JP2003002858A - Liquid crystalline compound having difuluoropropyleneoxy group as bonding group, liquid crystal composition and liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid crystalline compound having large absolute value of an anisotropy of permittivity (|Δε|) and relatively small value of anisotropy of refraction index, a liquid crystal composition containing the compound and capable of being driven at low voltage in various display system, and a liquid crystal display element using the liquid crystal composition. SOLUTION: The new liquid crystalline compound is characterized by having a difluoropropyleneoxy group as a bonding group and having formula (1) (wherein, R<1> and R<2> represent each hydrogen, an alkyl group, or the like, ring A<1> to ring A<5> represent each 1,4-cyclohexylene group, 1,4-phenylene group, or the like, Z<1> to Z<4> represent each a single bond, or the like, Y<1> to Y<4> are each hydrogen or fluorine, and (k)-(n) are each 0 or 1).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid crystal compound and a liquid crystal composition, more specifically a liquid crystal composition, particularly for TN mode, STN mode, TFT mode,
The present invention relates to a liquid crystal compound having a difluoropropyleneoxy group as a bonding group, which exhibits liquid crystal physical properties suitable as a component of a liquid crystal composition for OCB mode, a liquid crystal composition containing the same, and a liquid crystal display device formed by using the liquid crystal composition. In the present invention, the term liquid crystal compound is used as a general term for a compound having a liquid crystal phase and a compound which does not exhibit a liquid crystal phase but is useful as a constituent component of a liquid crystal composition.

[0002]

BACKGROUND ART A liquid crystal display device utilizes optical anisotropy and dielectric anisotropy of a liquid crystal substance. Depending on its display system, a twisted nematic (TN) mode, a dynamic scattering (DS) mode, a guest Host (GH) mode, orientational phase change (DAP) mode, super twisted nematic (STN)
Mode, voltage controlled birefringence (VCB, ECB or TB)
Mode, vertical alignment (VA) mode, multi-domain vertical alignment (MVA) mode, OCB mode, etc., and the properties of the liquid crystal material suitable for each mode are different. Regardless of which method is used, the following properties are required as properties common to all liquid crystal substances.

1) Stable against external environmental factors such as moisture, air, heat and light. 2) To exhibit a liquid crystal phase in a wide temperature range centered on room temperature. 3) Low viscosity. 4) When the display element is driven, the driving voltage can be lowered. 5) It has an optimum dielectric anisotropy (Δε). 6) Having an optimum refractive index anisotropy (Δn).

However, at present, no single compound satisfies all of the above characteristics, and a liquid crystal composition obtained by mixing several to twenty or more kinds of liquid crystalline compounds is used. It is currently used for display devices. Therefore, the liquid crystal compounds used as the composition components are required to exhibit good compatibility with each other. Since it has recently been required that it can be used in various environments, it is desired to exhibit good compatibility especially at extremely low temperatures.

In recent years, there has been a demand for liquid crystal display elements having higher display performance such as contrast, display capacity, response time, etc. In order to meet such requirements, active matrix type display elements typified by TFT (thin film transistor) type are required. The demand is increasing mainly in fields such as televisions and viewfinders. The STN type display element is also widely used in the display field of mobile phones, personal computers, etc. because it has a large display capacity, a simple manufacturing process, and low cost.
Recent development trends in these fields are centered on miniaturization and portability of liquid crystal display elements such as those found in televisions and notebook personal computers that are portable due to their small size and light weight. A liquid crystal material used with this is required to have a low driving voltage, that is, a liquid crystal compound capable of lowering a threshold voltage and a liquid crystal composition containing the same and having a low threshold voltage.

As is well known, the threshold voltage (Vth) is represented by the following equation (HJ Deuling, et a.
L., Mol. Cryst. Liq. Cryst., 27 (1975) 81). Vth = π (K / ε0Δε) ^{1/2 In the} above equation, K is the elastic constant of the liquid crystal material, and ε0 is the dielectric constant in vacuum. As can be seen from the equation, two methods of decreasing Vth can be considered: increasing Δε or decreasing K. However, it is still difficult to actually control the elastic constant K of the liquid crystal material by the current technology, and the requirement is usually met by using a liquid crystal material having a large Δε. Under such circumstances, liquid crystal compounds having large Δε have been actively developed.

As a method of increasing Δε in a liquid crystal compound, a method of retaining a substituent having a large dipole moment, such as a cyano group or a trifluoromethyl group, as a molecular terminal group is well known. Further, a method of substituting fluorine for the 1,4-phenylene group constituting the compound is also effective so that the direction of the dipole moment is the same as the direction of the dipole moment of the terminal substituent. However, in general, there is a proportional relationship between the number of fluorines substituted on the 1,4-phenylene group and the viscosity, and the clearing point of the compound decreases as the number of substituted fluorines increases. It has been considered difficult to improve only Δε while suppressing the decrease in points.

In recent years, liquid crystal display elements have become popular for use as information terminals, portable game machines and the like. Since these display elements are driven by batteries, they are required to have low threshold voltage and low power consumption for pursuit of long-term use. In particular, in order to reduce the power consumption of the element itself, recently, a reflective display element that does not require a backlight has been actively developed, and it is expected that its use in mobile phones will increase in the future. The liquid crystal composition used for these reflective display elements is required to have a low threshold voltage and a small refractive index anisotropy value (Δn). Therefore, the development of a liquid crystal compound having a large dielectric anisotropy value and a small refractive index anisotropy value as a liquid crystal material constituting the composition is the key to this field. The following compounds (13) and (14) are representative of low-voltage driving liquid crystal materials used for a TFT type liquid crystal display element (Japanese Patent Laid-Open No. 23362/1990).
No. 6 publication).

[0009]

[Chemical 7] (In the formula, R represents an alkyl group.)

The compounds (13) and (14) each have a 3,4,5-trifluorophenyl group at the terminal of the molecule,
It is expected as a liquid crystal material for low voltage driving. However, the compound (13) has a small dielectric anisotropy value (Δε = ˜10) for the above-mentioned reflective display device,
The compound (14) has a dielectric anisotropy value (Δε = ∼12).
However, the refractive index anisotropy value is as large as about 0.12, and it is considered difficult to prepare a liquid crystal composition sufficiently satisfying the above requirements by using these compounds.

In recent years, as a method of overcoming the narrowing of the viewing angle, which is the biggest problem of the liquid crystal display device, an in-plane switching (IPS) mode, a vertical alignment (VA) mode, a multi-domain vertical alignment (MVA) mode, OCB
New methods such as modes have been announced. Among these modes, in particular, the VA mode and the MVA mode are excellent in responsiveness in addition to a wide viewing angle, and further have high contrast, so that they are actively developed by each display manufacturer. A characteristic of the liquid crystal composition used for the liquid crystal display element of these systems is that the liquid crystal composition has a relatively small anisotropy of refractive index and a negative dielectric anisotropy. As a compound exhibiting a large negative dielectric anisotropy, for example, the following compound (15) has been reported (V. Reiffen
rath et al., Liq. Cryst., 5 (1), 159 (1989)).

[0012]

[Chemical 8]

Although it is known from the document that the compound (15) has a large negative dielectric anisotropy value of Δε = -4.1, its refractive index anisotropy value is Δn = 0. It is expected that it will be difficult to meet the requirements of the above-mentioned VA mode or MVA mode as large as 0.18.

As described above, a liquid crystal compound having a large positive and negative dielectric anisotropy and a relatively small refractive index anisotropy is desired.

