JP2008088164A - Chlorofluorobenzene-based liquid crystal compound, liquid crystal composition and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal compound stable to heat, light, etc., taking nematic phase over a wide temperature range, having low viscosity, large optical anisotropy, moderate elastic constants K<SB>33</SB>and K<SB>11</SB>and moderate negative dielectric anisotropy and exhibiting excellent compatibility with other liquid crystal compounds, and provide a liquid crystal composition containing the above compound, stable to heat, light, etc., and having low viscosity, moderate negative dielectric anisotropy, low threshold voltage and high upper limit temperature of nematic phase (phase-transition temperature between nematic phase and isotropic phase) and low lower-limit temperature of nematic phase. <P>SOLUTION: The invention provides a liquid crystal compound having a cyclohexenylene exemplified by a compound obtained by the chemical reaction formula and 1,4-phenylene wherein one of 2- and 3-hydrogen atoms is substituted with fluorine and the other hydrogen atom is substituted with chlorine, and a liquid crystal composition containing the liquid crystal compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a liquid crystal compound, a liquid crystal composition, and a liquid crystal display element. More specifically, the present invention relates to a chlorofluorobenzene derivative which is a liquid crystal compound, a liquid crystal composition having a nematic phase containing this compound, and a liquid crystal display device containing this composition.

  A liquid crystal display element typified by a liquid crystal display panel, a liquid crystal display module or the like is a liquid crystal compound (in the present invention, a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and a component of a liquid crystal composition that does not have a liquid crystal phase. As an operation mode of the liquid crystal display element, including a PC (phase change) mode, a TN mode, and a TN mode. (Twisted nematic) mode, STN (super twisted nematic) mode, BTN (bistable twisted nematic) mode, ECB (electrically controlled birefringence) mode, OCB (optically compensated bend) mode, IPS (in-plane switching) mode, VA (vertical) Various modes such as an alignment mode are known.

  Among these operation modes, the ECB mode, IPS mode, VA mode, etc. are operation modes utilizing the vertical alignment of liquid crystal molecules, and in particular, the IPS mode and VA mode are conventional display modes such as TN mode, STN mode, etc. It is known that the narrow viewing angle, which is a drawback, can be improved.

  As a component of a liquid crystal composition having a negative dielectric anisotropy that can be used in liquid crystal display elements of these operation modes, many liquid crystal compounds in which hydrogen on the benzene ring is replaced with fluorine have been studied. (For example, see Patent Documents 1 to 9.)

  For example, a compound (A) represented by the following structural formula has been studied (see Patent Document 1), but a compound in which hydrogen on the benzene ring exemplified by this compound (A) is replaced with chlorine and fluorine. Does not have a high clearing point and has a high viscosity. Moreover, it also applies to the stability against ultraviolet rays.

  Also disclosed is a compound (B) in which hydrogen on the benzene ring is replaced with chlorine and fluorine as a dopant for a liquid crystal medium used for electro-optic display, and the terminal group has a branched structure (for example, (See Patent Document 2). The mesophase range in which the compound exhibits liquid crystallinity is extremely narrow.

  Further, as a compound having hydrogen on the benzene ring replaced with fluorine and having cyclohexenylene, for example, compound (C) or compound (D) has been reported (for example, Patent Document 3 or 4). However, compound (C) and compound (D) are poorly compatible with other liquid crystal compounds in a low temperature range.

  Patent Documents 7, 8, and 9 report compounds having cyclohexenylene in which hydrogen on the benzene ring is replaced with fluorine as an intermediate.

International Publication No. 98/23561 Pamphlet Japanese Patent Laid-Open No. 10-158652 Japanese Patent Laid-Open No. 02-4723 JP 2002-193853 A Japanese Patent Laid-Open No. 10-237075 Japanese Patent Laid-Open No. 02-4725 International Publication No. 89/08633 Pamphlet International Publication No. 89/08687 Pamphlet EP1333301

  Accordingly, even a liquid crystal display element in an operation mode such as the IPS mode and the VA mode still has problems as a display element as compared with a CRT. For example, an improvement in response speed, an improvement in contrast, and a reduction in driving voltage are caused. It is desired.

The display element operating in the above-described IPS mode or VA mode is mainly composed of a liquid crystal composition having a negative dielectric anisotropy. In order to further improve the above characteristics and the like, the above liquid crystal composition is used. It is necessary that the liquid crystalline compound contained in the product has the following properties (1) to (8). That is,
(1) being chemically stable and physically stable;
(2) having a high clearing point (liquid crystal phase-isotropic phase transition temperature);
(3) The lower limit temperature of the liquid crystal phase (nematic phase, smectic phase, etc.), especially the lower limit temperature of the nematic phase is low,
(4) low viscosity,
(5) having appropriate optical anisotropy;
(6) having an appropriate negative dielectric anisotropy;
(7) having appropriate elastic constants K ₃₃ and K ₁₁ (K ₃₃ : bend elastic constant, K ₁₁ : splay elastic constant), and (8) excellent compatibility with other liquid crystal compounds,
It is.

When a composition containing a chemically and physically stable liquid crystal compound as in (1) is used for a display element, the voltage holding ratio can be increased.
In addition, as in (2) and (3), a composition containing a liquid crystal compound having a high clearing point or a low lower limit temperature of the liquid crystal phase can expand the temperature range of the nematic phase, and in a wide temperature range. It can be used as a display element.

Further, when a composition containing a compound having a low viscosity as in (4) or a compound having a large elastic constant K ₃₃ as in (7) is used as a display element, the response speed can be improved, and (5) In the case of a display element using a composition containing a compound having an appropriate optical anisotropy, the contrast of the display element can be improved. In addition, depending on the design of the display element, the optical anisotropy needs to be small to large, but recently the cell thickness tends to be thin in order to improve the response speed. There is a need for a composition having anisotropy.

In addition, when the liquid crystal compound has a large negative dielectric anisotropy, the threshold voltage of the liquid crystal composition containing this compound can be lowered, so that an appropriate negative voltage can be obtained as in (6). In the case of a display element using a composition containing a compound having a dielectric anisotropy, the driving voltage of the display element can be lowered and the power consumption can be reduced. Further (7) a composition comprising a compound having a suitable elastic constant K ₃₃ that the drive voltage of the display element can be adjusted with the use as a display element as described above, power consumption can be adjusted.

  The liquid crystal compound is generally used as a composition prepared by mixing with many other liquid crystal compounds in order to develop characteristics that are difficult to be exhibited by a single compound. Therefore, it is preferable that the liquid crystalline compound used for the display element has good compatibility with other liquid crystalline compounds as shown in (8). In addition, since the display element may be used in a wide temperature range including below freezing point, it may be preferable that the display element is a compound showing good compatibility from a low temperature range.

The first object of the present invention is to have stability to heat, light, etc., to become a nematic phase over a wide temperature range, to have a small viscosity, to have a large optical anisotropy, and appropriate elastic constants K ₃₃ and K ₁₁ . Furthermore, it is to provide a liquid crystal compound having appropriate negative dielectric anisotropy and excellent compatibility with other liquid crystal compounds.

  The second object of the present invention is to have stability against heat, light, etc., low viscosity, appropriate negative dielectric anisotropy, low threshold voltage, and upper limit of nematic phase. The object is to provide a liquid crystal composition containing the above compound having a high temperature (nematic phase-isotropic phase transition temperature) and a low minimum temperature of the nematic phase.

  The third object of the present invention is to provide a liquid crystal display device containing the above composition, which has a short response time, low power consumption and low driving voltage, high contrast, and can be used in a wide temperature range. It is.

As a result of intensive studies in view of the above problems, the present inventors have found that a liquid crystalline compound having a specific structure in which cyclohexenylene is contained and hydrogen on the benzene ring is replaced by chlorine and fluorine is obtained by heat, light. And has a nematic phase over a wide temperature range, a small viscosity, a large optical anisotropy, and appropriate elastic constants K ₃₃ and K ₁₁ (K ₃₃ : bend elastic constant, K ₁₁ : splay elastic constant) ), An appropriate negative dielectric anisotropy, and excellent compatibility with other liquid crystal compounds, and the liquid crystal composition containing the above compound has heat, It has stability to light, etc., has low viscosity, has an appropriate negative dielectric anisotropy, has a low threshold voltage, has a high nematic phase maximum temperature, and has a low nematic phase minimum temperature. And the above composition It has been found that the liquid crystal display element has a short response time, low power consumption and drive voltage, a high contrast ratio, and can be used in a wide temperature range, and the present invention has been completed.

That is, the present invention includes the following items.
That is, the present invention includes the following items [1] to [18].
[1]: A liquid crystal compound selected from the group of compounds represented by the following formula (a).

(In the formula (a), Ra and Rb are independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxyalkyl having 2 to 9 carbons, alkenyl having 2 to 10 carbons, and carbon. Alkenyloxy having 2 to 9 carbon atoms, fluoroalkyl having 1 to 10 carbon atoms, or fluoroalkoxy having 1 to 9 carbon atoms;
Ring A ¹ , Ring A ² , and Ring A ³ are independently trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, trans-tetrahydropyran-2,5- Diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1, 4-phenylene, pyridine-2,5-diyl, 6-fluoropyridine-2,5-diyl, or pyridazine-2,5-diyl;
Z ¹ , Z ² , and Z ³ are each independently a single bond, — (CH ₂ ) ₂ —, —CH═CH—, —C≡.
_{C -, - CH 2 O -} , - OCH 2 -, - COO -, - OCO -, - OCF 2 -, - CF 2 O -, - CH 2 CH 2 OCF 2 -, or -CF ₂ OCH ₂ CH ₂ -Either;
l, m, and n are independently 0, 1, or 2, but l + m + n is 0, 1, 2, or 3;
One of X ¹ and X ² is fluorine and the other is chlorine;
Q is

Is;
The atoms constituting these compounds may be their isotopes. )
[2]: Ring A ¹ , Ring A ² , and Ring A ³ are independently trans-1,4-cyclohexylene or 1,4-phenylene;
Z ¹ , Z ² , and Z ³ are independently a single bond or — (CH ₂ ) ₂ —;
Q is

The liquid crystalline compound according to item [1].
[3]: A liquid crystalline compound selected from the group of compounds represented by the following formula (a-1).

(In formula (a-1), Ra ₁ is a linear alkyl having 1 to 10 carbon atoms or a linear alkenyl having 2 to 10 carbon atoms, and Rb ₁ is a linear alkyl having 1 to 10 carbon atoms, Or carbon number 1-9
Is a straight-chain alkoxy. )
[4]: A liquid crystalline compound selected from the group of compounds represented by the following formula (b-1).

(In Formula (b-1), Ra ₁ is a linear alkyl having 1 to 10 carbon atoms or a linear alkenyl having 2 to 10 carbon atoms, and Rb ₁ is a linear alkyl having 1 to 10 carbon atoms, Or carbon number 1-9
Is a straight-chain alkoxy. )
[5]: A liquid crystal compound selected from the group of compounds represented by the following formula (a-2).

(In formula (a-2), Ra ₁ is a linear alkyl having 1 to 10 carbon atoms or a linear alkenyl having 2 to 10 carbon atoms, and Rb ₁ is a linear alkyl having 1 to 10 carbon atoms, Or carbon number 1-9
Is a straight-chain alkoxy. )
[6]: A liquid crystal compound selected from the group of compounds represented by the following formula (b-2).

(In Formula (b-2), Ra ₁ is a linear alkyl having 1 to 10 carbon atoms or a linear alkenyl having 2 to 10 carbon atoms, and Rb ₁ is a linear alkyl having 1 to 10 carbon atoms, Or carbon number 1-9
Is a straight-chain alkoxy. )
[7] A liquid crystal composition containing at least one compound according to any one of items [1] to [6].

  [8]: A first component comprising at least one compound selected from the compound group described in any one of items [1] to [6], the following formula (e-1), and formula (e- 2) and a liquid crystal composition having a negative dielectric anisotropy, comprising a second component comprising at least one compound selected from the compound group consisting of formula (e-3).

(In formula (e-1) to formula (e-3), Ra ₁₁ and Rb ₁₁ are independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxy having 2 to 9 carbons. Alkyl, alkenyl having 2 to 10 carbons, alkenyloxy having 2 to 9 carbons, fluoroalkyl having 1 to 10 carbons, or fluoroalkoxy having 1 to 9 carbons;
Ring A ¹¹ , Ring A ¹² , Ring A ¹³ , and Ring A ¹⁴ are independently trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, trans-tetrahydropyran- 2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or pyridine-2,5-diyl;
Z ¹¹ , Z ¹² , and Z ¹³ are each independently a single bond, —CH ₂ —CH ₂ —, —CH═CH—, —C≡C—, —COO—, or —CH ₂ O—. . )
[9]: represented by the following formula (a-1), formula (a-2), formula (a-3), formula (b-1), formula (b-2), and formula (b-3) A first component consisting of at least one compound selected from the group of compounds and at least one selected from the group of compounds consisting of the following formulas (e-1), (e-2), and (e-3) A liquid crystal composition having a negative dielectric anisotropy, comprising a second component comprising a compound.

(In Formula (a-1) to Formula (a-3) and Formula (b-1) to Formula (b-3), Ra ₁ is a linear alkyl having 1 to 10 carbon atoms, or 2 to 2 carbon atoms. 10 straight chain alkenyl, Rb ₁ is
It is a C1-C10 linear alkyl or a C1-C9 linear alkoxy. )

(In formula (e-1) to formula (e-3), Ra ₁₁ and Rb ₁₁ are independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxy having 2 to 9 carbons. Alkyl, alkenyl having 2 to 10 carbons, alkenyloxy having 2 to 9 carbons, fluoroalkyl having 1 to 10 carbons, or fluoroalkoxy having 1 to 9 carbons;
Ring A ¹¹ , Ring A ¹² , Ring A ¹³ , and Ring A ¹⁴ are independently trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, trans-tetrahydropyran- 2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or pyridine-2,5-diyl;
Z ¹¹ , Z ¹² , and Z ¹³ are each independently a single bond, —CH ₂ —CH ₂ —, —CH═CH—, —C≡C—, —COO—, or —CH ₂ O—. . )
[10]: Based on the total weight of the liquid crystal composition, the content ratio of the first component is in the range of 30 to 85% by weight, and the content ratio of the second component is in the range of 15 to 70% by weight. , Item [8] or [9].

  [11]: In addition to the first component and the second component, compounds represented by the following formula (g-1), formula (g-2), formula (g-3), and formula (g-4) Item 8. The liquid crystal composition according to item [8] or [9], comprising a third component comprising at least one compound selected from the group.

(In Formula (g-1) to Formula (g-4), Ra ₂₁ and Rb ₂₁ are independently hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or 2 to 9 carbons. An alkoxyalkyl having 2 to 10 carbon atoms, an alkenyloxy having 2 to 9 carbon atoms, a fluoroalkyl having 1 to 10 carbon atoms, or a fluoroalkoxy having 1 to 9 carbon atoms;
Ring A ²¹ , Ring A ²² , and Ring A ²³ are independently trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, trans-tetrahydropyran-2,5- Diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1, 4-phenylene, pyridine-2,5-diyl, 6-fluoropyridine-2,5-diyl, or pyridazine-2,5-diyl;
Z ²¹ , Z ²² and Z ²³ are each independently a single bond, —CH ₂ —CH ₂ —, —CH═CH—, —C≡C—, —OCF ₂ —, —CF ₂ O—, — OCF ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CF ₂ O—, —COO—, —OCO—, —OCH ₂ —, or —CH ₂ O—; Y ¹ , Y ² , Y ³ ,
And Y ⁴ are independently fluorine or chlorine;
q, r, and s are independently 0, 1, or 2, but q + r + s is 1, 2, or 3;
t is 0, 1, or 2. )
[12]: The third component is represented by the following formula (h-1), formula (h-2), formula (h-3), formula (h-4), and formula (h-5). Item [11] is a liquid crystal composition comprising at least one compound selected from the group of compounds.

