total weight of the liquid crystal compound, the content ratio of the first component is 10 to 65% by weight, the content ratio of the second component is 25 to 60% by weight, and the content ratio of the third component is 5 to 35%. The liquid crystal composition according to claim 14, wherein the liquid crystal composition is wt%.   The liquid crystal compound component is the above formula (1-1-1), formula (1-1-2), formula (1-2-1), formula (1-2-2), formula (1-2-3). ) And at least one compound selected from the group of compounds represented by formula (1-3-1), the above formula (2-1-1), and formula (2-2-1) And a second component that is at least one compound selected from the group of compounds represented by formula (2-3-1), and a compound represented by formula (3-1) to formula (3-3) above A liquid crystal composition having negative dielectric anisotropy, comprising only a third component which is at least one compound selected from the group.   The liquid crystal compound component is the above formula (1-1-1), formula (1-1-2), formula (1-2-1), formula (1-2-2), formula (1-2-3). ) And at least one compound selected from the group of compounds represented by formula (1-3-1), the above formula (2-1-1), and formula (2-2-1) And a liquid crystal composition having negative dielectric anisotropy, and the second component which is at least one compound selected from the group of compounds represented by formula (2-3-1).   The liquid crystal composition according to any one of claims 1 to 19, wherein a value of dielectric anisotropy is in a range of -6.5 to -2.0.   21. The liquid crystal composition according to claim 1, wherein the value of optical anisotropy is in the range of 0.080 to 0.120.   The liquid crystal display element containing the liquid-crystal composition of any one of Claims 1-21.   The liquid crystal display element according to claim 22, wherein the liquid crystal display element is displayed in a VA mode or an IPS mode and is driven in an active matrix system.