[0015]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned drawbacks of the prior art and to provide the absolute value of dielectric anisotropy (|
To provide a liquid crystal compound having a large Δε |) and a relatively small refractive index anisotropy value, and to provide a liquid crystal composition containing the compound, which enables low voltage driving in various display systems. And to provide a liquid crystal display device using this liquid crystal composition.

[0016]

Means for Solving the Problems As a result of intensive studies made by the present inventors in order to achieve the above object, the compound represented by the formula (1) having a difluoropropyleneoxy group as a bonding group has an anisotropic dielectric constant. It has been found that the absolute value of the property (| Δε |) is large and the refractive index anisotropy value is relatively small.
Further, they have found that a liquid crystal composition using these compounds is an optimum material for driving various liquid crystal display devices at a low voltage, and completed the present invention. That is, the structure of the present invention is as follows.

The first aspect of the present invention is [1] Formula (1)

[Chemical 9] (In the formula, R ¹ and R ² are each independently hydrogen, halogen,
A cyano group or an alkyl group having 1 to 20 carbon atoms, one or more -CH ₂ in the alkyl group - is -CH = CH
-, -C≡C-, -O- or -S- may be substituted, but -O- is not continuous, and 1 in the group
One or more hydrogens may be replaced by halogens; Ring A
¹ to ring A ⁵ are each independently one or more non-adjacent -C.
H ₂ — may be substituted with —O— or —S— 1,
4-cyclohexylene group, 1,4-cyclohexenylene group, or one or more = CH- may be substituted with = N-, or hydrogen on the ring may be substituted with halogen 1. , 4-phenylene group; Z ^{1 to} Z ⁴ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —O.
_{CH 2 -, - COO -,} - OCO -, - CH = CH-,
-C≡C-, -CF ₂ O-, or -OCF _2- ;
Y ¹ , Y ² , Y ³ and Y ⁴ are each independently hydrogen or fluorine; k, l, m and n are each independently 0 or 1).

The first aspect of the present invention is described in the following items [2] to [10]. [2] Formulas (1-1) to (1-6)

[Chemical 10] (Wherein R ¹ , R ² , rings A ^{1 to} A ⁵ , Z ^{1 to} Z ⁴ , and Y ¹ to
Y ⁴ represents the same meaning as described above).

[3] In formula (1), ring A ³ is 1,4-
A liquid crystal compound having a cyclohexylene group.

[4] A liquid crystal compound in which Y ¹ and Y ³ are both fluorine and Y ² and Y ⁴ are both hydrogen in the formula (1).

[5] A liquid crystal compound in which both Y ¹ and Y ² in formula (1) are hydrogen.

[6] In the formula (1-1), the ring A ³ is 1,
4-cyclohexylene group, Y ¹ and Y ³ are both fluorine, Y ²
And a liquid crystal compound in which Y ⁴ is both hydrogen.

[7] In the formula (1-1), the ring A ³ is 1,
4-cyclohexylene group, a liquid crystal compound in which both Y ¹ and Y ² are hydrogen.

[8] A liquid crystal in which ring A ² and ring A ³ are both 1,4-cyclohexylene groups in formula (1-2), Y ¹ and Y ³ are both fluorine, and Y ² and Y ⁴ are both hydrogen. Sex compounds.

[9] A liquid crystal compound in which ring A ² and ring A ³ are both 1,4-cyclohexylene groups in formula (1-2), and Y ¹ and Y ² are both hydrogen.

[10] A liquid crystal compound in which ring A ³ in the formula (1-3) is a 2,3-difluoro-1,4-phenylene group.

The second aspect of the present invention is [11], [1] to
A liquid crystal composition containing at least one kind of the liquid crystalline compound according to any one of the items [10], and its aspects are described in the following items [12] to [18].

[12] In the item [11], as the second component, equations (2), (3) and (4) are used.

[Chemical 11] (In the formula, R ³ is an alkyl group having 1 to 10 carbon atoms, and any —CH ₂ — which is not adjacent to each other in this group may be substituted with —O— or —CH═CH—. any hydrogen in this group may be substituted by fluorine; X ¹ is fluorine, _{chlorine, -OCF 3, -OCF 2 H,} -CF 3, -CF 2
_{H, -CFH 2, -OCF 2 CF} 2 H or -OCF ₂ CF
HCF ₃ ; L ¹ and L ² are each independently hydrogen or fluorine; Z ⁵ and Z ⁶ are independently-(C
_{H 2) 2 -, - (} CH 2) 4 -, - COO -, - CF 2 O -, -
OCF ₂ —, —CH═CH— or a single bond; ring A
And ring B are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, or 1,4-phenylene in which hydrogen may be replaced by fluorine, and ring C is 1 A liquid crystal composition containing at least one compound selected from the group consisting of compounds consisting of 1,4-cyclohexylene or 1,4-phenylene in which hydrogen may be replaced by fluorine.

[13] A liquid crystal composition containing at least one compound selected from the compound group consisting of formulas (5) and (6) as the second component in the item [11].

[0030]

[Chemical 12] (In the formula, R ⁴ and R ⁵ are each independently an alkyl group having 1 to 10 carbon atoms, and any —C which is not adjacent to each other in this group.
H ₂ — may be substituted with —O— or —CH═CH—, and any hydrogen in this group may be substituted with fluorine; X ² is —CN or —C≡C—CN. Ring D is 1,4-cyclohexylene, 1,4-phenylene,
1,3-dioxane-2,5-diyl or pyrimidine-
2,5-diyl; ring E is 1,4-cyclohexylene, 1,4-phenylene in which hydrogen may be replaced by fluorine, or pyrimidine-2,5-diyl; ring F is 1,4 - it is cyclohexylene or 1,4-phenylene; Z ⁷ is _{- (CH 2) 2 -,} - COO -, - CF 2 O -, -
OCF ₂ — or a single bond; L ³ , L ⁴ and L ⁵ are each independently hydrogen or fluorine; b, c and d are each independently 0 or 1. )

[14] A liquid crystal composition containing at least one compound selected from the compound group consisting of formulas (7), (8) and (9) as the second component in the item [11].

[0032]

[Chemical 13] (In the formula, R ⁶ and R ⁷ are each independently an alkyl group having 1 to 10 carbon atoms, and any —C which is not adjacent to each other in this group.
H ₂ — may be substituted with —O— or —CH═CH—, and any hydrogen in this group may be substituted with fluorine; ring G and ring I are each independently 1 , 4-cyclohexylene or 1,4-phenylene; L ⁶ and L ⁷ are each independently hydrogen or fluorine, but L ⁶ and L ⁷ are not hydrogen at the same time; Z ⁸ and Z ⁹ are each independently _{- (CH 2) 2 -,} - COO- or a single bond. )

[15] In the item [11], at least one compound selected from the compound group consisting of the formulas (2), (3) and (4) is contained as the second component, and the third component As equations (10), (11) and (1
A liquid crystal composition containing at least one compound selected from the compound group consisting of 2).

[0034]

[Chemical 14] (In the formula, R ⁸ and R ⁹ are each independently an alkyl group having 1 to 10 carbon atoms, and any —C which is not adjacent to each other in this group.
H ₂ — may be substituted with —O— or —CH═CH—, and any hydrogen in this group may be substituted with fluorine; ring J, ring K and ring M are each independently , 1,4
- cyclohexylene, pyrimidine-2,5-diyl or hydrogen is to be or 1,4-phenylene substituted by fluorine,; Z ^{1 0} and Z ¹¹ are each independently, -C≡C
-, - COO -, - ( CH 2) 2 -, - is CH = CH- or a single bond. )

[16] In the item [11], as the second component, at least one compound selected from the compound group consisting of the formulas (5) and (6) is contained, and as the third component, the formula A liquid crystal composition containing at least one compound selected from the compound group consisting of (10), (11) and (12).