(In the formulas (h-1) to (h-5), Ra ₂₂ is a linear alkyl having 1 to 8 carbon atoms or a linear alkenyl having 2 to 8 carbon atoms;
Rb ₂₂ is a straight-chain alkyl having 1 to 8 carbon atoms, a straight chain alkenyl, or alkoxy having 1 to 7 carbon atoms of 2 to 8 carbon atoms;
Z ²⁴ is a single bond or —CH ₂ CH ₂ —;
Y ¹ and Y ² are both fluorine, or one is fluorine and the other is chlorine. )
[13]: a compound comprising at least one compound selected from the group of compounds represented by the following formulas (a-1) to (a-3) and formulas (b-1) to (b-3): One ingredient,
A second component comprising at least one compound selected from the group consisting of the compounds of formula (e-1), formula (e-2), and formula (e-3) described in item [8]; 12] is selected from the group of compounds represented by formula (h-1), formula (h-2), formula (h-3), formula (h-4), and formula (h-5) A liquid crystal composition having a negative dielectric anisotropy, comprising a third component comprising at least one compound.

(In the above formula (a-1) to formula (a-3) and formula (b-1) to formula (b-3), Ra ₁ is
A straight-chain alkyl having 1 to 10 carbon atoms or a straight-chain alkenyl having 2 to 10 carbon atoms, Rb ₁
Is straight-chain alkyl having 1 to 10 carbons or straight-chain alkoxy having 1 to 9 carbons. )
[14]: Based on the total weight of the liquid crystal composition, the content ratio of the first component is in the range of 10 to 80% by weight, and the content ratio of the second component is in the range of 10 to 80% by weight. The liquid crystal composition according to any one of items [11] to [13], wherein the content ratio of the third component is in the range of 10 to 80% by weight.

[15]: The liquid crystal composition according to any one of items [7] to [14], further comprising an antioxidant and / or an ultraviolet absorber.
[16] The liquid crystal composition according to item [15], comprising an antioxidant represented by the following formula (I).

(In formula (I), w represents an integer of 1 to 15)
[17]: A liquid crystal display device containing the liquid crystal composition according to any one of items [7] to [16].

  [18] The liquid crystal display element according to item [17], wherein an operation mode of the liquid crystal display element is a VA mode or an IPS mode, and a driving method of the liquid crystal display element is an active matrix method.

The liquid crystalline compound of the present invention has stability against heat, light and the like, becomes a nematic phase over a wide temperature range, has a low viscosity, a large optical anisotropy, and appropriate elastic constants K ₃₃ and K ₁₁ (K _33). : Bend elastic constant, K ₁₁ : splay elastic constant), and also has an appropriate negative dielectric anisotropy and excellent compatibility with other liquid crystal compounds. In particular, it is excellent in that it has a large optical anisotropy and an appropriate negative dielectric anisotropy and has an excellent compatibility with other liquid crystal compounds.

  The liquid crystal composition of the present invention has stability against heat, light, etc., has a small viscosity, has an appropriate negative dielectric anisotropy, has a low threshold voltage, and further has a nematic phase. The upper limit temperature of the nematic phase is high and the lower limit temperature of the nematic phase is low. In particular, the liquid crystalline compound of the present invention has a large optical anisotropy and an appropriate negative dielectric anisotropy, and has excellent compatibility with other liquid crystalline compounds. The compound of the invention can be used, and it is excellent in that a liquid crystal composition having an appropriate negative dielectric anisotropy can be prepared.

  Furthermore, the liquid crystal display device of the present invention is characterized by containing the above-mentioned composition, has a short response time, low power consumption and driving voltage, a large contrast ratio, and can be used in a wide temperature range. It can be suitably used for liquid crystal display elements in display modes such as TN mode, STN mode, ECB mode, OCB mode, IPS mode, and VA mode, and particularly suitable for liquid crystal display elements in IPS mode and VA mode. be able to.

  Hereinafter, the present invention will be described more specifically. In the following description, unless otherwise specified, the amount of the compound expressed as a percentage means a weight percentage (% by weight) based on the total weight of the composition.

[Liquid crystal compound (a)]
The liquid crystalline compound of the present invention has a structure represented by the following formula (a) (hereinafter, these compounds are also referred to as “liquid crystalline compound (a)”).

  In the formula (a), Ra and Rb are independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxyalkyl having 2 to 9 carbons, alkenyl having 2 to 10 carbons, or carbon. These are alkenyloxy having 2 to 9 carbon atoms, fluoroalkyl having 1 to 10 carbon atoms, or fluoroalkoxy having 1 to 9 carbon atoms.

In the above formula (a), ring A ¹ , ring A ² , and ring A ³ are independently trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, trans- Tetrahydropyran-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene,
2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyridine-2,5-diyl, 6-fluoropyridine-2 , 5-diyl or pyridazine-2,5-diyl.

In the above formula (a), Z ¹ , Z ² , and Z ³ are each independently a single bond, — (CH ₂ ) ₂ —, —C
H═CH—, —C≡C—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —OCF ₂ —, —CF ₂ O—, —CH ₂ CH ₂ OCF ₂ —, Or —CF ₂ OCH ₂ CH ₂ —.

In the above formula (a), l, m, and n are independently 0, 1, or 2, but l + m + n is 0, 1, 2, or 3.
In the above formula (a), ^one of X ¹ and X ² is fluorine and the other is chlorine.

  And Q is

It is.
In addition, the isotope may be sufficient as the atom which comprises these compounds.
As described above, the compound (a) has cyclohexenylene and 1,4-phenylene in which one hydrogen at the 2nd and 3rd positions is replaced with fluorine and the other hydrogen is replaced with chlorine. By having such a structure, it exhibits a large optical anisotropy and an appropriate negative dielectric anisotropy, and further has an excellent compatibility with other liquid crystal compounds. Moreover, it has excellent stability against heat and light.

  In the above formula (a), Ra and Rb are the above groups, and the carbon-carbon bond chain in these groups is preferably a straight chain. When the carbon-carbon bond chain is a straight chain, the temperature range of the liquid crystal phase can be widened, and the viscosity can be reduced. In addition, when either Ra or Rb is an optically active group, it is useful as a chiral dopant. By adding the compound to a liquid crystal composition, a reverse twist domain (Reverse domain) generated in a liquid crystal display device is obtained. twisted domain) can be prevented.

In the above formula (a), Ra and Rb are the above groups, and alkenyl in these groups has a preferred configuration of —CH═CH— depending on the position of the double bond in alkenyl. _{-CH = CHCH 3, -CH = CHC} 2 H 5, -CH = CHC 3 H 7, -CH = CHC 4 H 9, -
In alkenyl having a double bond at odd positions such as C ₂ H ₄ CH═CHCH ₃ and —C ₂ H ₄ CH═CHC ₂ H ₅ , the steric configuration is preferably a trans configuration.

On the other _{hand, -CH 2 CH = CHCH 3,} -CH 2 CH = CHC 2 H 5, in the alkenyl having a double bond at an even position, such as _{-CH 2 CH = CHC 3 H 7} , stereochemistry is cis configuration preferable. The alkenyl compound having the preferred configuration as described above has a wide temperature range of the liquid crystal phase, a large elastic constant ratio K ₃₃ / K ₁₁ (K ₃₃ : bend elastic constant, K ₁₁ : spray elastic constant), and compound Further, when this liquid crystal compound is added to the liquid crystal composition, the upper limit temperature (T _NI ) of the nematic phase can be increased.

Specific examples of the alkyl include —CH ₃ , —C ₂ H ₅ , —C ₃ H ₇ , —C ₄ H ₉ , —C ₅ H _{11.
, -C 6 H 13, -C 7} H 15, -C 8 H 17, -C 9 H 19, and -C ₁₀ H ₂₁ can be cited;
Specific examples of the _{alkoxy, -OCH 3, -OC 2 H 5} , -OC 3 H 7, -OC 4 H 9,
_{-OC 5 H 11, -OC 6 H} 13, -OC 7 H 15, -OC 8 H 17, and can be exemplified -OC ₉ H _19;
Specific examples of the _{alkoxyalkyl, -CH 2 OCH 3, -CH 2} OC 2 H 5, -CH 2 OC 3 H 7, - (CH 2) 2 OCH 3, - (CH 2) 2 OC 2 H 5 _{, - (CH 2) 2 OC} 3 H 7, - (
_{CH 2) 3 OCH 3, -} (CH 2) 4 OCH 3, and - (CH _{2) 5} OCH ₃ can be cited;
Specific examples of the alkenyl include —CH═CH ₂ , —CH═CHCH ₃ , —CH ₂ CH═.
_{CH 2, -CH = CHC 2 H} 5, -CH 2 CH = CHCH 3, - (CH 2) 2 CH = CH 2, -CH = CHC 3 H 7, -CH 2 CH = CHC 2 H 5, - ( _{CH 2) 2 CH = CHCH 3} , - (CH 2
) ₃ CH═CH ₂ , —CH═CHC ₅ H ₁₁ , — (CH ₂ ) ₂ CH═CHC ₃ H ₇ , and — (C
H ₂ ) ₇ CH═CH ₂ may be mentioned;
Specific examples of the _{alkenyloxy, -OCH 2 CH = CH 2,} -OCH 2 CH = CH
Mention may be made of CH ₃ , —O (CH ₂ ) ₂ CH═CH ₂ , and —OCH ₂ CH═CHC ₂ H ₅ .

Specific examples of alkyl in which hydrogen is replaced with halogen include —CH ₂ F, —CHF ₂ , —CF ₃ , — (CH ₂ ) ₂ F, —CF ₂ CH ₂ F, —CF ₂ CHF ₂ , — _{CH 2 CF 3, -CF 2 CF} 3, - (CH 2) 3 F, - (CF 2) 2 CF 3, -CF 2 CHFCF 3, and -CHFCF ₂ CF ₃ can be cited;
Specific examples of alkoxy in which hydrogen is replaced with halogen include —OCF ₃ , —OCHF ₂ , —OCH ₂ F, —OCF ₂ CF ₃ , —OCF ₂ CHF ₂ , —OCF ₂ CH ₂ F, —OCF ₂ CF ₂ C
F _3, -OCF ₂ CHFCF _3, and -OCHFCF ₂ CF ₃ can be cited;
Specific examples of the alkenyl replacing the hydrogen with a halogen, -CH = CHF, -CH = CF 2, -CF = CHF, -CH = CHCH 2 F, -CH = CHCF 3, and - (CH _{2) 2}
CH = CF ₂ may be mentioned.

Among the specific examples of Ra and Rb, —CH ₃ , —C ₂ H ₅ , —C ₃ H ₇ , —C ₄ H ₉ ,
_{-C 5 H 11, -OCH 3,} -OC 2 H 5, -OC 3 H 7, -OC 4 H 9, -OC 5 H 11, -CH 2 OCH 3, - (CH 2) 2 OCH 3, - _{(CH 2) 3 OCH 3,} -CH = CH 2, -CH = CHCH 3, -CH 2 CH = CH 2, -CH = CHC 2 H 5, -CH 2 CH = CHCH 3, - (CH 2) 2
_{CH = CH 2, -CH = CHC} 3 H 7, -CH 2 CH = CHC 2 H 5, - (CH 2) 2 CH = CHCH 3, - (CH 2) 3 CH = CH 2, -OCH 2 CH = _{CH 2, -OCH 2 CH = CHCH} 3, -OCH 2 CH = CHC 2 H 5, -CF 3, -CHF 2, -CH 2 F, -OCF 3, -OCHF 2, -OCH 2 F, -OCF 2 CF ₃ , —OCF ₂ CHF ₂ , —OCF ₂ CH ₂ F, —OCF ₂ CF ₂ CF ₃ , —OCF ₂ CHFCF ₃ , and —OCHFCF ₂ CF ₃ are preferred, —CH ₃ , —
_{C 2 H 5, -C 3 H} 7, -C 4 H 9, -C 5 H 11, -OCH 3, -OC 2 H 5, -OC 3 H 7, -OC 4 H 9, -OC 5 H 11 , —CH ₂ OCH ₃ , —CH═CH ₂ , —CH═CHCH ₃ , —CH ₂ CH═CH ₂ , —CH═CHC ₂ H ₅ , —CH ₂ CH═CHCH ₃ , — (CH ₂ ) ₂ CH ═CH ₂ , —CH═CHC ₃ H ₇ , —CH ₂ CH═CHC ₂ H ₅ , — (CH ₂ ) ₂ CH═CHCH ₃ , and — (CH ₂ ) ₃ CH═CH ₂ are more preferred, —CH _{2 3, -C 2 H 5, -C} 3 H 7, -C 4 H 9, -C 5 H 11, -OCH 3, -OC 2 H 5, -OC 3 H 7, -OC 4 H 9, -CH = CH _2, -CH = C
More preferred are HCH ₃ , — (CH ₂ ) ₂ CH═CH ₂ , and — (CH ₂ ) ₂ CH═CHCH ₃ .

Ring A ¹ , Ring A ² , and Ring A ³ are independently trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, trans-tetrahydropyran-2,5- Diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1, 4-phenylene, pyridine-2,5-diyl, 6-fluoropyridine-2,5-diyl, or pyridazine-2,5-diyl.

  Among these rings, trans-1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, and 2,3-difluoro-1,4-phenylene are more preferable, and trans-1, 4-cyclohexylene and 1,4-phenylene are most preferred.

In particular, when at least two of these rings are trans-1,4-cyclohexylene, the viscosity can be reduced, and when this liquid crystalline compound is added to the liquid crystal composition, the upper limit of the nematic phase is increased. The temperature (T _NI ) can be increased.

In addition, when at least one of these rings is 1,4-phenylene, the orientational order parameter can be increased. further,
When at least two rings are 1,4-phenylene, the optical anisotropy can be further increased.

Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) ₂ —, —CH═CH—,
—C≡C—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —OCF ₂ —, —C
F ₂ O—, —CH ₂ CH ₂ OCF ₂ —, or —CF ₂ OCH ₂ CH ₂ —.

Here, when Z ¹ , Z ² , and Z ³ are a linking group such as —CH═CH—, the steric configuration of the other group with respect to the double bond is preferably a trans configuration. By such a configuration, the temperature range of the liquid crystal phase of the liquid crystal compound can be expanded, and further, when this liquid crystal compound is added to the liquid crystal composition, the upper limit temperature (T _NI ) of the nematic phase is increased. Can be high.

Among these, Z ¹ , Z ² , and Z ³ , a single bond, — (CH ₂ ) ₂ —, and —CH═C
H- is preferred. Z ¹ , Z ² , and Z ³ are a single bond, — (CH ₂ ) ₂ —, and —CH.
When ═CH—, it is stable against heat and light, and the maximum temperature (T _NI ) of the nematic phase can be increased and the viscosity of the compound can be decreased. In particular, the above Z ¹ , Z ² , and Z ³
Is a single bond or — (CH ₂ ) ₂ —, it is more stable to heat and light.

When -CH = CH- is contained in Z ¹ , Z ² , and Z ³ , the temperature range of the liquid crystal phase is widened, the elastic constant ratio K ₃₃ / K ₁₁ is increased, The viscosity of the compound can be decreased, the optical anisotropy (Δn) can be increased, and the upper limit temperature (T _NI ) of the nematic phase can be increased when this liquid crystalline compound is added to the liquid crystal composition. it can.