[17] In the item [11], as the second component, at least one compound selected from the group of compounds consisting of the formulas (7), (8) and (9) is contained, and the third component As a liquid crystal composition containing at least one compound selected from the compound group consisting of the formulas (10), (11) and (12).

[18] In the item [11], as the second component, at least one compound selected from the group of compounds consisting of the formulas (2), (3) and (4) is contained, and the third component Containing at least one compound selected from the compound group consisting of the above formulas (5) and (6), and as a fourth component, a compound group consisting of the above formulas (10), (11) and (12) A liquid crystal composition containing at least one selected compound.

The third aspect of the present invention is [19] th [11]-
The liquid crystal composition according to any one of the items [18], further containing one or more optically active compounds.

The fourth aspect of the present invention is [20] the above-mentioned [1]
A liquid crystal display device using the liquid crystal composition according to any one of items 1 to 19 !.

[0040]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention represented by the formula (1) is a moiety in which --O-- in a difluoropropyleneoxy group is directly bonded to a 1,4-phenylene group which may be substituted by fluorine. It is characterized by having a structure. In the compound of formula (1), the compound in which the ring A ³ is a 1,4-cyclohexylene group has a high clearing point, and the compound in which the ring A ³ is a 1,4-phenylene group is a dielectric anisotropy. The absolute value of is large. The compound of the formula (1) in which both Y ¹ and Y ² are hydrogen exhibits neutral or positive dielectric anisotropy. Among them, a compound in which at least one of Y ³ and Y ⁴ is fluorine exhibits a positively large dielectric anisotropy. For example, the compound of the present application (Compound N
o.40), the dielectric anisotropy of which is Δε = 13.7, and the bonding group corresponding to the difluoropropyleneoxy group is a single bond ((13-1): Δε = 9.7). Compared with, it shows a much larger value.

[0041]

[Chemical 15]

On the other hand, the compound of formula (1) in which both Y ¹ and Y ³ are fluorine and both Y ² and Y ⁴ are hydrogen show a large negative dielectric anisotropy. Further, the compound of the formula (1) has a high clearing point and substantially the same refractive index anisotropy as compared with, for example, a compound having a single bond of a difluoropropyleneoxy group, which is a feature of the present invention. From these facts, the compound of the formula (1) is not limited to the liquid crystal display device of the reflection type described in the background art, V
It can be seen that the liquid crystal composition has suitable characteristics as a liquid crystal compound constituting a liquid crystal composition for A and MVA systems.

Although some compounds having a difluoropropyleneoxy group as a bonding group are described in WO97 / 37959 by a general formula of compounds similar to the present invention, disclosure of structural formulas and physical property values of specific compounds However, the present inventors have first discovered the excellent properties of the compound of the present invention.

The liquid crystal compound represented by the formula (1) is represented by the following formulas (1-1) to (1-6) by appropriately selecting k, l, m and n in the formula. Expands to a group of compounds.

[0045]

[Chemical 16] (In the formula, R ¹ , R ² , rings A ^{1 to} A ⁵ , Z ^{1 to} Z ⁴ and Y ¹ to
Y ⁴ has the same meaning as described above. )

In the compounds of these subordinate formulas, the formula (1-
The bicyclic compound of 1) has a relatively large absolute value of Δε and a relatively small Δn, has low viscosity, and has good compatibility at low temperatures. When this compound is used as a component of a liquid crystal composition, its viscosity can be reduced while maintaining the absolute value of Δε of the composition, so that a liquid crystal composition for high-speed response can also be provided.

Further, the tricyclic compound represented by the formula (1-2) or the formula (1-3) has a large absolute value of Δε, a relatively small Δn, and a temperature range showing a liquid crystal phase. Is relatively wide. When this compound is used as a component of a liquid crystal composition, the absolute value of Δε can be increased without lowering the clearing point of the composition, so that a liquid crystal composition for low voltage driving can be provided.

The tetracyclic compounds represented by the formulas (1-4) to (1-6) have a large absolute value of Δε and a relatively small Δn.
Indicates. Further, the temperature range showing the liquid crystal phase is wide on the high temperature side. Therefore, when these compounds are used as a component of a liquid crystal composition, the absolute value of Δε of the composition can be increased and the liquid crystal phase temperature range of the liquid crystal composition can be expanded to the high temperature side. Furthermore, in these formulas, a compound in which at least one of Y ¹ , Y ² , Y ³ and Y ⁴ is fluorine has excellent low temperature compatibility.

In the compound represented by formula (1) of the present invention, R ¹ and R ² are each independently hydrogen, halogen, a cyano group, or —CH ₂ — in the group is —CH═CH—, — C
A carbon which may be substituted with ≡C-, -O- or -S-, but is not continuous with -O-, and one or more hydrogens in the group may be substituted with halogen. Number 1
20 alkyl groups; ring A ¹ to ring A ⁵ are each independently 1,4-unsubstituted one or more —CH ₂ — may be substituted with —O— or —S—, 1,4- A cyclohexylene group, a 1,4-cyclohexenylene group, or one or more ═CH— may be substituted with ═N—, and hydrogen on the ring may be substituted with halogen 1,4 A phenylene group; Z ^{1 to} Z ⁴ are each independently a single bond;
_{CH 2 CH 2 -, - CH} 2 O -, - OCH 2 -, - COO
-, -OCO-, -CH = CH-, -C≡C-, -CF
₂ O— or —OCF ₂ —; Y ¹ , Y ² , Y ³ and Y ⁴ are each independently hydrogen or fluorine; k,
l, m and n are each independently 0 or 1.

In the above, R ¹ and R ² are specifically hydrogen, halogen, cyano group, alkyl group, alkoxy group,
Alkoxyalkyl group, alkylthio group, alkylthioalkyl group, alkenyl group, alkenyloxy group, alkenylthio group, alkynyl group, fluorine-substituted alkyl group,
A fluorine-substituted alkoxy group, a fluorine-substituted alkenyl group, a fluorine-substituted alkenyloxy group, a fluorine-substituted alkenylthio group, a fluorine-substituted alkynyl group and the like are shown.

More specifically, fluorine, chlorine, bromine, methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, methoxy group, Ethoxy group, propoxy group, butoxy group, pentoxy group, heptyloxy group, octyloxy group, methoxymethyl group, ethoxymethyl group, propoxymethyl group, propoxyethyl group,
Methoxypropyl group, ethoxypropyl group, propoxypropyl group, methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, methylthiomethyl group, ethylthiomethyl group, propylthiomethyl group, Butylthiomethyl group, methylthioethyl group, ethylthioethyl group, propylthioethyl group, methylthiopropyl group, ethylthiopropyl group, propylthiopropyl group,
Vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 3-butenyl group, 3-pentenyl group, ethynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group , Allyloxy group, trifluoromethyl group, fluoromethyl group, 2-fluoroethyl group, difluoromethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 2-fluoro Ethyl group, 3-fluoropropyl group, 4-fluorobutyl group, 5-fluoropentyl group, fluoromethoxy group, trifluoromethoxy group, difluoromethoxy group, pentafluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group Group, heptafluoropropoxy group,
1,1,2,3,3,3-hexafluoropropoxy group, trifluoromethoxymethyl group, 2-fluoroethenyl group, 2,2-difluoroethenyl group, 1,2,2-trifluoroethenyl group, 3-fluoro-1-butenyl group, 4
-Fluoro-1-butenyl group, trifluoromethylthio group, difluoromethylthio group, 1,1,2,2-tetrafluoroethylthio group, 2,2,2-trifluoroethylthio group and the like.

As the rings A ¹ to A ^{5 in the} above, specifically, those having a ring structure represented by (r-1) to (r-24) are preferable.

[0053]

[Table 1]

The liquid crystal composition provided by the present invention may include only the first component containing at least one liquid crystalline compound of the formula (1), but in addition to this, the second component may be represented by the above-mentioned formula (2). ), At least one compound selected from the group consisting of (3) and (4) (hereinafter referred to as the second component A) and / or at least one compound selected from the group consisting of formulas (5) and (6) Those containing a compound (hereinafter referred to as the second component B) are preferable, and further for the purpose of adjusting the threshold voltage, the liquid crystal phase temperature range, the refractive index anisotropy value, the dielectric anisotropy value and the viscosity. , Equations (7), (8)
Also, at least one compound selected from the group consisting of (9) and (9) can be contained as the third component. In addition, since each component of the liquid crystal composition used in the present invention has no great difference in physical properties, it may be an analog of an isotope of each element.

Of the above-mentioned second component A, the following compounds (2-1) to (2-9) are preferred examples of the compound contained in the formula (2).
Preferred examples of the compound contained in the formula (3) include (3-1) to
(4-1) to (4-33) can be mentioned as suitable examples of the compound contained in (3-97) and the formula (4).

[0056]

[Chemical 17]

[0057]

[Chemical 18]

[0058]

[Chemical 19]

[0059]

[Chemical 20]

[0060]

[Chemical 21]

[0061]

[Chemical formula 22]

[0062]

[Chemical formula 23]

[0063]

[Chemical formula 24]

[0064]

[Chemical 25]

[0065]

[Chemical formula 26]

[0066]

[Chemical 27]

[0067]

[Chemical 28]

[0068]

[Chemical 29] (In the formula, R ³ and X ¹ have the same meanings as described above.)

Since the compounds represented by the formulas (2) to (4) have positive dielectric anisotropy values and are very excellent in thermal stability and chemical stability, they are mainly used for TFTs. Used in liquid crystal compositions. When a liquid crystal composition for TFT is prepared, the amount of the compound used is preferably in the range of 1 to 99% by weight based on the total weight of the liquid crystal composition. More preferably 10 to 97% by weight, even more preferably 40 to 9
It is in the range of 5% by weight. Further, the compounds represented by the formulas (10) to (12) may be further contained for the purpose of adjusting the viscosity.

Next, among the second component B, preferable examples of the compounds contained in the formulas (5) and (6) are (5-1) to (5-58) and (6-1) to (6-1). (6-
3) can be mentioned.

[0071]

[Chemical 30]

[0072]

[Chemical 31]

[0073]

[Chemical 32]

[0074]

[Chemical 33]

[0075]

[Chemical 34]

[0076]

[Chemical 35] (In the formula, R ⁴ , R ⁵ and X ² have the same meanings as described above.)

Since the compounds represented by the formulas (5) and (6) have a positive dielectric anisotropy value and a very large value, they are mainly used for liquid crystal compositions for STN and TN. These compounds are used as a composition component particularly for the purpose of reducing the threshold voltage. Also, adjustment of viscosity,
It is also used for the purpose of adjusting the refractive index anisotropy value, widening the temperature range of the liquid crystal phase, and for improving steepness. When preparing a liquid crystal composition for STN or TN, the amount of the compounds represented by formulas (5) and (6) used is preferably in the range of 0.1 to 99.9% by weight. More preferably 10 to 97% by weight, still more preferably 40
Is in the range of up to 95% by weight. Further, a third component described later may be contained for the purpose of adjusting the threshold voltage, the liquid crystal phase temperature range, the refractive index anisotropy value, the dielectric anisotropy value, the viscosity and the like.

When a liquid crystal composition having a negative dielectric anisotropy used for a vertical alignment mode (VA mode) or the like is prepared, the liquid crystal composition of the present invention has formulas (7) to (9). Those containing at least one kind of compound (hereinafter referred to as the second C component) selected from the group consisting of are preferred. Suitable examples of the compounds contained in the formula (7) to (9) of the second component C are (7-1) to (7-3) and (8-1) to (8-5), respectively.
And (9-1) to (9-3).

[0079]

[Chemical 36] (In the formula, R ⁶ and R ⁷ have the same meanings as described above.)

The compounds represented by the formulas (7) to (9) are compounds having a negative dielectric anisotropy value. Since the compound represented by the formula (7) is a bicyclic compound, it is mainly used for the purpose of adjusting the threshold voltage, adjusting the viscosity or adjusting the anisotropy of refractive index. The compound represented by the formula (8) is used for the purpose of widening the nematic range, lowering the threshold voltage and increasing the anisotropy of refractive index.

The compounds represented by the formulas (7) to (9) are mainly used for a VA mode liquid crystal composition having a negative value of dielectric anisotropy. Increasing the amount used lowers the threshold voltage of the composition but increases the viscosity. Therefore,
As long as the required value of the threshold voltage is satisfied, it is preferable to reduce the amount used. However, since the absolute value of the dielectric anisotropy value is 5 or less, the liquid crystal composition may not be driven when the amount of the compounds represented by the formulas (7) to (9) is less than 40% by weight. Therefore, when preparing the composition for the VA mode, the amount of the compounds represented by the formulas (7) to (9) used is preferably 40% by weight or more. It is more preferably in the range of 50 to 95% by weight.

For the purpose of controlling the elastic constant and controlling the voltage transmittance curve of the composition, the compounds represented by the formulas (7) to (9) are added to the composition having a positive dielectric anisotropy value. It may be included. In this case, the amount of the compounds represented by the formulas (7) to (9) used is preferably 30% by weight or less.

Among the third components of the liquid crystal composition of the present invention, preferred examples of the compounds contained in the formulas (10) to (12) are:
(10-1) to (10-11), (11-1)
To (11-12) and (12-1) to (12-6).

[0084]

[Chemical 37]

[0085]

[Chemical 38]

[0086]

[Chemical Formula 39] (In the formula, R ⁸ and R ⁹ have the same meanings as described above.)

The compounds represented by the formulas (10) to (12) are compounds having a small absolute value of dielectric anisotropy and being close to neutral. The compound represented by the formula (10) is mainly used for the purpose of adjusting the viscosity or adjusting the refractive index anisotropy value.
The compounds represented by the formulas (11) and (12) are used for the purpose of broadening the nematic range such as increasing the clearing point or adjusting the anisotropy of refractive index.

When the amount of the compounds represented by the formulas (10) to (12) is increased, the threshold voltage of the liquid crystal composition becomes high and the viscosity becomes low. Therefore, in order to enable low voltage driving, a large amount of the compounds represented by the formulas (10) to (12) should be used as long as the required threshold voltage value of the liquid crystal composition is satisfied. desirable. When preparing a liquid crystal composition for a TFT, the amount of the compounds represented by the formulas (10) to (12) used is preferably 40% by weight or less, more preferably 35% by weight or less. Also, STN or TN
In the case of preparing a liquid crystal composition for use in a liquid crystal display device, the formulas (10) to (1
The amount of the compound represented by 2) used is preferably 70% by weight or less, more preferably 60% by weight or less.