In the above formula (a), ^one of X ¹ and X ² is fluorine and the other is chlorine. In this way, when one is fluorine and the other is chlorine, compatibility with other liquid crystal compounds can be improved as compared with the case where the same halogen, particularly X ¹ and X ² are fluorine. It becomes. Therefore, the liquid crystal compound (a) can be added more than the other liquid crystal compounds, so that the optical anisotropy (Δn) is large and the dielectric constant is anisotropic compared to the conventional liquid crystal composition. A liquid crystal composition having negatively large properties (Δε) can be obtained.

Further, when X ¹ is chlorine and X ² is fluorine, the compatibility with other liquid crystal compounds is further excellent. Since there is no significant difference in the physical properties of the compounds, the liquid crystalline compound (a) is ² H
(Deuterium), ¹³ C and other isotopes may be included in an amount greater than the natural abundance.

In these liquid crystalline compounds (a), terminal groups Ra and Rb, ring A ¹ , ring A ² , and ring A ³
, Linking groups Z ¹ , Z ² , and Z ³ are appropriately selected within the above range, thereby permitting dielectric anisotropy (Δ
It is possible to adjust a physical property such as ε) to a desired physical property.

  Among these liquid crystalline compounds (a), compounds represented by the following formulas (a-1) to (a-3) and formulas (b-1) to (b-3) are preferable.

In the above formula (a-1) to formula (a-3) and formula (b-1) to formula (b-3), Ra ₁ is
A straight-chain alkyl having 1 to 10 carbon atoms or a straight-chain alkenyl having 2 to 10 carbon atoms, Rb ₁
Is straight-chain alkyl having 1 to 10 carbons or straight-chain alkoxy having 1 to 9 carbons.

  When the liquid crystal compound (a) is represented by the above formulas (a-1) and (b-1), when it is added to the liquid crystal composition, it is particularly excellent in compatibility and has a dielectric anisotropy. Is preferable because it can be negatively increased.

  When the liquid crystal compound (a) is represented by the above formula (a-2), when it is added to the liquid crystal composition, the compatibility is excellent and the dielectric anisotropy can be negatively increased. The optical anisotropy can be increased, and the upper limit temperature of the nematic phase can be increased, which is preferable.

  When the liquid crystal compound (a) is represented by the above formula (a-3), when this is added to the liquid crystal composition, the dielectric anisotropy can be increased negatively, and the optical anisotropy can be increased. Can be increased, and the upper limit temperature of the nematic phase can be increased.

When the liquid crystal compound (a) is represented by the above formula (b-2), when it is added to the liquid crystal composition, the compatibility is excellent and the dielectric anisotropy can be negatively increased. The optical anisotropy can be increased, and the upper limit temperature of the nematic phase can be increased, which is preferable.

  When the liquid crystal compound (a) is represented by the above formula (b-3), when it is added to the liquid crystal composition, the compatibility is excellent and the dielectric anisotropy can be negatively increased. The optical anisotropy can be further increased, and the upper limit temperature of the nematic phase can be increased, which is preferable.

When the liquid crystalline compound has a structure represented by these liquid crystalline compounds (a), it has an appropriate negative dielectric anisotropy and is extremely compatible with other liquid crystalline compounds. Furthermore, it has stability against heat, light, etc., has a nematic phase over a wide temperature range, has a low viscosity, has a large optical anisotropy, and appropriate elastic constants K ₃₃ and K ₁₁ . In addition, the liquid crystal composition containing the liquid crystal compound (a) is stable under the conditions in which the liquid crystal display device is normally used, and the compound precipitates as crystals (or smectic phases) even when stored at a low temperature. There is nothing to do.

  Therefore, the liquid crystalline compound (a) can be suitably applied to a liquid crystal composition used in a liquid crystal display element of a display mode such as PC, TN, STN, ECB, OCB, IPS, VA, and the like, such as IPS, VA, etc. The present invention can be particularly preferably applied to a liquid crystal composition used in a display mode liquid crystal display element.

[Synthesis of Liquid Crystalline Compound (a)]
The liquid crystalline compound (a) can be synthesized by appropriately combining synthetic methods of organic synthetic chemistry. Methods for introducing the desired end groups, rings and linking groups into the starting material include, for example, Organic Synthesis (John Wiley & Sons, Inc), Organic Reactions (Organic Reactions, John Wiley & Sons, Inc), Comple Hensive Organic Synthesis (Pergamon Press)
It is described in books such as the New Experimental Chemistry Course (Maruzen).

<Formation of bonding groups Z ¹ , Z ² , and Z ³ >
An example of a method for forming the linking groups Z ¹ , Z ² , and Z ³ is shown. A scheme for forming a linking group is shown below. In this scheme, MSG ¹ or MSG ² is a monovalent organic group. A plurality of MSG ¹ (or MSG ² ) used in the scheme may be the same or different. From compound (1A) to compound (1J) corresponds to liquid crystal compound (a).

<Generation of double bond # 1>
An organic halogen compound (a1) having a monovalent organic group MSG ² is reacted with magnesium to prepare a Grignard reagent. By reacting the prepared Grignard reagent with the aldehyde derivative (a4) or (a5), a corresponding alcohol derivative is synthesized. Next, by dehydrating the resulting alcohol derivative using an acid catalyst such as p-toluenesulfonic acid, the corresponding compound (1A) or compound (1B) having a double bond can be synthesized. .

<Generation of double bond # 2>
A compound obtained by treating an organic halogen compound (a1) with butyllithium or magnesium is reacted with formamide such as N, N-dimethylformamide (DMF) to obtain aldehyde (a6). Subsequently, the obtained aldehyde (a6) is reacted with a phosphoryl ylide obtained by treating the phosphonium salt (a7) or (a8) with a base such as potassium t-butoxide (t-BuOK), and the corresponding double-layer. A compound (1A) or a compound (1B) having a bond can be synthesized. In the above reaction, a cis isomer may be generated depending on the reaction conditions. Therefore, when it is necessary to obtain a trans isomer, the cis isomer is isomerized into a trans isomer by a known method as necessary.

<Generation of single bond # 1>
An organic halogen compound (a1) and magnesium are reacted to prepare a Grignard reagent. By reacting this prepared Grignard reagent with the cyclohexanone derivative (a2), the corresponding alcohol derivative is synthesized. Next, the resulting alcohol derivative is dehydrated using an acid catalyst such as p-toluenesulfonic acid to synthesize the corresponding compound (a3) having a double bond. Compound (1C) can be synthesized by hydrogenating the obtained compound (a3) in the presence of a catalyst such as Raney-Ni. The cyclohexanone derivative (a2) can be synthesized, for example, according to the method described in JP-A-59-7122.

<Generation of single bond # 2>
An organic halogen compound (a9) having a monovalent organic group MSG ¹ is reacted with magnesium or butyllithium to prepare a Grignard reagent or a lithium salt. The dihydroxyborane derivative (a10) is synthesized by reacting the prepared Grignard reagent or lithium salt with a boric acid ester such as trimethyl borate and hydrolyzing with an acid such as hydrochloric acid. By reacting the dihydroxyborane derivative (a10) with the organic halogen compound (a1) in the presence of a catalyst comprising, for example, an aqueous carbonate solution and tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ). Compound (1F) can be synthesized.

Further, after reacting the organic halogen compound (a9) with butyl lithium and further with zinc chloride, the resulting compound is converted into, for example, the presence of a bistriphenylphosphine dichloropalladium (Pd (PPh ₃ ) ₂ Cl ₂ ) catalyst. By reacting with compound (a1) under
Compound (1F) can also be synthesized.

<Generation of-(CH ₂ ) _2- >
Compound (1D) can be synthesized by hydrogenating compound (1A) in the presence of a catalyst such as palladium on carbon (Pd / C).

<- (CH _{2) 4} - Generation of>
Compound (1E) can be synthesized by hydrogenating compound (1B) in the presence of a catalyst such as Pd / C.

<Formation of —CH ₂ O— or —OCH ₂ —>
The dihydroxyborane derivative (a10) is oxidized with an oxidizing agent such as hydrogen peroxide to obtain the alcohol derivative (a11). Separately, the aldehyde derivative (a6) is reduced with a reducing agent such as sodium borohydride to obtain the compound (a12). The obtained compound (a12) is halogenated with hydrobromic acid or the like to obtain an organic halogen compound (a13). The compound (1G) can be synthesized by reacting the compound (a11) thus obtained with the compound (a13) in the presence of potassium carbonate or the like.

<Generation of -COO- and -OCO->
The compound (a9) is reacted with n-butyllithium and subsequently with carbon dioxide to obtain a carboxylic acid (a14). The compound (a14) and the phenol (a15) synthesized by a method that gives the compound (a11) are dehydrated in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine). Thus, a compound (1H) having —COO— can be synthesized. A compound having —OCO— can also be synthesized by this method.

<Formation of -CF ₂ O- and -OCF _2- >
Compound (a16) is obtained by treating compound (1H) with a sulfurizing agent such as Lawesson's reagent. The compound (a16) is fluorinated with a hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize a compound (1I) having —CF ₂ O—. See M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1I) can also be synthesized by fluorinating compound (a16) with (diethylamino) sulfur trifluoride (DAST). See WH Bunnelle et al., J. Org. Chem. 1990, 55, 768. A compound having —OCF ₂ — is also synthesized by this method. These linking groups can also be generated by the method described in Peer. Kirsch et al., Anbew. Chem. Int. Ed. 2001, 40, 1480.

<Generation of -C≡C->
In the presence of a catalyst of dichloropalladium and copper halide, the compound (a9) is reacted with 2-methyl-3-butyn-2-ol and then deprotected under basic conditions to obtain the compound (a17). . Compound (1J) is synthesized by reacting compound (a17) with compound (a1) in the presence of a catalyst of dichloropalladium and copper halide.

[Method for Producing Liquid Crystalline Compound (a)]
Hereinafter, production examples of the liquid crystalline compound (a), that is, the liquid crystalline compound represented by the above formula (a) are shown.

  A Grignard reagent is prepared by reacting compound (b1) with magnesium. The Grignard reagent is reacted with the carbonyl derivative (b2) to obtain the alcohol derivative (b3). A liquid crystalline compound (b4) which is an example of the liquid crystalline compound (a) of the present invention by dehydrating the alcohol derivative (b3) obtained in the presence of an acid catalyst such as p-toluenesulfonic acid (PTS). Can be manufactured.

A dihydroxyborane derivative (b6) is obtained by reacting compound (b5) with sec-butyllithium to prepare a lithium salt, reacting it with a borate ester, and hydrolyzing in an acidic atmosphere. Separately, the alcohol derivative (b8) is synthesized by reacting the dihalogen derivative with n-butyllithium and then reacting with the carbonyl derivative (b2). Subsequently, the cyclohexene derivative (b9) can be obtained by dehydrating the alcohol derivative (b8) obtained in the presence of an acid catalyst such as p-toluenesulfonic acid (PTS). This compound (b9) and the dihydroxyborane derivative (b6) are present in the presence of a base such as potassium carbonate and sodium hydroxide, and a catalyst such as Pd / C, Pd (PPh ₃ ) ₄ or Pd (PPh ₃ ) ₂ Cl ₂ . By reacting, a liquid crystal compound (b10) which is an example of the liquid crystal compound (a) of the present invention can be produced.

  A Grignard reagent is prepared by reacting compound (b11) with magnesium. This Grignard reagent is reacted with the carbonyl derivative (b2) to obtain the alcohol derivative (b12). Subsequently, the cyclohexene derivative (b13) can be obtained by performing a dehydration reaction of the obtained alcohol derivative (b12) in the presence of an acid catalyst such as p-toluenesulfonic acid (PTS). Next, a phenol derivative (b14) is obtained by performing a cleavage reaction of the compound (b13) with a Lewis acid such as boron tribromide, and the compound (b14) is obtained in the presence of a base such as potassium carbonate. The liquid crystalline compound (b16) which is an example of the liquid crystalline compound (a) of the present invention can be produced by etherification with the compound (b15).

Compound (b14) is obtained by reacting compound (b14) with trifluoromethanesulfonic anhydride in the presence of a base such as pyridine. Subsequently, the compound (b17) is reacted with the dihydroxyborane derivative (b18) using Pd (PPh ₃ ) ₄ or Pd / C as a catalyst in the presence of a base such as potassium carbonate, thereby obtaining the liquid crystalline compound of the present invention. A liquid crystal compound (b19) which is an example of (a) can be produced.

  A Grignard reagent is prepared by reacting compound (b1) with magnesium. This Grignard reagent and the carbonyl derivative (b20) are reacted to obtain an alcohol derivative (b21). The resulting alcohol derivative (b21) is subjected to a dehydration reaction in the presence of an acid catalyst such as p-toluenesulfonic acid to obtain a cyclohexene derivative (b22). The compound (b22) is hydrolyzed in an acid atmosphere such as formic acid to obtain a carbonyl derivative (b23). The obtained carbonyl derivative (b23) is subjected to Wittig reaction with phosphoyllide prepared from a base such as methoxymethyltriphenylphosphonium chloride and potassium t-butoxide (t-BuOK) to obtain an enol ether derivative (b24). . The obtained enol ether derivative (b24) is hydrolyzed in an acid atmosphere and, if necessary, further isomerized under basic conditions to obtain an aldehyde derivative (b25). By reacting this aldehyde derivative (b25) with a phosphorus ylide prepared from methyltriphonylphosphonium bromide and a base such as t-BuOK, a liquid crystal compound which is an example of the liquid crystal compound (a) of the present invention (B26) can be manufactured.

[Liquid crystal composition]
Hereinafter, the liquid crystal composition of the present invention will be described. The component of the liquid crystal composition is characterized by containing at least one liquid crystal compound (a), but may contain two or more liquid crystal compounds (a), and only from the liquid crystal compound (a). It may be configured.

  The liquid crystal composition is stable to heat and light, has a low viscosity, has an appropriate negative dielectric anisotropy, has a low threshold voltage, and further has an upper limit temperature of a nematic phase (nematic phase). -Phase transition temperature of isotropic phase) is high, and minimum temperature of nematic phase is low.

[Liquid crystal composition (1)]
In addition to the liquid crystal compound (a) as a first component, the liquid crystal composition of the present invention has a liquid crystal compound represented by the following formula (e-1) to formula (e-3) as a second component (hereinafter referred to as compound ( A composition further containing at least one compound selected from the group of e-1) to compound (e-3)) is preferred (hereinafter also referred to as liquid crystal composition (1)).

In the above formulas (e-1) to (e-3), Ra ₁₁ and Rb ₁₁ are independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or alkoxy having 2 to 9 carbons. Alkyl, alkenyl having 2 to 10 carbons, alkenyloxy having 2 to 9 carbons, fluoroalkyl having 1 to 10 carbons, or fluoroalkoxy having 1 to 9 carbons.

In the above formulas (e-1) to (e-3), ring A ¹¹ , ring A ¹² , ring A ¹³ , and ring A ¹⁴ are independently trans-1,4-cyclohexylene, trans-1 , 3-dioxane-2,5-diyl, trans-tetrahydropyran-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or pyridine-2,5-diyl.

In the above formulas (e-1) to (e-3), Z ¹¹ , Z ¹² , and Z ¹³ are each independently a single bond, —CH ₂ —CH ₂ —, —CH═CH—, —C ≡C—, —COO—, or —CH ₂ O—.

  By containing the second component in the liquid crystal compound (a), the viscosity of the liquid crystal composition can be reduced, and the nematic phase region can be expanded. For example, the compound (e-1) is an effective compound for reducing the viscosity of the liquid crystal composition containing the compound (e-1) and increasing the specific resistance value.