The liquid crystal composition provided in accordance with the present invention contains at least one liquid crystal compound represented by the formula (1) in a proportion of 0.1 to 99% by weight so that it can be driven at a low voltage. Preferred for expression.

The liquid crystal composition is generally prepared by a known method, for example, a method in which various components are mutually dissolved at high temperature. Further, if necessary, a chiral dopant can be added to improve and optimize according to the application. The chiral dopant may be any chiral dopant having an effect of inducing a helical structure of liquid crystal to adjust a necessary twist angle and preventing reverse twist. For example, the following optically active compounds can be mentioned as the chiral dopant.

[0091]

[Chemical 40]

In the liquid crystal composition of the present invention, these optically active compounds are usually added to adjust the twist pitch.
The twist pitch is preferably adjusted in the range of 40 to 200 μm in the case of a liquid crystal composition for TFT and TN. In the case of a liquid crystal composition for STN, it is preferable to adjust it in the range of 6 to 20 μm. In addition, bistable TN (Bist
In the case of the Able TN) mode, it is preferable to adjust it in the range of 1.5 to 4 μm. Further, two or more kinds of optically active compounds may be added for the purpose of adjusting the temperature dependence of pitch.

Further, if a dichroic dye such as merocyanine type, styryl type, azo type, azomethine type, azoxy type, quinophthalone type, anthraquinone type and tetrazine type is added, it can be used as a GH type liquid crystal composition. You can also The composition according to the present invention includes NCAP prepared by encapsulating nematic liquid crystal, and polymer dispersed liquid crystal display device (PDLCD) prepared by forming a three-dimensional network polymer in the liquid crystal, for example, polymer network liquid crystal display. It can also be used as a liquid crystal composition for a device (PNLCD), a birefringence control (ECB) type or a DS type.

The compound represented by the formula (1) of the present invention is, for example, 4th edition Experimental Chemistry Course (Maruzen), Organic Synthesis.
(John Wiley & Sons, Inc) or Organic Reactions
(John Wiley & Sons, Inc) and the like can be produced by appropriately selecting and combining methods described in the textbooks of organic synthesis or known literatures.

For example, the compound represented by the formula (1) can be produced by the following method. First, JP-A-59-76
No. 027, JP-A-60-197637 or JP-A-60-204743, a propionic acid ester derivative (16) obtained by the method described in JP-A-10-204016.
Lawson's reagent (Fieser
It is converted to the thioester derivative (17) at 13, 38).
Further, in accordance with the method disclosed in JP-A-5-255165, (17) is treated with HF-pyridine in the presence of an oxidizing agent such as N-bromosuccinimide (hereinafter abbreviated as NBS) to fluorinate the compound of formula (1). Obtain the compound.

[0096]

[Chemical 41] (In the formula, R ¹ , R ² , rings A ^{1 to} A ⁵ , Z ^{1 to} Z ⁴ , Y ^{1 to} Y ⁴ ,
k, l, m and n have the same meanings as described above. )

The compound represented by the formula (1) can also be preferably produced by the following method. That is, JP-A-10-1
According to the method described in No. 7544, the halobenzene derivative (1
After preparing the Grignard reagent from 8), the dithiocarboxylic acid derivative (19) is produced by acting carbon disulfide. Then, the thioester derivative (17) can be produced by reacting (19) with sodium hydride in the coexistence with the phenol derivative (20) and further oxidizing with sodium. In (17) thus obtained, H 2 is added in the presence of an oxidizing agent such as NBS.
The target compound (1) can be produced by fluorinating F-pyridine.

[0098]

[Chemical 42] (In the formula, R ¹ , R ² , rings A ^{1 to} A ⁵ , Z ^{1 to} Z ⁴ , Y ^{1 to} Y ⁴ ,
k, l, m and n have the same meanings as described above, and hydrogen on the benzene ring may be replaced by fluorine. X represents chlorine or bromine. )

Regarding the phenol derivative (20) used above, for example, the method of RL Kidwell (Or
g. Synth., V, 918 (1973)), trialkyl borate is allowed to act on a Grignard reagent prepared from a benzene derivative (21) to prepare a boronic acid ester derivative. It can be produced by oxidizing with a peroxide.

[0100]

[Chemical 43] (In the formula, R ² , rings A ⁴ , A ⁵ , Z ³ , Z ⁴ , Y ^{1 to} Y ⁴ , m and n represent the same meaning as described above, R ¹⁰ represents an alkyl group,
X'represents a chlorine atom or a bromine atom. )

The compound represented by the formula (1) can also be preferably produced by the following method. That is, first, a dithianium salt (23) is produced by reacting a carboxylic acid derivative (22) with a strong acid such as propanedithiol and trifluoroacetic acid in a suitable solvent represented by toluene. The reaction in this case is carried out at a temperature from room temperature to about the boiling point of the solvent as a guide, but it is preferable to carry out the reaction at 100 ° C. or higher while removing water, because the salt is stably isolated. ((2
In addition to dithianium trifluoromethanesulfonate, 3) may be tetrafluoroborate or perchlorate. Then, (23) is led to a dithioorthoester derivative (24) by acting a base such as triethylamine in the presence of a phenol derivative (20) in a suitable solvent such as methylene chloride, and triethylamine-3H is added to this system.
By subjecting a fluorinating agent such as F to an oxidizing agent such as NBS or bromine to effect oxidative fluorination, the target compound (1) can be produced. The reaction at this time is carried out at the lowest temperature possible, and practically -50 ° C to -1.
About 00 ° C is desirable.

[0102]

[Chemical 44] (In the formula, R ¹ , R ² , rings A ^{1 to} A ⁵ , Z ^{1 to} Z ⁴ , Y ^{1 to} Y ⁴ ,
k, l, m and n have the same meanings as described above, and hydrogen on the benzene ring may be replaced by fluorine. )

[0103]

The present invention will be described in more detail with reference to the following examples. In each example, Cr is a crystal, N is a nematic phase, and Iso is an isotropic liquid phase.

Example 1 1- (3- (trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) -1,1-difluoropropyleneoxy) -3,4,5-trifluorobenzene (formula (1) In 1 = 1, k = m = n = 0, R ¹ is an n-pentyl group, and ring A ² and ring A ³ are both trans-
Production of 1,4-cyclohexylene group, compound in which Z ² is a single bond, Y ¹ and Y ² are both hydrogen atoms, and Y ³ , Y ⁴ and R ² are both fluorine atoms (Compound No. 40))

First Step In a 1 L three-necked flask equipped with a stirrer, thermometer and dropping funnel, under nitrogen atmosphere, diethylphosphinoethyl acetate 27.6
g (122.9 mmol) was dissolved in 350 ml of tetrahydrofuran (hereinafter abbreviated as THF), cooled to −5 ° C. with stirring, and 15.2 g of potassium t-butoxide (135.
2 mmol) was added and the mixture was stirred at room temperature for 2 hours. 0 ° C again
Cooled to trans-4- (trans-4-pentylcyclohexyl) cyclohexanecarbaldehyde 25.0 g
A solution of (94.5 mmol) in 100 ml of THF was added dropwise. After further stirring at room temperature for 14 hours, the reaction mixture is mixed with water 20
0 ml and toluene 400 ml were added and stirred. The separated toluene layer was washed twice with 200 ml of water and dried over anhydrous magnesium sulfate, and toluene was distilled off under reduced pressure. The residue was purified by silica gel column chromatography using toluene as a developing solvent to obtain 12.8 g of ethyl 3- (trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) propenoate (yellow oil).