  The compound (e-2) is an effective compound for increasing the maximum temperature of the nematic phase of the liquid crystal composition containing it and increasing the specific resistance value. Further, the compound (e-3) is an effective compound for increasing the upper limit temperature of the nematic phase of the liquid crystal composition containing the compound and increasing the specific resistance value.

In ring A ¹¹ , ring A ¹² , ring A ¹³ , and ring A ¹⁴ , when two or more rings are trans-1,4-cyclohexylene, the upper limit temperature of the nematic phase of the liquid crystal composition containing the ring is set to In the case where two or more rings are 1,4-phenylene, the optical anisotropy of the composition containing the ring can be increased.

Among the second components, more preferable compounds are compounds represented by the following formulas (2-1) to (2-74) (hereinafter also referred to as compounds (2-1) to (2-74)). ). In these compounds, Ra ₁₁ and Rb ₁₁ have the same meaning as in the case of the compounds (e-1) to (e-3).

  When the second component is the compound (2-1) to the compound (2-74), a liquid crystal composition having a higher specific resistance value and a wide nematic phase can be prepared. The content of the second component in the liquid crystal composition (1) of the present invention is not particularly limited, but the content is preferably increased from the viewpoint of lowering the viscosity. However, since the threshold voltage of the liquid crystal composition tends to increase when the content of the second component is increased, for example, when the liquid crystal composition of the present invention is used in a VA mode liquid crystal element, The content of the second component is in the range of 15 to 70% by weight with respect to the total weight of the liquid crystal composition, and the content of the first component is 30 to 85 with respect to the total weight of the liquid crystal composition. A range of% by weight is more preferred.

  In particular, the first component is at least one compound selected from the group of compounds represented by formula (a-1) to formula (a-3) and formula (b-1) to formula (b-3). The liquid crystal composition (1), in which the second component is at least one compound selected from the group of compounds represented by the compounds (e-1) to (e-3), has a wide nematic phase. The specific resistance value is large and the viscosity is small.

[Liquid crystal composition (2)]
In addition to the first component and the second component, the liquid crystal composition of the invention further includes a liquid crystal compound represented by the following formula (g-1) to formula (g-4) (hereinafter referred to as a compound) as a third component. At least one compound selected from the group of (g-1) to compound (g-4)) is also preferable (hereinafter also referred to as liquid crystal composition (2)).

In the above formulas (g-1) to (g-4), Ra ₂₁ and Rb ₂₁ are independently hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or 2 to 9 carbons. An alkoxyalkyl having 2 to 10 carbon atoms, an alkenyloxy having 2 to 9 carbon atoms, a fluoroalkyl having 1 to 10 carbon atoms, or a fluoroalkoxy having 1 to 9 carbon atoms.

In the above formulas (g-1) to (g-4), ring A ²¹ , ring A ²² , and ring A ²³ are independently trans-1,4-cyclohexylene, trans-1,3-dioxane. -2,5-diyl, trans-tetrahydropyran-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5- Difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyridine-2,5-diyl, 6-fluoropyridine-2,5-diyl, or pyridazine-2,5-diyl.

In the above formulas (g-1) to (g-4), Z ²¹ , Z ²² , and Z ²³ are each independently a single bond,
_{-CH 2 -CH 2 -, - CH} = CH -, - C≡C -, - OCF 2 -, - CF 2 O -, - OCF 2 CH 2 CH 2 -, - CH 2 CH 2 CF 2 O-, -COO -, - OCO -, - OCH 2 -, or -CH ₂ O-;
In the above formulas (g-1) to (g-4), Y ¹ , Y ² , Y ³ , and Y ⁴ are independently fluorine or chlorine.

  In the above formulas (g-1) to (g-4), q, r, and s are independently 0, 1, or 2, but q + r + s is 1, 2, or 3, and t is 0, 1, or 2. The liquid crystal composition (2) further containing the third component has a large negative dielectric anisotropy.

  In addition, a liquid crystal composition having a wide nematic phase temperature range, a low viscosity, a large negative dielectric anisotropy and a large specific resistance value can be obtained, and a liquid crystal composition in which these physical properties are appropriately balanced Things are obtained.

  Among the third components, from the viewpoint of low viscosity, excellent heat resistance and light resistance, and increasing the upper limit temperature of the nematic phase, the following formulas (h-1) to (h-5) And at least one compound selected from the group of compounds represented by the formula (hereinafter also referred to as compound (h-1) to compound (h-5)) is preferred.

In the above formulas (h-1) to (h-5), Ra ₂₂ is linear alkyl having 1 to 8 carbons or linear alkenyl having 2 to 8 carbons, and Rb ₂₂ is carbon 1 8 linear alkyl, linear alkenyl or alkoxy having 1 to 7 carbon atoms, 2 to 8 carbon atoms, Z ²⁴ is a single bond, or -CH ₂ CH ₂ -.

In formulas (h-1) to (h-5), Y ¹ and Y ² are both fluorine, or one is fluorine and the other is chlorine. For example, a compound having a condensed ring such as compound (g-2) to compound (g-4) can lower the threshold voltage value of the liquid crystal composition containing the compound.

  For example, the compound (h-1) and the compound (h-2) can reduce the viscosity of the liquid crystal composition containing the compound and lower the threshold voltage value. The compound (h-2) and the compound (h-3) can increase the upper limit temperature of the nematic phase of the liquid crystal composition containing the compound (h-3) and lower the threshold voltage value.

Compound (h-4) and compound (h-5) can increase the maximum temperature of the nematic phase of the liquid crystal composition containing the compound, increase the optical anisotropy, and decrease the threshold voltage value.
In particular, at least selected from the group of compounds represented by formula (a-1) to formula (a-3) and formula (b-1) to formula (b-3) among the liquid crystal composition (2). A first component comprising one compound, and a second component comprising at least one compound selected from the compound group consisting of the above formula (e-1), formula (e-2), and formula (e-3) At least one selected from the group of compounds represented by formula (h-1), formula (h-2), formula (h-3), formula (h-4), and formula (h-5). A liquid crystal composition containing a third component composed of a compound is stable to heat and light, has a wide temperature range of the nematic phase, a low viscosity, a large negative dielectric anisotropy, and a specific resistance value. large. Furthermore, it is preferable in terms of a liquid crystal composition in which these physical properties are appropriately balanced.

Among the third components, more preferable compounds are the compound (3-1) to the compound (3-68). In these compounds, Ra ₂₂ and Rb ₂₂ have the same meaning as in the above compounds (g-1) to (g-5).

Although there is no restriction | limiting in particular in content of the said 3rd component in the liquid-crystal composition of this invention, It is preferable to increase content from a viewpoint that the absolute value of negative dielectric constant anisotropy is not made small.
The content ratios of the first component, the second component, and the third component of the liquid crystal composition (2) according to the present invention are not particularly limited, but based on the total weight of the liquid crystal composition (2), It is preferable that the content ratio of the compound (a) is in the range of 10 to 80% by weight, the content ratio of the second component is in the range of 10 to 80% by weight, and the content ratio of the third component is in the range of 10 to 80% by weight. Furthermore, the content ratio of the first component is in the range of 10 to 70% by weight, the content ratio of the second component is in the range of 10 to 50% by weight, and the content ratio of the third component is in the range of 20 to 60% by weight. Is more preferable.

  When the content ratio of the first component, the second component, and the third component of the liquid crystal composition (2) is in the above range, the temperature range of the nematic phase is wide, the viscosity is small, and the dielectric anisotropy is Negatively large and specific resistance value is large. Furthermore, a liquid crystal composition in which these physical properties are more appropriately balanced can be obtained.

[Mode of liquid crystal composition, etc.]
In the liquid crystal composition according to the present invention, in addition to the first component, and the liquid crystal compounds constituting the second component and the third component added as necessary, for example, for the purpose of further adjusting the characteristics of the liquid crystal composition. In some cases, other liquid crystal compounds are 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 compounds constituting the first component and the second component and the third component added as necessary is not added. It may be used for

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 the 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 having a GH (Guest host) mode.
When the antifoaming agent is added to the liquid crystal composition according to the present invention, it becomes possible to suppress foaming during the transportation of the liquid crystal composition or during the production process of the liquid crystal display element from the liquid crystal composition. .

  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, an antioxidant can suppress a decrease in specific resistance when the liquid crystal composition is heated, and an ultraviolet absorber suppresses a decrease in specific resistance when the liquid crystal composition is irradiated with light. It is possible. Moreover, when an ultraviolet absorber and antioxidant are added to a liquid crystal composition, it is preferable at the point which can prevent the said problem by heating and the deterioration by the light at the time of liquid crystal element use.

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-n-octoxybenzophenone.

A specific example of the benzoate ultraviolet absorber is 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.

  As said antioxidant, a phenolic antioxidant, an organic sulfur type antioxidant, etc. can be mentioned. In particular, from the viewpoint that the antioxidant effect is high without changing the physical properties of the liquid crystal composition, an antioxidant represented by the following formula is preferable.

In the above formula (I), w represents an integer of 1 to 15.
Specific examples of the phenolic antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl- 4-propylphenol, 2,6-di-t-butyl-4-butylphenol, 2,6-di-t-butyl-4-pentylphenol, 2,6-di-t-butyl-4-hexylphenol, 2 , 6-di-t-butyl-4-heptylphenol, 2,6-di-t-butyl-4-octylphenol, 2,6-di-t-butyl-4-nonylphenol, 2,6-di-t- Butyl-4-decylphenol, 2,6-di-tert-butyl-4-undecylphenol, 2,6-di-tert-butyl-4-dodecylphenol, 2,6-di-tert-butyl-4- Tridecylphenol, 2,6-di-t Butyl-4-tetradecylphenol, 2,6-di-t-butyl-4-pentadecylphenol, 2,2′-methylenebis (6-t-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].

  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 amount of the additive typified by an ultraviolet absorber, an antioxidant and the like can be added and used within a range that does not impair the purpose of the present invention and can achieve the purpose of adding the additive.

  For example, when the ultraviolet absorber or the antioxidant is added, the addition ratio is usually in the range of 10 ppm to 500 ppm, preferably 30 to 300 ppm, based on the total weight of the liquid crystal composition according to the present invention. The range is more preferably 40 to 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 the compound constituting each component is a liquid, the respective compounds are mixed and shaken, and when the compound includes a solid, the respective compounds are mixed. It can be prepared by making each liquid by heating and then shaking. The liquid crystal composition according to the present invention can also be prepared by other known methods.

[Characteristics of liquid crystal composition]
In the liquid crystal composition according to the present invention, the upper limit temperature of the nematic phase can be set to 70 ° C. or more, the lower limit temperature of the nematic phase can be set to −20 ° C. or less, and the temperature range of the nematic phase is wide. Therefore, a liquid crystal display element including this liquid crystal composition can be used in a wide temperature range.

In the liquid crystal composition according to the present invention, the optical anisotropy can be set in the range of 0.08 to 0.14, and further in the range of 0.05 to 0.18, 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 -5.0 to -2.0, preferably the dielectric anisotropy in the range of -4.5 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 that operates in the IPS mode and the VA mode.

[Liquid crystal display element]
The liquid crystalline composition according to the present invention has an operation mode such as a PC mode, a TN mode, an STN mode, and an OCB mode, and not only a liquid crystal display element driven by an AM mode, but also a PC mode, a TN mode, an STN mode, It can also be used for a liquid crystal display element that has an operation mode such as an OCB mode, a VA mode, an IPS mode, and is driven by a passive matrix (PM) method.

These AM-type and PM-type liquid crystal display elements 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 prepared 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.

  In particular, since the liquid crystal composition according to the present invention has the above-described characteristics, an AM mode liquid crystal driven in an operation mode using a liquid crystal composition having a negative dielectric anisotropy such as a VA mode or an IPS mode. The present invention can be suitably used for a display element, and in particular, can be suitably used for an AM liquid crystal display element driven in a VA mode.

  Note that in a liquid crystal display element driven in a TN mode, a 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 driven 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 driven 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 driven in the IPS mode is reported in International Publication No. 91/10936 pamphlet (family: US5576867).

[Examples of liquid crystal compound (a)]
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited by these Examples. Unless otherwise specified, “%” means “% by weight”.

Since the obtained compound was identified by a nuclear magnetic resonance spectrum obtained by ¹ H-NMR analysis, a gas chromatogram obtained by gas chromatography (GC) analysis, etc., the analysis method will be described first.

¹ H-NMR analysis DRX-500 (Bruker Biospin Co., Ltd.) was used as the measurement apparatus. The measurement was carried out by dissolving the sample produced in Examples and the like in a deuterated solvent in which a sample such as CDCl ₃ is soluble, and at room temperature under conditions of 500 MHz and 24 times of integration. In the description of the obtained nuclear magnetic resonance spectrum, s is a singlet, d is a doublet, t is a triplet, q is a quartet, and m is a multiplet. Tetramethylsilane (TMS) was used as a reference material for the zero point of the chemical shift δ value.

GC analysis As a measuring apparatus, a GC-14B gas chromatograph manufactured by Shimadzu Corporation was used. As the column, a capillary column CBP1-M25-025 (length 25 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Shimadzu Corporation; dimethylpolysiloxane; nonpolar) was used as the stationary liquid phase.
Helium was used as the carrier gas, and the flow rate was adjusted to 1 ml / 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 toluene to prepare a 1% by weight solution, and 1 μl of the resulting solution was injected into the sample vaporization chamber. As a recorder, a C-R6A 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., HP manufactured by Agilent Technologies Inc.
-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.

  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 analysis sample is not completely the same as the area% of each peak of the analysis sample. However, when the above-described column is used in the present invention, the correction factor is substantially 1. Therefore, the weight% of the component compound in the analysis sample substantially corresponds to the area% of each peak in the analysis sample. This is because there is no significant difference in the correction coefficients of the component liquid crystal compounds. 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.

[Samples for measuring physical properties of liquid crystal compounds, etc.]
There are two types of samples for measuring the physical property values of the liquid crystal compound: when the compound itself is used as a sample, and when the compound is mixed with a mother liquid crystal as a sample.

  In the latter case using a sample in which a compound is mixed with mother liquid crystals, the measurement is performed by the following method. First, 15% by weight of the obtained liquid crystal compound and 85% by weight of the mother liquid crystal are mixed to prepare a sample. Then, an extrapolated value is calculated from the measured value of the obtained sample according to the extrapolation method shown in the following equation. This extrapolated value is taken as the physical property value of this compound.

<Extrapolated value> = (100 × <Measured value of sample> − <Weight% of mother liquid crystal> × <Measured value of mother liquid crystal>) / <Weight% of liquid crystalline compound>
Even when the ratio between the liquid crystal compound and the mother liquid crystal is this ratio, when the smectic phase or crystal is precipitated at 25 ° C., the ratio of the liquid crystal compound and the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% by weight. The physical properties of the sample were measured with a composition in which the smectic phase or crystals did not precipitate at 25 ° C. An interpolated value is obtained and used as a physical property value of the liquid crystal compound.

There are various types of mother liquid crystals used for the measurement. For example, the compositions of mother liquid crystals (ii) and mother liquid crystals (i-ii) are as follows.
Mother liquid crystal (ii):

  Mother liquid crystal (i-ii):

Note that the liquid crystal composition itself was used as a sample for measuring physical properties of the liquid crystal composition.
[Method for measuring physical properties of liquid crystal compounds, etc.]
The physical property values were measured by the method described later. 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. Moreover, TFT was not attached to the TN element or VA element used for the measurement.

  Among the measured values, the values obtained using the liquid crystal compound itself as a sample and the values obtained using the liquid crystal composition itself as a sample are described as experimental data. When the compound was mixed with mother liquid crystals and obtained as a sample, the value obtained by extrapolation was taken as the extrapolated value.

Phase structure and transition temperature (℃)
Measurement was carried out by the methods (1) and (2) below.
(1) A compound is placed on a hot plate (Mettler FP-52 type hot stage) equipped with a polarizing microscope, and the phase state and its change are observed with a polarizing microscope while heating at a rate of 3 ° C./min. , Identified the type of phase.
(2) Perkin Elmer scanning calorimeter DSC-7 system or Diamond D
Using the SC system, the temperature was raised and lowered at a rate of 3 ° C./min, the endothermic peak accompanying the phase change of the sample, or the starting point of the exothermic peak was determined by extrapolation (on set), and the transition temperature was determined.

Hereinafter, the crystal was expressed as C. When the crystal could be distinguished, it was expressed as C ₁ or C ₂ , respectively. Further, the smectic phase is represented as S and the nematic phase is represented as N. The liquid (isotropic) was designated as I. In the smectic phase, when the smectic B phase or the smectic A phase can be distinguished, they are represented as S _B or S _A , respectively. As a notation of the transition temperature, for example, “C 50.0 N 100.0 I” means that the transition temperature (CN) from the crystal to the nematic phase is 50.0 ° C., and the transition temperature from the nematic phase to the liquid ( NI) is 100.0 ° C. The same applies to other notations.

Maximum temperature of nematic phase (T _NI ; ° C)
A sample (liquid crystalline composition or a mixture of a liquid crystal compound and a mother liquid crystal) is placed on a hot plate (Mettler FP-52 hot stage) of a melting point measuring apparatus equipped with a polarizing microscope at a rate of 1 ° C./min. A polarizing microscope was observed while heating. The temperature at which a part of the sample changed from a nematic phase to an isotropic liquid was defined as the upper limit temperature of the nematic phase. Hereinafter, the upper limit temperature of the nematic phase may be simply abbreviated as “upper limit temperature”.

Low-temperature compatibility Sample in which mother liquid crystal and liquid crystal compound are mixed so that the liquid crystal compound is 20% by weight, 15% by weight, 10% by weight, 5% by weight, 3% by weight, and 1% by weight. And put the sample in a glass bottle. The glass bottle was stored in a freezer at −10 ° C. or −20 ° C. for a certain period, and then it was observed whether a crystal or smectic phase was precipitated.

Viscosity (η; measured at 20 ° C .; mPa · s)
It measured using the E-type rotational viscometer.
Rotational viscosity (γ1; measured at 25 ° C .; mPa · s)
The measurement followed the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample (a liquid crystal composition or a mixture of a liquid crystal compound and a mother liquid crystal) was put in a VA device having a distance (cell gap) between two glass substrates of 20 μm. This element was applied stepwise in increments of 1 volt in the range of 30 to 50 volts. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. The value of rotational viscosity was obtained from these measured values and the paper by M. Imai et al., Formula (8) on page 40. The dielectric anisotropy necessary for this calculation was a value measured in the dielectric anisotropy section described later.

Optical anisotropy (refractive index anisotropy; measured at 25 ° C .; Δn)
The measurement was performed at 25 ° C. using an Abbe refractometer using light with a wavelength of 589 nm and a polarizing plate attached to the eyepiece. After rubbing the surface of the main prism in one direction, a sample (a liquid crystalline composition or a mixture of a liquid crystal compound and a mother liquid crystal) was dropped onto the main prism. The refractive index (n‖) was measured when the direction of polarized light was parallel to the direction of rubbing. The refractive index (n⊥) was measured when the direction of polarized light was perpendicular to the direction of rubbing. The value of optical anisotropy (Δn) was calculated from the equation: Δn = n∥−n⊥.

Dielectric anisotropy (Δε; measured at 25 ° C)
The dielectric anisotropy was measured by the following method.
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 (a liquid crystal composition or a mixture of a liquid crystal compound and a mother liquid crystal) is placed in the obtained VA element, 0.5 V (1 kHz, sine wave) is applied, and the dielectric constant (in the major axis direction of the liquid crystal molecules ( ε‖) was measured. In addition, a sample (a liquid crystal composition or a mixture of a liquid crystal compound and a mother liquid crystal) is put into the obtained TN device, 0.5 V (1 kHz, sine wave) is applied, and the dielectric in the minor axis direction of the liquid crystal molecules The rate (ε⊥) was measured.

The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.
Ultraviolet current value (Juv; measured at 25 ° C .; μA)
A glass substrate on which silicon dioxide was obliquely deposited was prepared. A sample was put in a cell having a distance (cell gap) between the two glass substrates obtained of 10 μm to produce a TN device. This TN device was irradiated with 12 mW / cm ² of ultraviolet light for 20 minutes (the distance between the light source and the subject was 20 cm). Measurement was performed by applying a 3 V, 32 Hz rectangular wave to the TN device. This ultraviolet irradiation test is an accelerated test, and was used as a test corresponding to the light resistance test of the TN device.

[Example 1]
Synthesis of 2-chloro-1-ethoxy-3-fluoro-4- (4-pentylcyclohex-1-enyl) benzene (No. 23)

First Step 2.9 g of well-dried magnesium and 20 ml of THF were added to a reactor under a nitrogen atmosphere and heated to 43 ° C. There, 1-bromo-3-dissolved in 80 ml of THF.
30.0 g of chloro-4-ethoxy-2-fluoro-benzene (1)
The solution was slowly added dropwise in the temperature range of 0 ° C. and further stirred for 90 minutes. Thereafter, 19.0 g of 4-pentyl-cyclohexanone (2) dissolved in 20 ml of THF was slowly added dropwise in a temperature range of 38 ° C. to 44 ° C., and further stirred for 60 minutes. The obtained reaction mixture was cooled to 30 ° C., added to a container containing 3N-hydrochloric acid 100 ml and toluene 100 ml, mixed and then allowed to stand to separate into an organic layer and an aqueous layer, and an extraction operation. Went. The obtained organic layer was separated, washed with water, 2N aqueous sodium hydroxide solution, saturated aqueous sodium hydrogen carbonate, and water, and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain 39.5 g of 1- (3-chloro-4-ethoxy-2-fluorophenyl) -4-pentylcyclohexanol (3).
The resulting compound (3) was a yellow oil.

Second Step 39.5 g of Compound (3), 0.4 g of p-toluenesulfonic acid, and toluene 12
0 ml was mixed, and this mixture was heated to reflux for 2 hours while removing distilled water. After cooling the reaction mixture to 30 ° C., 200 ml of water and 100 ml of toluene were added to and mixed with the resulting liquid, and then allowed to stand to separate into two layers, an organic layer and an aqueous layer, and an extraction operation into the organic layer Went. The obtained organic layer was separated, washed with 2N aqueous sodium hydroxide solution, saturated aqueous sodium bicarbonate, and water, and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain a residue. The obtained residue was purified by a preparative operation by column chromatography using heptane as a developing solvent and silica gel as a filler, and further purified by recrystallization from Solmix A-11 (manufactured by Nippon Alcohol Sales Co., Ltd.) 21.5 g of 2-chloro-1-ethoxy-3-fluoro-4- (4-pentylcyclohex-1-enyl) benzene (No. 23) was obtained. The yield based on the compound (2) was 58.7%.

The transition temperature of compound (No. 23) obtained is as described below.
Transition temperature: C 24.8 (N 10.9) I
The chemical shift δ (ppm) of ¹ H-NMR analysis is as follows, and the obtained compound is
It could be identified as 2-chloro-1-ethoxy-3-fluoro-4- (4-pentylcyclohex-1-enyl) benzene. The measurement solvent is CDCl ₃ .

Chemical shift δ (ppm); 7.04 (t, 1H), 6.64 (dd, 1H), 5.85 (t, 1H), 4.09 (q, 2H), 2.43-2.27 (M, 3H), 1.87-1.77 (m, 2H), 1.61-1.55 (m, 1H), 1.46 (t, 3H), 1.37-1.25 (m , 9H), 0.90 (t, 3H).
[Example 2]
Synthesis of 4- (3-chloro-4-ethoxy-2-fluorophenyl) -trans-4'-propylbicyclohexyl-3-ene (No. 74)

First Step 2.6 g of well-dried magnesium and 20 ml of THF were added to a reactor under a nitrogen atmosphere and heated to 40 ° C. Thereto, 26.6 g of the compound (1) dissolved in 80 ml of THF was slowly dropped in a temperature range of 30 ° C. to 45 ° C., and further stirred for 30 minutes. Thereafter, 22.2 g of 4′-propylbicyclohexyl-4-one (4) dissolved in 40 ml of THF was slowly added dropwise in the temperature range of 30 ° C. to 50 ° C. and further stirred for 60 minutes. The obtained reaction mixture was cooled to 25 ° C., added to a container containing 100 ml of 3N-hydrochloric acid and 100 ml of toluene, mixed and then allowed to stand to separate into an organic layer and an aqueous layer for extraction operation. Went. The obtained organic layer was separated, washed with water, 2N aqueous sodium hydroxide solution, saturated aqueous sodium hydrogen carbonate, and water, and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain 45.8 g of 4- (3-chloro-4-ethoxy-2-fluorophenyl) -trans-4′-propylbicyclohexyl-4-ol (5). The obtained compound (5) was a yellow solid.

Second Step Compound (5) 45.8 g, p-toluenesulfonic acid 0.5 g, and toluene 15
0 ml was mixed, and this mixture was heated to reflux for 1 hour while removing distilled water. After cooling the reaction mixture to 25 ° C., 200 ml of water and 100 ml of toluene were added to the obtained liquid and mixed, and then allowed to stand to separate into two layers, an organic layer and an aqueous layer, and an extraction operation into the organic layer Went. The obtained organic layer was separated, washed with 2N aqueous sodium hydroxide solution, saturated aqueous sodium bicarbonate, and water, and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain a residue. The obtained residue was purified by a column chromatography fractionation operation using a mixed solvent of heptane and toluene (volume ratio heptane: toluene = 4: 1) as a developing solvent and silica gel as a filler. Further, heptane and ethanol and Was purified by recrystallization from a mixed solvent (volume ratio of heptane: ethanol = 2: 1) to give 4- (3-chloro-4-ethoxy-2-fluorophenyl) -trans-4′-propylbicyclohexyl-3. -28.5g of ene (b74) was obtained. The yield based on the compound (4) was 68.4%.

The transition temperature of compound (No. 74) obtained is as follows.
Transition temperature: C ₁ 69.4 C ₂ 81.8 C ₃ 89.4 S _A 122.1 N 160.8 I
The chemical shift δ (ppm) of ¹ H-NMR analysis is as follows, and the obtained compound is
It could be identified as 4- (3-chloro-4-ethoxy-2-fluorophenyl) -trans-4′-propylbicyclohexyl-3-ene. The measurement solvent is CDCl ₃ .

Chemical shift δ (ppm); 7.04 (t, 1H), 6.64 (dd, 1H), 5.87 (t, 1H), 4.09 (q, 2H), 2.38-2.34 (M, 3H), 1.93-1.74 (m, 6H), 1.47-0.86 (m, 18H).
Example 3
2-Chloro-4-ethoxy-3-fluoro-1- {4- [2- (trans-4-propylcyclohexyl) -2-ethyl] -cyclohex-1-enyl} benzene (No. 10
3) Synthesis

First Step: 1.0 g of well-dried magnesium and 30 ml of THF were added to a reactor under a nitrogen atmosphere and heated to 43 ° C. 10.0 g of 1-bromo-2-chloro-4-ethoxy-3-fluorobenzene (6) dissolved in 20 ml of THF was slowly added dropwise in the temperature range of 43 ° C. to 51 ° C., and the mixture was further stirred for 30 minutes. Thereafter, 21.2 g of 4- [2- (trans-4-propyl-cyclohexyl) -ethyl] -cyclohexanone (7) dissolved in 20 ml of THF was slowly added dropwise in the temperature range of 50 ° C. to 55 ° C., and further stirred for 30 minutes. did. The obtained reaction mixture was cooled to 25 ° C., and added and mixed in a container containing 3N-hydrochloric acid 100 ml and toluene 100 ml. Then, the obtained liquid was allowed to stand, and an organic layer, an aqueous layer, And the extraction operation into the organic layer was performed. The obtained organic layer was separated, washed with water, 2N aqueous sodium hydroxide solution, saturated aqueous sodium hydrogen carbonate, and water, and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to give 1- (2-chloro-4-ethoxy-3-fluorophenyl) -4- [2- (trans-4-propylcyclohexyl) -ethyl] -cyclohexanol (8). 16.4 g was obtained. The obtained compound (8) was a yellow solid.

Second Step Compound (8) 16.4 g, p-toluenesulfonic acid 0.2 g, and toluene 80
ml was mixed, and this mixture was heated to reflux for 2 hours while removing distilled water. After cooling the reaction mixture to 25 ° C., 200 ml of water and 200 ml of toluene were added to and mixed with the resulting liquid, and then allowed to stand to separate into two layers, an organic layer and an aqueous layer, and an extraction operation into the organic layer Went. The obtained organic layer was separated, washed with 2N aqueous sodium hydroxide solution, saturated aqueous sodium bicarbonate, and water, and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain a residue.
The obtained residue was mixed with heptane and toluene (volume ratio heptane: toluene = 4: 1).
) By a preparative operation by column chromatography using a developing solvent and silica gel as a packing material, and further by recrystallization from a mixed solvent of heptane and ethanol (volume ratio heptane: ethanol = 2: 1). 2-chloro-4-ethoxy-3-fluoro-1- {4- [2- (trans-4-propylcyclohexyl) -2-ethyl] -cyclohex-1-enyl} benzene (No. 103) 6.2 g Got. The yield based on the compound (7) was 42.4%.

The transition temperature of the obtained compound (No. 103) is as follows.
Transition temperature: C ₁ 58.7 C ₂ 63.3 N 102.2 I
The chemical shift δ (ppm) of ¹ H-NMR analysis is as follows, and the obtained compound is
It could be identified as 2-chloro-4-ethoxy-3-fluoro-1- {4- [2- (trans-4-propylcyclohexyl) -2-ethyl] -cyclohex-1-enyl} benzene. The measurement solvent is CDCl ₃ .

Chemical shift δ (ppm); 6.85 (dd, 1H), 6.79 (t, 1H), 5.62 (t, 1H), 4.09 (q, 2H), 2.28-2.17 (M, 3H), 1.73 (m, 6H), 1.44 (t, 3H), 1.32-1.13 (m, 12H), 0.88-0.86 (m, 7H).
Example 4
Synthesis of 4- (3-chloro-2-fluoro-4-methylphenyl) -trans-4 ″ pentyl- [1,1 ′; 4 ′, 1 ″] tercyclohexane-3-ene (No. 177)

First Step 1.1 g of well-dried magnesium and 20 ml of THF were added to a reactor under a nitrogen atmosphere and heated to 53 ° C. To this, 9.3 g of 1-bromo-3-chloro-2-fluoro-4-methylbenzene (9) dissolved in 80 ml of THF was dropped over a period of 60 minutes in the temperature range of 52 ° C. to 62 ° C., and further 30 minutes. Stir. Thereafter, trans-4-pentyl- [1,1 ′; 4′1 ″] tercyclohexane-4 ″ -one dissolved in 50 ml of THF (10) 10.0 g in a temperature range from 53 ° C. to 59 ° C. The solution was added dropwise over a period of time and stirred for another 30 minutes. The obtained reaction mixture was cooled to 25 ° C., added to a container containing 3N-hydrochloric acid 100 ml and toluene 200 ml and mixed, and then the obtained liquid was allowed to stand, and an organic layer, an aqueous layer, And the extraction operation into the organic layer was performed. The obtained organic layer was separated, washed with water, 2N aqueous sodium hydroxide solution, saturated aqueous sodium hydrogen carbonate, and water, and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to give 4- (3-chloro-2-fluoro-4-methylphenyl) -trans-4 ″ pentyl- [1,1 ′; 4 ′, 1 ″] tercyclohexane. 20.0 g of -4-ol (11) was obtained. The obtained compound (11) was a yellow solid.