Second step In a 100 ml flask, the 3- (trans-4-
Ethyl (trans-4-pentylcyclohexyl) cyclohexyl) propenoate 12.8 g (38.3 mmol) was dissolved in a mixed solution of toluene / ethanol (50 ml / 30 ml), 5% palladium-carbon catalyst 2.0 g was added, and hydrogen pressure was 0.1. Stirred at MPa for 8 hours at room temperature. The catalyst was collected by filtration and the filtrate was concentrated to give a yellow oil (13.5 g). Next, this oily substance was dissolved in 150 ml of ethanol, 50 ml (100 mmol) of 2M aqueous sodium hydroxide solution was added, and the mixture was heated under reflux for 3 hours. Water 300
ml was added, and the precipitated insoluble matter was collected by filtration and recrystallized from toluene to obtain 4.9 g of 3- (trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) propionic acid as pale yellow crystals.

Third step In a 100 ml three-necked flask equipped with a stirrer, a thermometer and a condenser, under a nitrogen atmosphere, the 3- (trans-4-
(Trans-4-pentylcyclohexyl) cyclohexyl) propionic acid 4.9 g (16.0 mmol), 3,4,5-trifluorophenol 2.9 g (19.2 mmol), 2-chloro-1-methylpyridinium iodide (Kazuhiko Saigo,
Teruaki Mukaiyama et al., Bull. Chem. Soc. Jpn., 5
0 (7), 1863 (1977)) 4.9 g (19.2 mmol) and triethylamine 3.9 g (38.4 mmol) were dissolved in 50 ml of toluene,
The mixture was heated under reflux for 3 hours with stirring. To the reaction mixture, 50 ml of 6M hydrochloric acid and 100 ml of toluene were added and stirred. The toluene layer was washed with water (150 ml × 3), dried over anhydrous magnesium sulfate, and the toluene was distilled off under reduced pressure. The residue was purified by silica gel column chromatography using a mixed solution of heptane / toluene (75/25) as a developing solvent, and 3,4,5-trifluorophenyl = 3- (trans-4- (trans-
6.4 g of 4-pentylcyclohexyl) cyclohexyl) propionate was obtained as colorless crystals.

Fourth Step In a 300 ml three-necked flask equipped with a stirrer, a thermometer and a cooling tube, under a nitrogen atmosphere, 3,4,5-trifluorophenyl obtained above was 3- (trans-4- (trans- 4-pentylcyclohexyl) cyclohexyl) propionate 6.4 g (14.5 mmol), Lawesson's reagent 11.7 g (29.0 mmo
l) and 85 ml of mesitylene were heated to reflux with stirring for 8 hours. After cooling to room temperature, insoluble materials were removed and the filtrate was extracted with toluene. The toluene layer was washed successively with 200 ml of water, 150 ml of saturated aqueous sodium carbonate solution and 200 ml of water twice, dried over anhydrous magnesium sulfate, and then the toluene was distilled off under reduced pressure. The residue was purified by silica gel column chromatography using heptane as a developing solvent, and 3,4,5-trifluorophenyl = 3- (trans-4- (trans-4-
Pentylcyclohexyl) cyclohexyl) thione-O
0.9 g of propionate as pale yellow crystals are obtained.

Step 5 Teflon ^(R) equipped with stirrer, thermometer and dropping funnel
In a 200 ml three-necked flask manufactured by NBS, 1.1 g (5.8 mmol) of NBS was dissolved in 15 ml of dichloromethane, 1 ml of 70% HF-pyridine was added at -60 ° C or lower with stirring, and the mixture was further stirred for 30 minutes. Then, 0.9 g (2.0 mmol) of 3,4,5-trifluorophenyl = 3- (trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) thione-O-propionate obtained in the previous step was dissolved in 20 ml of dichloromethane. The solution was added dropwise, and after the addition, the mixture was stirred at -10 to 0 ° C for 2 hours. The reaction mixture was poured into 100 ml of a saturated aqueous solution of sodium carbonate, the dichloromethane layer was separated, washed with 150 ml of water three times, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography using heptane as a developing solvent.
Recrystallize from an equal volume mixture of ethanol to give the desired 1-
0.7 g of (3- (trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) -1,1-difluoropropyleneoxy) -3,4,5-trifluorobenzene ((colorless crystalline substance) was obtained. The liquid crystal phase is as follows, and its transition point is shown below: Cr 65.5 (Sm
50.76); N 116.9 Iso

The measurement results of various spectral data strongly supported the structure. ¹ H-NMR (δppm, CDCl ₃ ): 0.8-2.2 (m, 35H), 6.85-6.88
(m, 2H) ¹⁹ F-NMR (δppm): -79.26 (t, 2F, -C F ₂ O-), -133.53--13
3.65 (m, 2F), -165.00--165.06 (m, 1F) GC-MS (EI): 460 (M ⁺ , 12.5%), 148 (92.4), 97 (93.6), 8
3 (100), 81 (55.0), 69 (54.9), 55 (76.4), 41 (30.7)

Example 2 1- (3- (2,6-difluoro-4- (4-pentylphenyl) phenyl) -1,1-difluoropropyleneoxy) -3-fluoro-4-trifluoromethoxybenzene (formula In (1), l = 1, k = m = n = 0, R
¹ is an n-pentyl group, ring A ² is a 1,4-phenylene group, ring A ³ is a 3,5-difluoro-1,4-phenylene group, Z ² is a single bond, and Y ¹ , Y ² and Y ⁴ are Production of compound (compound No. 66) in which both are hydrogen atoms, Y ³ is a fluorine atom, and R ² is a trifluoromethoxy group

First step In a 500 ml three-necked flask equipped with a stirrer, a thermometer and a dropping funnel, under a nitrogen atmosphere, 2,6-difluoro-4- (4-
Pentylphenyl) benzene 15.0 g (57.6 mmol) TH
Dissolve in 100 ml of F and stir with stirring at -65 ° C or below to n-BuLi
43 ml (69.1 mmol) of (1.6 M cyclohexane solution) was added dropwise, and the mixture was further stirred for 1 hour. Then formylpiperidine
7.2 g (63.4 mmol) was added dropwise at -65 ° C or lower, and the mixture was further stirred for 2 hours. 200 ml of water was added to the reaction mixture, and toluene 400 was added.
The mixture was extracted with 100 ml of water, the toluene layer was washed twice with 200 ml of water, and then dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography using toluene as a developing solvent.
13.1 g of 6-difluoro-4- (4-pentylphenyl) benzaldehyde was obtained.

Second step In a 500 ml three-necked flask equipped with a stirrer, a thermometer and a dropping funnel, 21.1 g (54.6 mmol) of methoxymethyltriphenylphosphonium chloride was suspended in 80 ml of THF under a nitrogen atmosphere and stirred at -30 6.4 g (57.3 mmol) of potassium t-butoxide was added at a temperature of not more than 0 ° C, and then the mixture was stirred at 0 ° C for 2 hours. This was cooled again to −30 ° C. or lower, and a THF solution containing 13.1 g (45.5 mmol) of 2,6-difluoro-4- (4-pentylphenyl) benzaldehyde obtained in the previous step.
After dropping 100 ml, the mixture was stirred at room temperature for 6 hours. After adding 150 ml of water and 200 ml of heptane to the reaction mixture to remove insoluble matter, the separated heptane layer was washed twice with 150 ml of water and dried over anhydrous magnesium sulfate. The concentrated residue obtained by distilling off heptane under reduced pressure was dissolved in a mixed solution of 150 ml of THF and 30 ml of 6M hydrochloric acid, and stirred at room temperature for 8 hours under a nitrogen atmosphere. Toluene (200 ml) was added to the concentrate obtained by distilling off THF under reduced pressure.
And 150 ml of water were added, and the separated toluene layer was washed twice with 150 ml of water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography using toluene as a developing solvent to obtain 9.5 g of 2- (2,6-difluoro-4- (4-pentylphenyl) phenyl) acetaldehyde. .