Second Step Compound (11) 20.0 g, p-toluenesulfonic acid 0.2 g, and toluene 1
00 ml was mixed, and this mixture was heated to reflux for 2 hours while removing distilled water. After cooling the reaction mixture to 30 ° C., 200 ml of water and 100 ml of toluene were added to and mixed with the resulting liquid, and then allowed to stand to separate into two layers, an organic layer and an aqueous layer, and an extraction operation into the organic layer Went. The obtained organic layer was separated, washed with 2N aqueous sodium hydroxide solution, saturated aqueous sodium bicarbonate, and water, and dried over anhydrous magnesium sulfate. After magnesium sulfate was filtered off, the obtained filtrate was developed in column chromatography using silica gel as a filler. The obtained eluent was concentrated under reduced pressure, and the residue was purified by recrystallization from a mixed solvent of toluene and ethanol (volume ratio: toluene: ethanol = 5: 1) to give 4- (3-chloro-2- 9.7 g of fluoro-4-methylphenyl) -trans-4 ″ pentyl- [1,1 ′; 4 ′, 1 ″] tercyclohexane-3-ene (No. 177) was obtained. The obtained compound (No. 177) was colorless crystals, and the yield based on the compound (10) was 70.3%.

The transition temperature of the obtained compound (No. 177) is as follows.
Transition temperature: C 105.4 S _A 252.2 N 268.3 I
The chemical shift δ (ppm) of ¹ H-NMR analysis is as follows, and the obtained compound is
4- (3-Chloro-2-fluoro-4-methylphenyl) -trans-4''pentyl-
It was possible to identify [1,1 ′; 4 ′, 1 ″] tercyclohexane-3-ene.
The measurement solvent is CDCl ₃ .

Chemical shift δ (ppm); 7.00 (t, 1H), 6.93 (dd, 1H), 5.90 (t, 1H), 2.36-2.31 (m, 5H), 2.23 (Dt, 1H), 1.96-1.69 (m, 10H), 1.42-1.201 (m, 8H), 1.16-1.11 (m, 4H), 1.05-0 .80 (m, 13H).
Example 5
Synthesis of 3-chloro-4-ethoxy-2-fluoro-4 '-(4-propylcyclohex-1-enyl) -biphenyl (No. 130)

First Step: 4.79 g of well-dried magnesium and 50 ml of THF were added to a reactor under a nitrogen atmosphere and heated to 50 ° C. Thereto, 50.0 g of Compound (1) dissolved in 200 ml of THF was added dropwise over a period of 60 minutes in a temperature range of 43 ° C. to 48 ° C., and the mixture was further stirred for 60 minutes. The reaction mixture was cooled to 25 ° C. Thereafter, the obtained reaction mixture was dropped into a solution of 24.6 g of trimethyl borate cooled to −50 ° C. and 100 ml of THF over 60 minutes in a temperature range of −60 ° C. to −40 ° C. in a nitrogen atmosphere. did. The reaction mixture was returned to 0 ° C. and then poured into 400 ml of 3N hydrochloric acid at 0 ° C. Then, 700 ml of ethyl acetate was added to this solution and mixed, and then allowed to stand to separate into an organic layer and an aqueous layer, and an extraction operation into the organic layer was performed. The obtained organic layer was separated, washed with saturated aqueous sodium hydrogen carbonate and water, and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain a residue. This residue was recrystallized from heptane. This recrystallization operation was repeated again to obtain 35.9 g of 3-chloro-4-ethoxy-2-fluorophenylboronic acid (12). Compound (12) obtained
Was a slightly yellow solid.

Second Step 37.7 g of 1,4-dibromobenzene (13) and 300 ml of THF were put into a reactor under a nitrogen atmosphere and stirred at -69 ° C. Thereto, 100 ml of 1.6M n-BuLi hexane solution was added dropwise over 1 hour in a temperature range of -69 ° C to -62 ° C, and the mixture was further stirred at -70 ° C for 1 hour. To the reaction mixture, 22.4 g of 4-propylcyclohexanone (14) dissolved in 20 ml of THF was slowly added dropwise in the temperature range of -70 ° C to -60 ° C. After gradually returning to 0 ° C., the reaction mixture was slowly poured into 1000 ml of 0 ° C. water and extracted with 500 ml of toluene. The obtained organic layer was washed with 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and water, and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain 50.1 g of 1- (4-bromophenyl) -4-propylcyclohexanol (15). The obtained compound (15) was a yellow oily substance.

Third Step Compound (15) 50.1 g, p-toluenesulfonic acid 0.5 g, and toluene 2
00 ml was mixed, and this mixture was heated to reflux for 3 hours while removing distilled water. After cooling the reaction mixture to 30 ° C., 200 ml of water and 100 ml of toluene were added to and mixed with the resulting liquid, and then allowed to stand to separate into two layers, an organic layer and an aqueous layer, and an extraction operation into the organic layer Went. The obtained organic layer was separated, washed with 2N aqueous sodium hydroxide solution, saturated aqueous sodium bicarbonate, and water, and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain a residue. The obtained residue was purified by a fractionation operation by column chromatography using heptane as a developing solvent and silica gel as a filler, and further purified by recrystallization from Solmix A-11 to give 1-bromo-4- (4 -Propylcyclohex-1-enyl) benzene (16) 27.2 g was obtained.

Fourth Step Under a nitrogen atmosphere, into a reactor containing 60 ml of IPA, 6.0 g of Compound (16), 5.5 g of Compound (12), 5.9 g of potassium carbonate, and 0.13 g of Pd (PPh ₃ ) ₂ Cl ₂ Was added. These were stirred for 3 hours under heating to reflux. After cooling the obtained reaction mixture to 25 ° C., 200 ml of toluene and then 200 ml of water were added, and the obtained toluene solution was washed with 2N sodium hydroxide aqueous solution, saturated aqueous sodium hydrogen carbonate, and water. Thereafter, the solvent was distilled off under reduced pressure to obtain a residue. This residue was mixed with toluene and ethyl acetate (volume ratio: toluene:
Purification by recrystallization from ethyl acetate = 1: 1). The obtained crystals were purified by a fractionation operation by column chromatography using toluene as a developing solvent and silica gel as a filler, and further from a mixed solvent of heptane and ethanol (volume ratio heptane: ethanol = 5: 1). Purification by recrystallization gave 5.9 g of 3-chloro-4-ethoxy-2-fluoro-4 ′-(4-propylcyclohex-1-enyl) -biphenyl (No. 130). The obtained compound (No. 130) was colorless crystals, and the yield based on the compound (13) was 45.0%.

The transition temperature of compound (No. 130) obtained is as follows.
Phase transition temperature (° C.): C 100.1 N 162.2 I
The chemical shift δ (ppm) of ¹ H-NMR analysis is as follows, and the obtained compound is
It could be identified as 3-chloro-4-ethoxy-2-fluoro-4 ′-(4-propylcyclohex-1-enyl) -biphenyl. The measurement solvent is CDCl ₃ .
Chemical shift δ (ppm); 7.44 (s, 4H), 7.25 (t, 1H), 6.77 (dd, 1H), 6.17 (m, 1H), 4.14 (q, 2H) ), 2.47 (m, 2H), 2
. 33 (dt, 1H), 1.92 (m, 1H), 1.87-1.81 (m, 1H), 1.59 (m, 1H), 1.49 (t, 3H), 1.43 -1.27 (m, 5H), 0.93 (t, 3H).
Example 6
Synthesis of 2-chloro-1-ethoxy-3-fluoro-4- (4-vinylcyclohex-1-enyl) benzene (No. 286)

First Step To a reactor under a nitrogen atmosphere, 200.0 g of 1,4-dioxaspiro [4.5] decan-8-one (17), 301.4 g of ethyl ethyl diethylphosphonoacetate and 1,000 ml of toluene were added. The mixture was stirred at 5 ° C. under ice cooling. Thereto, 457.5 g of a 20% sodium ethoxide ethanol solution was dropped in a temperature range of 5 ° C. to 11 ° C. over 2 hours, and further stirred at 10 ° C. for 3 hours. The reaction mixture was then poured into 2,000 ml of 0 ° C. water and mixed. Thereafter, the mixture was allowed to stand to separate into an organic layer and an aqueous layer, and an extraction operation into the organic layer was performed. The obtained organic layer was separated, washed with water, and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain a residue. The obtained residue was purified by a preparative operation by column chromatography using heptane as a developing solvent and silica gel as a filler, and the solvent was distilled off under reduced pressure to give (1,4-dioxaspiro [1,4-dioxaspiro [ 4,5] dec-8-ylidene) acetic acid ethyl ester (18) (267.3 g) was obtained.

Second Step 267.3 g of Compound (18), 5.0 g of Pd / C, 500 ml of isopropyl alcohol (IPA) and 500 ml of toluene were added to the reactor, and the mixture was stirred under a hydrogen atmosphere for 24 hours. After confirming the completion of the reaction by GC analysis, Pd / C was filtered off and the solvent was distilled off under reduced pressure to obtain a residue. The obtained residue was purified by a preparative operation by column chromatography using heptane as a developing solvent and silica gel as a filler, and the solvent was distilled off under reduced pressure to give a colorless transparent liquid (1,4-dioxaspiro). There were obtained 255.2 g of [4,5] dec-8-yl) acetic acid ethyl ester (19).

Step 3 To the reactor under nitrogen atmosphere, 20.0 g of lithium aluminum hydride (LAH) and TH
F (800 ml) was added, and the mixture was stirred at 3 ° C. under ice cooling. Thereto, 190.0 g of the compound (19) dissolved in 200 ml of THF was added dropwise in the temperature range of 0 ° C. to 7 ° C. over 2 hours, and further stirred at 0 ° C. for 3 hours. After confirming the completion of the reaction by GC analysis, a mixture of 60 ml of THF and 60 ml of acetone was added dropwise at 0 ° C. over 30 minutes, and 100 ml of 2N sodium hydroxide aqueous solution was added dropwise at 10 ° C. over 30 minutes. did. The precipitated white solid was filtered off,
To the filtrate, 300 ml of toluene and 1,000 ml of brine were added and mixed. Thereafter, the mixture was allowed to stand to separate into an organic layer and an aqueous layer, and an extraction operation into the organic layer was performed. The obtained organic layer was separated, washed with brine, and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain 152.7 g of colorless transparent liquid 2- (1,4-dioxaspiro [4,5] dec-8-yl) ethanol (20).

Fourth Step To a reactor under a nitrogen atmosphere, 150.0 g of compound (20), triphenylphosphine (
(Ph ₃ P) 274.3 g, 71.3 g of imidazole and 900 ml of toluene were added, and the mixture was stirred at 3 ° C. under ice cooling. Thereto, 255.5 g of iodine was divided into 10 portions and added in a temperature range of 3 ° C. to 10 ° C. over 2 hours, and further stirred at 0 ° C. for 3 hours. After confirming that the reaction was completed by GC analysis, the precipitated reddish brown solid was filtered off and the filtrate was concentrated. To the obtained residue, 400 ml of heptane was added, the precipitated pale yellow solid was filtered off, and the filtrate was concentrated to obtain a residue. The residue was purified by a preparative operation by column chromatography using toluene as a developing solvent and silica gel as a filler, and the solvent was distilled off under reduced pressure, whereby 8- (2-iodoethyl)- 223.9 g of 1,4-dioxaspiro [4,5] decane (21) was obtained.

Step 5 223.0 g of Compound (21) and 800 ml of DMF were added to a reactor under a nitrogen atmosphere, and the mixture was stirred at 3 ° C. under ice cooling. Potassium t-butoxide (t-BuOK) 92.9 there
g was added in 10 portions over 2 hours in the temperature range of 3 ° C. to 10 ° C., and further stirred at 0 ° C. for 3 hours. After confirming the completion of the reaction by GC analysis, the reaction mixture was poured into a mixture of 1,500 ml of heptane and 1,500 ml of water at 0 ° C. and mixed. Thereafter, the mixture was allowed to stand to separate into an organic layer and an aqueous layer, and an extraction operation into the organic layer was performed. The obtained organic layer was separated, washed with water, and dried over anhydrous magnesium sulfate. The obtained organic layer was purified by a fractionation operation by column chromatography using heptane as a developing solvent and silica gel as a filler, and the solvent was distilled off under reduced pressure. The obtained residue was distilled under reduced pressure to obtain 103.3 g of colorless and transparent liquid 8-vinyl-1,4-dioxaspiro [4,5] decane (22).

Step 6 To a reactor under a nitrogen atmosphere, 103.3 g of Compound (22), 86.5 g of 98% formic acid and 200 ml of toluene were added, heated and stirred for 2 hours under reflux. After confirming that the reaction was complete by GC analysis, the reaction mixture was poured into 500 ml of 0 ° C. saline and mixed. Thereafter, the mixture was allowed to stand to separate into an organic layer and an aqueous layer, and an extraction operation into the organic layer was performed. The obtained organic layer was separated, washed with brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was distilled under reduced pressure to obtain 66.7 g of colorless and transparent liquid 4-vinylcyclohexanone (23).

Step 7 1.5 g of well-dried magnesium and 30 ml of THF were added to a reactor under a nitrogen atmosphere and heated to 40 ° C. Thereto, 15.3 g of the compound (1) dissolved in 30 ml of THF was slowly dropped in a temperature range of 35 ° C. to 49 ° C., and further stirred for 30 minutes. Thereafter, 5.0 g of the compound (23) dissolved in 5 ml of THF was slowly added dropwise in the temperature range of 30 ° C. to 40 ° C. and further stirred for 30 minutes. The resulting reaction mixture was cooled to 25 ° C., and poured into a mixture of 100 ml of 1N hydrochloric acid and 100 ml of toluene and mixed. Then, it left still and was made to isolate | separate into an organic layer and a water layer, and extraction operation to an organic layer was performed. The obtained organic layer was separated, washed with water, 2N aqueous sodium hydroxide solution, saturated aqueous sodium hydrogen carbonate, and water, and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain 16.0 g of 1- (3-chloro-4-ethoxy-2-fluorophenyl) -4-vinylcyclohexanol (24) as a yellow liquid.

Step 8 Compound (24) 16.0 g, p-toluenesulfonic acid 0.3 g, and toluene 8
0 ml was mixed, and this mixture was heated to reflux for 1 hour while removing distilled water. After the reaction mixture was cooled to 25 ° C., 100 ml of water and 100 ml of toluene were added to and mixed with the resulting liquid. Then, it left still and isolate | separated into two layers, an organic layer and an aqueous layer, and extraction operation to the organic layer was performed. The obtained organic layer was separated, washed with 2N aqueous sodium hydroxide solution, saturated aqueous sodium bicarbonate, and water, and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain a residue. The obtained residue was purified by preparative operation by column chromatography using a mixed solvent of heptane and toluene (volume ratio heptane: toluene = 2: 1) as a developing solvent and silica gel as a packing material. Purification by crystals and drying gave 5.11 g of white 2-chloro-1-ethoxy-3-fluoro-4- (4-vinylcyclohex-1-enyl) benzene (No. 286). The yield based on the compound (23) was 45.2%.

The transition temperature of compound (No. 286) obtained is as follows.
Transition temperature: C ₁ 14.5 C ₂ 29.4 I
The chemical shift δ (ppm) of ¹ H-NMR analysis is as follows, and the obtained compound is
It could be identified as 2-chloro-1-ethoxy-3-fluoro-4- (4-vinylcyclohex-1-enyl) benzene. The measurement solvent is CDCl ₃ .