Third step 2- (2,6-difluoro-4- (4-pentylphenyl) phenyl) obtained in the previous step under a nitrogen atmosphere in a 100 ml three-necked flask equipped with a stirrer, thermometer and cooling tube. Acetaldehyde 9.5 g (31.4 mmol) was dissolved in methanol 150 ml, and sodium borohydride 1.8 was added while stirring at 5 ° C.
g (47.1 mmol) was added, and the mixture was further stirred for 2 hours. 50 ml of 6M hydrochloric acid and 150 ml of toluene were added to the reaction mixture, and the separated toluene layer was washed 3 times with 150 ml of water and dried over anhydrous magnesium sulfate. 2- (2,
9.5 g of 6-difluoro-4- (4-pentylphenyl) phenyl) ethanol was obtained.

Fourth Step In a 300 ml three-necked flask equipped with a stirrer, a condenser tube and a Dean Stark dehydration tube, 9.5 g of 2- (2,6-difluoro-4- (4-pentylphenyl) phenyl) ethanol obtained in the preceding step Dissolve (31.2 mmol) in 100 ml of toluene and
% -Hydrobromic acid (13.4 g, 78.0 mmol) was added and the mixture was heated under reflux for 4 hours. After cooling to room temperature, 100 ml of water and 100 of toluene
ml was added, and the separated toluene layer was washed successively with 100 ml of a saturated aqueous sodium carbonate solution and 150 ml of water, and then dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography using heptane as a developing solvent to give 2- (2,6-difluoro-4-).
(4-pentylphenyl) phenyl) bromoethane 6.5
g was obtained.

Step 5 In a 200 ml three-necked flask equipped with a stirrer, a thermometer and a dropping funnel, 0.5 g (1
9.6 mmol) was suspended in 10 ml of THF, and 6.5 g (17.8 mmol) of 2- (2,6-difluoro-4- (4-pentylphenyl) phenyl) bromoethane obtained in the previous step was stirred while stirring.
A Grignard reagent was prepared by dropping the mixture at a temperature of not higher than 0 ° C. The Grignard reagent was then cooled to 5 ° C and carbon disulfide 3.4 g (4
(4.5 mmol) was added dropwise, and the mixture was stirred at room temperature for 2 hours. To the reaction mixture were added 6M hydrochloric acid (50 ml) and diethyl ether (150 ml), the separated ether layer was washed twice with 100 ml of water and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure,
By recrystallizing the residue from heptane, 3- (2,6
4.8 g of -difluoro-4- (4-pentylphenyl) phenyl) dithiopropionic acid were obtained.

Step 6 In a 300 ml three-necked flask equipped with a stirrer, a thermometer and a dropping funnel, 0.7 g (27.7 mmol) of sodium hydride (60% oily) was suspended in 10 ml of THF under a nitrogen atmosphere. 10 ml of a THF solution containing 2.6 g (13.2 mmol) of 3-fluoro-4-trifluoromethoxyphenol was added dropwise with stirring, and the mixture was stirred at room temperature for 30 minutes. There 3- (4) of the previous process
-(4-Pentylphenyl) -2,6-difluorophenyl) dithiopropionic acid 4.8 g (13.2 mmol) THF
Add 20 ml of the solution dropwise, stir at 60 ° C for 1 hour, and then add iodine 4.0
25 ml of a THF solution containing g (15.8 mmol) was added dropwise at 60 ° C., and the mixture was further stirred for 2 hours. 100 ml of water and 1 toluene in the reaction mixture
50 ml was added, and the separated toluene layer was washed successively with 50 ml of 10% aqueous sodium hydrogen sulfite solution and 100 ml of water twice, and then dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography using a heptane / toluene (95/5) mixed solvent as a developing solvent, and 3-fluoro-4-trifluoromethoxyphenyl = 3- (2,6 -Difluoro-4- (4-pentylphenyl) phenyl) thione-O-propionate
4.4 g was obtained.

Step 7 Teflon ^(R) equipped with stirrer, thermometer and dropping funnel
In a 200 ml three-necked flask manufactured by K.K., 4.6 g (25.3 mmol) of NBS was dissolved in 50 ml of dichloromethane, and while stirring, 5 ml of 70% HF-pyridine was added at -60 ° C or lower and the mixture was further stirred for 30 minutes. Then, in the previous step, 3-fluoro-4-trifluoromethoxyphenyl = 3- (2,6-difluoro-4-)
40 ml of a solution of 4.4 g (8.4 mmol) of (4-pentylphenyl) phenyl) thione-O-propionate in dichloromethane
Was added dropwise, and then the mixture was stirred at −10 to 0 ° C. for 2 hours. The reaction mixture was poured into 200 ml of a saturated aqueous solution of sodium carbonate, the separated dichloromethane layer was washed 3 times with 150 ml of water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography using a heptane / toluene (95/5) mixed solvent as a developing solvent.
And recrystallize from an equal volume mixture of heptane / ethanol to give the desired 1- (3- (2,6-
Difluoro-4- (4-pentylphenyl) phenyl)
2.1 g of -1,1-difluoropropyleneoxy) -3-fluoro-4-trifluoromethoxybenzene was obtained.

[0119]Example 3 1- (3- (trans-4-propylcyclohexyl)
Cyclohexyl) -1,1-difluoropropylene oxy
Si) -3,4,5-trifluorobenzene (in formula (1)
L = 1, k = m = n = 0, R¹Is an n-propyl group,
Ring A²And ring A ³Both trans-1,4-cyclo
Xylene group, Z²Is a single bond, Y¹And Y²Are both hydrogen
Atom, Y³, Y^FourAnd R²Both are fluorine atoms
Compound (Compound No. 39))

First step In a flask equipped with a stirrer, a thermometer and a dropping funnel, sodium hydride (3.36 g) was dissolved in tetrahydrofuran (hereinafter abbreviated as THF, 50 ml) under a nitrogen atmosphere, and the mixture was stirred at -5. After cooling to ° C, a solution of diethylphosphinoethyl acetate (18.8 g) in THF (30 ml) was added dropwise thereto. The reaction solution was further stirred for 2 hours, generation of hydrogen gas was confirmed, and trans-4- (trans-4-propylcyclohexyl) cyclohexanecarbaldehyde (16.5
A solution of g) in THF (50 ml) was added dropwise. The reaction solution was warmed to room temperature and stirred for 3 hours. After completion of stirring, water was added to the reaction solution, and the mixture was extracted with toluene (50 ml × 3). The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give ethyl 3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) propenoate (1
0.0 g) was obtained.