Chemical shift δ (ppm); 7.04 (t, 1H), 6.64 (dd, 1H), 5.90-5.83 (m, 2H), 5.05 (dt, 1H), 4.97 (Dt, 1H) 4.10 (q, 2H), 2.48-2.27 (m, 4H), 2.06-2.00 (m, 1H), 1.93-1.88 (m, 1H), 1.56-1.49 (m, 1H), 1.42 (t, 3H).
Example 7
The compound (No. 1) shown below by the same method as the synthesis method described in Examples 1 to 6
) To (No. 476) can be synthesized. In the above compound group, Examples 1 to
The compound obtained in 6 is also described. The appended data is a value measured according to the method described above. The transition temperature is a measured value of the compound itself, and the upper limit temperature (T _NI ), dielectric anisotropy (Δε), and optical anisotropy (Δn) are samples obtained by mixing the compound with the base liquid crystal (ii). Is an extrapolated value obtained by converting the measured value according to the extrapolation method.

[Comparative Example 1]
As a comparative example, trans-4- (3-chloro-4-ethoxy-2-fluorophenyl)-in which hydrogen at the 2-position on the benzene ring is substituted with fluorine and hydrogen at the 3-position is substituted with chlorine and does not have a cyclohexenylene group Trans-4′-propylbicyclohexyl (E) was synthesized.

Five compounds described as the mother liquid crystals (ii) described above were mixed to prepare a mother liquid crystal (ii) having a nematic phase. The physical properties of the mother liquid crystal (ii) were as follows.
Maximum temperature (T _NI ) = 74.0 ° C .;
Viscosity (η ₂₀ ) = 18.9 mPa · s;
Optical anisotropy (Δn) = 0.087;
Dielectric anisotropy (Δε) = − 1.3.

85% by weight of the mother liquid crystal (ii) and 15% by weight of the synthesized trans-4- (3-chloro-4-ethoxy-2-difluorophenyl) -trans-4′-propylbicyclohexyl (E) A liquid crystal composition (ii) comprising: The physical property value of the obtained liquid crystal composition (ii) was measured, and the extrapolated value of the physical property of the comparative compound (E) was calculated by extrapolating the measured value. The values were as follows:
Maximum temperature (T _NI ) = 146.5 ° C .;
Optical anisotropy (Δn) = 0.108;
Dielectric anisotropy (Δε) = − 5.5;
Viscosity (η) = 70.8 mPa · s
Four compounds described as the mother liquid crystals (i-ii) described above were mixed to prepare a mother liquid crystal (i-ii) having a nematic phase. The current value of the mother liquid crystal (i-ii) after irradiation with ultraviolet rays was as follows.
Ultraviolet current value (Juv) = 0.64 μA
The mother liquid crystal (i-ii) 85% by weight and the synthesized trans-4- (3-chloro-4-
A liquid crystal composition (iii) consisting of 15% by weight of ethoxy-2-difluorophenyl) -trans-4′-propylbicyclohexyl (E) was prepared. The ultraviolet current value (Juv) of the obtained liquid crystal composition (iii) was measured.
Ultraviolet current value (Juv) = 10.38 μA
[Comparative Example 2]
As a comparative example, the 2-position hydrogen on the benzene ring is substituted with fluorine and the 3-position hydrogen with chlorine, and has no cyclohexenylene group 2-chloro-1-ethoxy-3-fluoro-4- (trans-4- Propylcyclohexyl) benzene (F) was synthesized.

A liquid crystal composition comprising 85% by weight of the mother liquid crystal (ii) and 15% by weight of the synthesized 2-chloro-1-ethoxy-3-fluoro-4- (trans-4-propylcyclohexyl) benzene (F) (Iv) was prepared. The physical property value of the obtained liquid crystal composition (iv) was measured, and the extrapolated value of the physical property of the comparative compound (F) was calculated by extrapolating the measured value. The values were as follows:
Maximum temperature (T _NI ) = 0.6 ° C;
Optical anisotropy (Δn) = 0.065;
Dielectric anisotropy (Δε) = − 5.3;
Viscosity (η) = 51.0 mPa · s
A liquid crystal composition comprising 85% by weight of mother liquid crystals (i-ii) and 15% by weight of synthesized 2-chloro-1-ethoxy-3-fluoro-4- (trans-4-propylcyclohexyl) benzene (F) (V) was prepared. The ultraviolet current value (Juv) of the obtained liquid crystal composition (v) was measured.
Ultraviolet current value (Juv) = 11.83 μA
[Comparative Example 3]
As a comparative example, 2-chloro-4-ethoxy-3-fluoro-1- {4- [2] in which 2-position hydrogen on the benzene ring is substituted with chlorine and 3-position hydrogen with fluorine and does not have a cyclohexenylene group -(Trans-4-propylcyclohexyl) ethyl] cyclohexyl} benzene (G) was synthesized.

Mother liquid crystal (ii) 85% by weight and synthesized 2-chloro-4-ethoxy-3-fluoro-1- {4- [2- (trans-4-propylcyclohexyl) ethyl] cyclohexyl} benzene (G) Liquid crystal composition (vi) and mother liquid crystal (ii) comprising 90% by weight of 2-chloro-4-ethoxy-3-fluoro-1- {4- [2- (trans A liquid crystal composition (vii) comprising 10% by weight of -4-propylcyclohexyl) ethyl] cyclohexyl} benzene (G) was prepared. When these liquid crystal compositions (vi) and (vii) were stored in a freezer at −10 ° C. for 30 days, crystals were precipitated in the liquid crystal composition (vi), and the liquid crystal composition (vii) had a nematic phase. It remained.
Example 8
Physical properties of liquid crystal compound (No. 74) 85% by weight of mother liquid crystal (ii) and 4- (3-chloro-4-ethoxy-2-fluorophenyl) -trans-4 ′ obtained in Example 2 -Propylbicyclohexyl-3-ene (
No. A liquid crystal composition (viii) consisting of 15% by weight of 74) was prepared. A liquid crystal compound (No. 74) was measured by measuring the physical property value of the obtained liquid crystal composition (viii) and extrapolating the measured value.
The extrapolated value of the physical property was calculated. The values were as follows:
Maximum temperature (T _NI ) = 145.6 ° C .;
Optical anisotropy (Δn) = 0.127;
Dielectric anisotropy (Δε) = − 5.1;
Viscosity (η) = 63.5 mPa · s
Therefore, the liquid crystalline compound (No. 74) is a compound that can increase the maximum temperature (T _NI ), increase the optical anisotropy (Δn), and negatively increase the dielectric anisotropy (Δε). I found out.

In addition, compared with the comparative compound (E), the nematic phase has the same maximum temperature (T _NI ), but has a large optical anisotropy (Δn) and a small viscosity (η). It was.

Base liquid crystal (i-ii) 85% by weight and 4- (3-chloro-4-ethoxy-2-fluorophenyl) -trans-4′-propylbicyclohexyl-3-ene (No.) obtained in Example 2 74) and 15% by weight of a liquid crystal composition (ix). The ultraviolet current value (Juv) of the obtained liquid crystal composition (ix) was measured.
Ultraviolet current value (Juv) = 2.04 μA
Compared with Comparative Example 1, the liquid crystal compound (No. 74) had a small ultraviolet current value (Juv), and thus was found to be a compound excellent in light resistance.

Example 9
Physical properties of liquid crystal compound (No. 18) 85% by weight of mother liquid crystal (ii) and 2-chloro-1-ethoxy-3 obtained in Example 6
-Fluoro-4- (4-propylcyclohex-1-enyl) -benzene (No. 18
A liquid crystal composition (x) consisting of 15% by weight of) was prepared. The physical property value of the obtained liquid crystal composition (x) was measured, and the extrapolated value of the physical property of the liquid crystal compound (No. 18) was calculated by extrapolating the measured value. The values were as follows:
Maximum temperature (T _NI ) = − 1.4 ° C .;
Optical anisotropy (Δn) = 0.087;
Dielectric anisotropy (Δε) = − 5.3;
Viscosity (η) = 47.7 mPa · s
From this, it was found that the liquid crystal compound (No. 18) was a compound capable of negatively increasing the dielectric anisotropy (Δε).

In addition, compared with Comparative Example Compound (F), the upper limit temperature (T _NI ) of the nematic phase is the same, but the compound has a large optical anisotropy (Δn) and a small viscosity (η). It was.

Mother liquid crystal (i-ii) 85% by weight and 2-chloro-1-ethoxy- obtained in Example 7
3-fluoro-4- (4-propylcyclohex-1-enyl) benzene (No. 18
A liquid crystal composition (xi) consisting of 15% by weight of) was prepared. The ultraviolet current value (Juv) of the obtained liquid crystal composition (xi) was measured.
Ultraviolet current value (Juv) = 1.54 μA
Compared with the comparative compound (F), the liquid crystal compound (No. 18) has an ultraviolet current value (Juv
) Was small, it was revealed that the compound was excellent in light resistance.

Example 10
Low-temperature compatibility of liquid crystal compound (No. 103) 85% by weight of mother liquid crystal (ii) and 2-chloro-1-ethoxy-3 obtained in Example 3
-Fluoro-4- (4-propylcyclohex-1-enyl) benzene (No. 103
A liquid crystal composition (xii) consisting of 15% by weight of) was prepared. When this liquid crystal composition (xii) was stored in a freezer at −10 ° C. for 30 days, the liquid crystal composition (xii) remained in a nematic phase.

It was revealed that the liquid crystal compound (No. 103) is a compound having excellent low-temperature compatibility as compared with the comparative example compound (G).
[Examples of liquid crystal composition]
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 composition 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 not described but is simply described as “-”, it means that this compound is another compound not corresponding 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 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 (a liquid crystal composition or a mixture of a liquid crystal compound and a mother liquid crystal) is put into the obtained VA element, 0.5 volt (1 kHz, sine wave) is applied, and the dielectric constant in the major axis direction of the liquid crystal molecules. (Ε‖) was measured. Further, a sample (liquid crystal composition or a mixture of a liquid crystal compound and a mother liquid crystal) is put into the obtained TN device, 0.5 volt (1 kHz, sine wave) is applied, and the liquid crystal molecules in the minor axis direction are applied. The dielectric constant (ε⊥) was measured. The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.

(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 there is a TN element) / (Area value when there is no TN element) × 100.

  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 was used as a test corresponding to the long-term durability test of the TN device.

[Comparative Example 4]
The following composition was prepared as a comparative example. The reason selected as the comparative example is that this composition contains the compound (2-1), the compound (3-7), the compound (3-29), and the compound (3-33). The components and properties of this composition are as follows.
3-HH-4 (2-1) 12%
3-HH-V (2-1) 24%
3-HB (2F, 3Cl) -O2 (3-7) 15%
5-HB (2F, 3Cl) -O2 (3-7) 14%
3-HHB (2F, 3Cl) -O2 (3-29) 5%
4-HHB (2F, 3Cl) -O2 (3-29) 5%
5-HHB (2F, 3Cl) -O2 (3-29) 5%
3-HBB (2F, 3Cl) -O2 (3-33) 10%
5-HBB (2F, 3Cl) -O2 (3-33) 10%
NI = 69.9 ° C .; TC ≦ −10 ° C .; Δn = 0.081; η = 32.3 mPa · s; Δε = −2.8.

Example 11
The composition of Example 11 has negatively large dielectric anisotropy and large optical anisotropy as compared with that of Comparative Example 4.
3-HChB (2F, 3Cl) -O2 (No. 74) 5%
4-HChB (2F, 3Cl) -O2 (No. 78) 5%
5-HChB (2F, 3Cl) -O2 (No. 80) 5%
3-HH-4 (2-1) 12%
3-HH-V (2-1) 24%
3-HB (2F, 3Cl) -O2 (3-7) 15%
5-HB (2F, 3Cl) -O2 (3-7) 14%
3-HBB (2F, 3Cl) -O2 (3-33) 10%
5-HBB (2F, 3Cl) -O2 (3-33) 10%
NI = 70.7 ° C .; Δn = 0.084; η = 33.7 mPa · s; Δε = −3.0.

Example 12
The composition of Example 12 has negatively large dielectric anisotropy and large optical anisotropy as compared with that of Comparative Example 4.
3-HChB (2F, 3Cl) -O2 (No. 74) 6%
4-HChB (2F, 3Cl) -O2 (No. 78) 6%
5-HChB (2F, 3Cl) -O2 (No. 80) 6%
3-ChB (2F, 3Cl) -O2 (No. 18) 15%
5-ChB (2F, 3Cl) -O2 (No. 23) 14%
3-HH-4 (2-1) 12%
3-HH-V (2-1) 21%
3-HBB (2F, 3Cl) -O2 (3-33) 10%
5-HBB (2F, 3Cl) -O2 (3-33) 10%
NI = 68.3 ° C .; Δn = 0.088; η = 32.8 mPa · s; Δε = −3.2.

Example 13
The composition of Example 13 has negatively large dielectric anisotropy and large optical anisotropy as compared with that of Comparative Example 4, and the lower limit temperature of the nematic phase is low.
4-HChB (2F, 3Cl) -O2 (No. 78) 5%
5-HChB (2F, 3Cl) -O2 (No. 80) 5%
3-ChB (2F, 3Cl) -O2 (No. 18) 10%
5-ChB (2F, 3Cl) -O2 (No. 23) 14%
3-HChB (2Cl, 3F) -O2 (No. 102) 5%
3-ChB (2Cl, 3F) -O2 (No. 46) 5%
3-HH-4 (2-1) 12%
3-HH-V (2-1) 24%
3-HBB (2F, 3Cl) -O2 (3-33) 10%
5-HBB (2F, 3Cl) -O2 (3-33) 10%
NI = 65.8 ° C .; TC ≦ −20 ° C .; Δn = 0.083; η = 33.0 mPa · s; Δε = −3.1.

Example 14
3-HChB (2F, 3Cl) -O2 (No. 74) 4%
4-HChB (2F, 3Cl) -O2 (No. 78) 4%
5-HChB (2F, 3Cl) -O2 (No. 80) 4%
3-HH-V (2-1) 16%
3-HH-V1 (2-1) 8%
V-HHB-1 (2-25) 2%
3-H2B (2F, 3F) -O2 (3-3) 19%
5-H2B (2F, 3F) -O2 (3-3) 19%
3-HBB (2F, 3Cl) -O2 (3-33) 12%
5-HBB (2F, 3Cl) -O2 (3-33) 12%
NI = 71.6 ° C .; Δn = 0.096; η = 24.8 mPa · s; Δε = −3.6.

Example 15
3-HChB (2F, 3Cl) -O2 (No. 74) 5%
5-HChB (2F, 3Cl) -O2 (No. 80) 5%
3-ChB (2F, 3Cl) -O2 (No. 18) 10%
5-ChB (2F, 3Cl) -O2 (No. 23) 10%
3-HH-4 (2-1) 10%
3-HB-O2 (2-4) 20%
5-HB (2F, 3F) -O2 (3-1) 10%
2-HHB (2F, 3F) -1 (3-19) 5%
3-HHB (2F, 3F) -O2 (3-19) 15%
5-HHB (2F, 3F) -O2 (3-19) 10%
NI = 74.5 ° C .; TC ≦ −20 ° C .; Δn = 0.089; η = 28.7 mPa · s; Δε = −3.9.

Example 16
3-HChB (2F, 3Cl) -O2 (No. 74) 5%
4-HChB (2F, 3Cl) -O2 (No. 78) 5%
5-HChB (2F, 3Cl) -O2 (No. 80) 5%
3-ChB (2F, 3Cl) -O2 (No. 18) 7%
5-ChB (2F, 3Cl) -O2 (No. 23) 8%
3-ChBB (2F, 3Cl) -O2 (No. 130) 5%
3-HChB (2Cl, 3F) -O2 (No. 102) 5%
3-ChB (2Cl, 3F) -O2 (No. 46) 5%
3-ChBB (2Cl, 3F) -O2 (No. 158) 8%
3-HH-V (2-1) 10%
2-H2H-3 (2-2) 5%
3-HB-O2 (2-4) 5%
3-HHB-1 (2-25) 5%
V-HHB-1 (2-25) 5%
3-HBB-2 (2-35) 4%
2-BB (3F) B-3 (2-44) 5%
V2-BB (3F) B-1 (2-44) 5%
5-HBB (3F) B-2 (2-73) 3%
NI = 89.5 ° C .; Δn = 0.128; η = 34.6 mPa · s; Δε = −3.0.

Example 17
3-HChB (2F, 3Cl) -O2 (No. 74) 5%
3-ChB (2F, 3Cl) -O2 (No. 18) 10%
5-ChB (2F, 3Cl) -O2 (No. 23) 10%
5-ChBB (2F, 3Cl) -O2 (No. 136) 5%
3-HChB (2Cl, 3F) -O2 (No. 102) 5%
5-HChB (2Cl, 3F) -O2 (No. 108) 5%
3-ChB (2Cl, 3F) -O2 (No. 46) 10%
3-ChBB (2Cl, 3F) -O2 (No. 158) 5%
3-HH-5 (2-1) 9%
3-HH-V1 (2-1) 10%
3-HH-O1 (2-1) 5%
3-HHB-O1 (2-25) 5%
2-BBB (2F) -3 (2-43) 5%
3-HHEH-3 (2-46) 3%
3-HHEH-5 (2-46) 3%
3-HHEBH-3 (2-74) 5%
NI = 84.3 ° C .; Δn = 0.099; η = 34.5 mPa · s; Δε = −3.0.

Example 18
3-HChB (2F, 3Cl) -O2 (No. 74) 5%
3-ChB (2F, 3Cl) -O2 (No. 18) 8%
3-ChBB (2F, 3Cl) -O2 (No. 130) 5%
3-HChB (2Cl, 3F) -O2 (No. 102) 5%
3-ChB (2Cl, 3F) -O2 (No. 46) 7%
3-HH-V1 (2-1) 10%
V-HHB-1 (2-25) 10%
5-HBB (3F) B-3 (2-73) 5%
3-HHEBH-5 (2-74) 5%
3-HB (2F, 3F) -O2 (3-1) 10%
3-H2B (2F, 3F) -O2 (3-3) 10%
3-HHB (2F, 3F) -O2 (3-19) 5%
3-HH2B (2F, 3F) -O2 (3-20) 5%
2-HBB (2F, 3F) -O2 (3-23) 5%
2-BB (2F, 3F) B-3 (3-27) 5%
NI = 93.6 ° C .; Δn = 0.115; η = 31.4 mPa · s; Δε = −3.6.

Example 19
5-HChB (2F, 3Cl) -O2 (No. 80) 5%
3-ChB (2F, 3Cl) -O2 (No. 18) 10%
5-ChB (2F, 3Cl) -O2 (No. 23) 10%
3-ChBB (2F, 3Cl) -O2 (No. 130) 5%
5-HChB (2Cl, 3F) -O2 (No. 108) 5%
3-ChB (2Cl, 3F) -O2 (No. 46) 10%
3-ChBB (2Cl, 3F) -O2 (No. 158) 5%
3-HH-V1 (2-1) 5%
3-HHB-1 (2-25) 10%
2-BB (3F) B-3 (2-44) 5%
5-HBB (3F) B-2 (2-73) 5%
3-HB (2F, 3Cl) -O2 (3-7) 10%
5-HB (2F, 3Cl) -O2 (3-7) 5%
3-HHB (2F, 3Cl) -O2 (3-29) 5%
3-HBB (2F, 3Cl) -O2 (3-33) 5%
NI = 78.3 ° C .; Δn = 0.119; η = 46.6 mPa · s; Δε = −4.1.

Example 20
5-HChB (2F, 3Cl) -O2 (No. 80) 7%
3-ChB (2F, 3Cl) -O2 (No. 18) 10%
3-ChBB (2F, 3Cl) -O2 (No. 130) 5%
3-HChB (2Cl, 3F) -O2 (No. 102) 5%
3-ChB (2Cl, 3F) -O2 (No. 46) 10%
5-ChBB (2Cl, 3F) -O2 (No. 164) 5%
3-HBB-2 (2-35) 10%
2-BBB (2F) -3 (2-43) 5%
2-BB (3F) B-3 (2-44) 5%
5-HBB (3F) B-2 (2-73) 5%
3-HHEBH-5 (2-74) 7%
3-HB (2Cl, 3F) -O2 (3-13) 7%
5-HB (2Cl, 3F) -O2 (3-13) 7%
3-HHB (2Cl, 3F) -O2 (3-39) 5%
3-HBB (2Cl, 3F) -O2 (3-43) 7%
NI = 99.6 ° C .; Δn = 0.136; η = 48.3 mPa · s; Δε = −3.5.

Example 21
3-HChB (2F, 3Cl) -O2 (No. 74) 5%
5-ChB (2F, 3Cl) -O2 (No. 23) 10%
3-ChBB (2F, 3Cl) -O2 (No. 130) 5%
3-HChB (2Cl, 3F) -O2 (No. 102) 5%
3-ChB (2Cl, 3F) -O2 (No. 46) 5%
3-ChBB (2Cl, 3F) -O2 (No. 158) 5%
5-HH-V (2-1) 5%
5-HBB (3F) B-2 (2-73) 5%
3-HHEBH-3 (2-74) 5%
3-H2B (2F, 3F) -O2 (3-3) 10%
3-HB (2F, 3Cl) -O2 (3-7) 10%
3-HB (2Cl, 3F) -O2 (3-13) 10%
3-HHB (2F, 3Cl) -O2 (3-29) 5%
3-HHB (2Cl, 3F) -O2 (3-39) 5%
3-HBB (2F, 3Cl) -O2 (3-33) 5%
5-HBB (2F, 3Cl) -O2 (3-33) 5%
NI = 82.6 ° C .; Δn = 0.109; η = 49.4 mPa · s; Δε = −4.6.

Claims (18)

A liquid crystal compound selected from the group of compounds represented by the following formula (a).

(In the formula (a), Ra and Rb are independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxyalkyl having 2 to 9 carbons, alkenyl having 2 to 10 carbons, and carbon. Alkenyloxy having 2 to 9 carbon atoms, fluoroalkyl having 1 to 10 carbon atoms, or fluoroalkoxy having 1 to 9 carbon atoms;
Ring A ¹ , Ring A ² , and Ring A ³ are independently trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, trans-tetrahydropyran-2,5- Diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1, 4-phenylene, pyridine-2,5-diyl, 6-fluoropyridine-2,5-diyl, or pyridazine-2,5-diyl; Z ¹ , Z ² , and Z ³ are independently
Single bond, — (CH ₂ ) ₂ —, —CH═CH—, —C≡C—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —OCF ₂ —, —CF _{2 O -, - CH 2 CH 2} OCF 2 -, or -
Any of CF ₂ OCH ₂ CH ₂ —;
l, m, and n are independently 0, 1, or 2, but l + m + n is 0, 1, 2, or 3;
One of X ¹ and X ² is fluorine and the other is chlorine;
Q is

Is;
The atoms constituting these compounds may be their isotopes. ) Ring A ¹ , Ring A ² , and Ring A ³ are independently trans-1,4-cyclohexylene or 1,4-phenylene;
Z ¹ , Z ² , and Z ³ are independently a single bond or — (CH ₂ ) ₂ —;
Q is

The liquid crystal compound according to claim 1. The liquid crystalline compound selected from the compound group represented by the following formula (a-1).

(In formula (a-1), Ra ₁ is a linear alkyl having 1 to 10 carbon atoms or a linear alkenyl having 2 to 10 carbon atoms, and Rb ₁ is a linear alkyl having 1 to 10 carbon atoms, Or carbon number 1-9
Is a straight-chain alkoxy. ) The liquid crystalline compound selected from the compound group represented by the following formula (b-1).

(In Formula (b-1), Ra ₁ is a linear alkyl having 1 to 10 carbon atoms or a linear alkenyl having 2 to 10 carbon atoms, and Rb ₁ is a linear alkyl having 1 to 10 carbon atoms, Or carbon number 1-9
Is a straight-chain alkoxy. ) The liquid crystalline compound selected from the compound group represented by the following formula (a-2).

(In formula (a-2), Ra ₁ is a linear alkyl having 1 to 10 carbon atoms or a linear alkenyl having 2 to 10 carbon atoms, and Rb ₁ is a linear alkyl having 1 to 10 carbon atoms, Or carbon number 1-9
Is a straight-chain alkoxy. ) The liquid crystalline compound selected from the compound group represented by the following formula (b-2).

(In Formula (b-2), Ra ₁ is a linear alkyl having 1 to 10 carbon atoms or a linear alkenyl having 2 to 10 carbon atoms, and Rb ₁ is a linear alkyl having 1 to 10 carbon atoms, Or carbon number 1-9
Is a straight-chain alkoxy. )   A liquid crystal composition comprising at least one compound according to any one of claims 1 to 6. A first component comprising at least one compound selected from the compound group described in any one of claims 1 to 6, and the following formula (e-1), formula (e-2), and formula (e A liquid crystal composition having a negative dielectric anisotropy, comprising a second component comprising at least one compound selected from the compound group consisting of 3).

(In formula (e-1) to formula (e-3), Ra ₁₁ and Rb ₁₁ are independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxy having 2 to 9 carbons. Alkyl, alkenyl having 2 to 10 carbons, alkenyloxy having 2 to 9 carbons, fluoroalkyl having 1 to 10 carbons, or fluoroalkoxy having 1 to 9 carbons;
Ring A ¹¹ , Ring A ¹² , Ring A ¹³ , and Ring A ¹⁴ are independently trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, trans-tetrahydropyran- 2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or pyridine-2,5-diyl;
Z ¹¹ , Z ¹² , and Z ¹³ are each independently a single bond, —CH ₂ —CH ₂ —, —CH═CH—, —C≡C—, —COO—, or —CH ₂ O—. . ) From the compound group represented by the following formula (a-1), formula (a-2), formula (a-3), formula (b-1), formula (b-2), and formula (b-3) A first component comprising at least one selected compound and a first component comprising at least one compound selected from the group of compounds comprising the following formula (e-1), formula (e-2), and formula (e-3): A liquid crystal composition having a negative dielectric anisotropy containing two components.

(In Formula (a-1) to Formula (a-3) and Formula (b-1) to Formula (b-3), Ra ₁ is a linear alkyl having 1 to 10 carbon atoms, or 2 to 2 carbon atoms. 10 straight chain alkenyl, Rb ₁ is
It is a C1-C10 linear alkyl or a C1-C9 linear alkoxy. )

(In formula (e-1) to formula (e-3), Ra ₁₁ and Rb ₁₁ are independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxy having 2 to 9 carbons. Alkyl, alkenyl having 2 to 10 carbons, alkenyloxy having 2 to 9 carbons, fluoroalkyl having 1 to 10 carbons, or fluoroalkoxy having 1 to 9 carbons;
Ring A ¹¹ , Ring A ¹² , Ring A ¹³ , and Ring A ¹⁴ are independently trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, trans-tetrahydropyran- 2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or pyridine-2,5-diyl;
Z ¹¹ , Z ¹² , and Z ¹³ are each independently a single bond, —CH ₂ —CH ₂ —, —CH═CH—, —C≡C—, —COO—, or —CH ₂ O—. . )   The content ratio of the first component is in the range of 30 to 85% by weight and the content ratio of the second component is in the range of 15 to 70% by weight based on the total weight of the liquid crystal composition. The liquid crystal composition described in 1. In addition to the first component and the second component, the compound is selected from the group of compounds represented by the following formula (g-1), formula (g-2), formula (g-3), and formula (g-4). The liquid crystal composition according to claim 9, comprising a third component comprising at least one compound.

(In Formula (g-1) to Formula (g-4), Ra ₂₁ and Rb ₂₁ are independently hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or 2 to 9 carbons. An alkoxyalkyl having 2 to 10 carbon atoms, an alkenyloxy having 2 to 9 carbon atoms, a fluoroalkyl having 1 to 10 carbon atoms, or a fluoroalkoxy having 1 to 9 carbon atoms;
Ring A ²¹ , Ring A ²² , and Ring A ²³ are independently trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, trans-tetrahydropyran-2,5- Diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1, 4-phenylene, pyridine-2,5-diyl, 6-fluoropyridine-2,5-diyl, or pyridazine-2,5-diyl;
Z ²¹ , Z ²² and Z ²³ are each independently a single bond, —CH ₂ —CH ₂ —, —CH═CH—, —C≡C—, —OCF ₂ —, —CF ₂ O—, — _{OCF 2 CH 2 CH 2 -,} - CH 2 CH 2 CF 2 O -, - COO -, - OCO -, - OCH 2 -, or -CH ₂ O-;
Y ¹ , Y ² , Y ³ , and Y ⁴ are independently fluorine or chlorine;
q, r, and s are independently 0, 1, or 2, but q + r + s is 1, 2, or 3;
t is 0, 1, or 2. ) The third component is selected from the group of compounds represented by the following formula (h-1), formula (h-2), formula (h-3), formula (h-4), and formula (h-5) The liquid crystal composition according to claim 11, comprising at least one compound.

(In the formulas (h-1) to (h-5), Ra ₂₂ is a linear alkyl having 1 to 8 carbon atoms or a linear alkenyl having 2 to 8 carbon atoms;
Rb ₂₂ is a straight-chain alkyl having 1 to 8 carbon atoms, a straight chain alkenyl, or alkoxy having 1 to 7 carbon atoms of 2 to 8 carbon atoms;
Z ²⁴ is a single bond or —CH ₂ CH ₂ —;
Y ¹ and Y ² are both fluorine, or one is fluorine and the other is chlorine. ) A first component comprising at least one compound selected from the group of compounds represented by the following formulas (a-1) to (a-3) and formulas (b-1) to (b-3);
A second component comprising at least one compound selected from the group of compounds consisting of formula (e-1), formula (e-2), and formula (e-3) according to claim 8;
Selected from the group of compounds represented by formula (h-1), formula (h-2), formula (h-3), formula (h-4), and formula (h-5) according to claim 12. A liquid crystal composition having a negative dielectric anisotropy containing a third component comprising at least one compound.

(In the above formula (a-1) to formula (a-3) and formula (b-1) to formula (b-3), Ra ₁ is
A straight-chain alkyl having 1 to 10 carbon atoms or a straight-chain alkenyl having 2 to 10 carbon atoms, Rb ₁
Is straight-chain alkyl having 1 to 10 carbons or straight-chain alkoxy having 1 to 9 carbons. )   Based on the total weight of the liquid crystal composition, the content of the first component is in the range of 10 to 80% by weight, the content of the second component is in the range of 10 to 80% by weight, and the third The liquid-crystal composition of Claim 13 whose content rate of a component is the range of 10 to 80 weight%.   The liquid crystal composition according to claim 13, further comprising an antioxidant and / or an ultraviolet absorber. The liquid crystal composition according to claim 15, comprising an antioxidant represented by the following formula (I).

(In formula (I), w represents an integer of 1 to 15)   The liquid crystal display element containing the liquid-crystal composition of any one of Claims 7-16.   The liquid crystal display element according to claim 17, wherein an operation mode of the liquid crystal display element is a VA mode or an IPS mode, and a driving method of the liquid crystal display element is an active matrix method.