Step 2 Ethyl 3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) propenoate (10.0 g) obtained above was mixed with a toluene: ethanol mixed solvent (1:
1, 80 ml) and dissolved in 5% palladium-carbon (1.8
g) was added and the mixture was stirred under a hydrogen atmosphere for 8 hours. After completion of stirring, the catalyst was removed by filtration, the filtrate was concentrated under reduced pressure,
The obtained yellow oily substance was dissolved in ethanol (80 ml) to give 2N.
A sodium hydroxide solution (30 ml) was added and the mixture was stirred at room temperature for 8 hours. After completion of stirring, water was added to the reaction solution to bring it to PH4 with 2N hydrochloric acid, and the precipitated crystals were filtered. The obtained crystals were recrystallized from THF-ether (1: 8, 50 ml) to give 3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) propionic acid (4.0 g) as white crystals.

Third Step 3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) propionic acid (5.0 g) obtained above was suspended in toluene to give 1,3-propanedithiol (2.5 g). Was added and the mixture was heated to 50 ° C. and stirred. Trifluoromethanesulfonic acid (3.5 g) was added dropwise to the suspension over 30 minutes, and after completion of the addition, the system was heated to reflux for 4 hours with a Dean Stark apparatus, and the distilled water was removed. The reaction mixture was concentrated under reduced pressure, diethyl ether was added, and the precipitated crystals were collected by filtration and used as 2- (2- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl).
Ethyl) -1,3-dithianilium triflate (4.0
g) was obtained.

Fourth Step 3,4,5-Trifluorophenol (1.27 g) and triethylamine (870 mg) were dissolved in methylene chloride (10 ml) and stirred at -78 ° C to obtain 2- (2) obtained above. -(Trans-4- (trans-4-propylcyclohexyl)
A solution of cyclohexyl) ethyl) -1,3-dithianilium triflate (3.8 g) in methylene chloride (5 ml) was added dropwise. After the addition was complete, the solution was stirred for an additional 1 hour, then Et.
₃ N · 3HF _(6.24ml) was added and further bromine (6.24 g)
Methylene chloride solution was added dropwise. The reaction solution was stirred at -70 ° C for 1 hour, gradually warmed, and poured into cold 3N sodium hydroxide solution (100ml) at 0 ° C to add methylene chloride (30ml x
Extracted in 3). The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting yellow oily substance was isolated and purified by silica gel column chromatography using heptane as a developing solvent, and 1- (3- (trans-4-propylcyclohexyl) cyclohexyl)-
1,1-Difluoropropyleneoxy) -3,4,5-trifluorobenzene (1.0 g) was obtained as colorless crystals.
The transition points of this product are shown below. Cr 68.6 N
113.16 I (° C)

The measurement results of various spectral data strongly supported the structure. ¹ H-NMR (δppm, CDCl ₃ ): 0.8-2.2 (31H, m), 6.85-6.88
(2H, m) ¹⁹ F-NMR (δppm, CDCl ₃ ): -79.26 (2F, t), -133.53--
133.65 (2F, m), -165.00--165.06 (1F, m,) GC-MS (EI): 432 (M +, 18.5%), 69 (100), 148 (80.1), 83
(75.5), 81 (47.5), 95 (42.7), 82 (42.8), 55 (39.0),

Example 4 1- (3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -1,1-difluoropropyleneoxy) -2,3-difluoro-4-ethoxybenzene (formula (1 ), L = 1, k = m = n =
0, R ¹ is an n-propyl group, both ring A ² and ring A ³ are trans-1,4-cyclohexylene groups, Z ² is a single bond, Y
^A compound in which ² and Y ⁴ are both hydrogen atoms, Y ¹ and Y ³ are both fluorine atoms, and R ² is an ethoxy group (Compound No. 4
6)) Manufacturing

First step In a 3 L three-necked flask equipped with a stirrer, a thermometer and a dropping funnel, under a nitrogen atmosphere, 3- (trans-4- (trans-
4-Propylcyclohexyl) cyclohexyl) propionic acid 32.0 g (114.9 mmol) and 2,3-difluoro-
20.0 g (114.9 mmol) of 4-ethoxyphenol was dissolved in 1000 ml of dichloromethane at room temperature, and 15.4 g (126.4 mmol) of 4-dimethylaminopyridine was added with stirring.
After addition, the mixture was stirred for 30 minutes, and then 26.1 g (126.4 m) of dicyclohexylcarbodiimide dissolved in 400 ml of dichloromethane.
mol) solution was added dropwise at room temperature, and after the mixture was stirred at room temperature for 14 hours. Water (500 ml) was added to the reaction solution, insoluble materials were collected by filtration, and the filtrate was washed with 3M hydrochloric acid (300 ml), water (300 ml), saturated aqueous sodium hydrogen carbonate solution (300 ml) and water (600 ml), and dried over anhydrous magnesium sulfate. The solvent was distilled off from the reaction solution under reduced pressure to obtain 56.4 g of a concentrate. The concentrate is then heptane /
Purified by silica gel column chromatography using a mixed solution of ethyl acetate (7/3) as a developing solvent, and 2,3-difluoro-4-ethoxyphenyl = 3 as colorless crystals.
51.4 g of-(trans-4- (trans-4-propylcyclohexyl) cyclohexyl) propionate was obtained.

Second step In a 2 L three-necked flask equipped with a stirrer, a thermometer and a dropping funnel, 2,3-difluoro-4-obtained above under a nitrogen atmosphere.
Ethoxyphenyl = 3- (trans-4- (trans-
4-Propylcyclohexyl) cyclohexyl) propionate 51.4 g (118.0 mmol), Laweson's reagent 95.5 g
(236.0 mmol) and 470 ml of mesitylene were mixed and heated under reflux for 4 hours with stirring. After cooling to room temperature, the insoluble matter was filtered off, 500 ml of water was added to the filtrate, and the mixture was extracted with 400 ml of toluene. The extract layer was washed successively with 500 ml of water, 300 ml of saturated aqueous sodium hydrogen carbonate solution and 1000 ml of water, and dried over anhydrous magnesium sulfate. The solvent of the reaction solution was distilled off under reduced pressure to obtain a concentrate. Next, the concentrate was purified by silica gel column chromatography using a mixed solution of toluene / heptane (1/1) as a developing solvent to obtain 2,2 as a yellow crystal.
14.2 g of 3-difluoro-4-ethoxyphenyl = 3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) thione-O-propionate was obtained.

Third step 500 made of Teflon ^(R) equipped with a stirrer, a thermometer, and a dropping funnel
5.5 ml of NBS (31.0 m
mol) in 130 ml of dichloromethane and with stirring-
Add 14% of 70% HF-pyridine below 60 ℃,
Stir for minutes. Then, 2,3-difluoro-4-ethoxyphenyl = 3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) obtained in the previous step
A solution of 7.00 g (15.5 mmol) of thione-O-propionate in 65 ml of dichloromethane was added dropwise, and after the addition, -10 ° C.
It was stirred for 3 hours. The reaction mixture was poured into 500 ml of saturated aqueous sodium carbonate solution, the dichloromethane layer was separated, washed with 200 ml of water three times, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography using a mixed solution of toluene / heptane (3/7) as a developing solvent, and further heptane /
Recrystallize from an equal volume mixture of ethanol to give the desired 1-
2.7 g of (3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -1,1-difluoropropyleneoxy) -2,3-difluoro-4-ethoxybenzene was obtained. This has a liquid crystal phase, and its transition point is shown below. Cr 47.4 Cr 51.9
S _A 99.5 N 164.0 Iso

The results of measurement of various spectral data strongly supported the structure. ¹ H-NMR (δppm, CDCl ₃ ): 0.82-1.12 (m, 13H), 1.12-1.3
4 (m, 5H), 1.45 (t, 3H), 1.50-1.55 (m, 3H), 1.68-1.80
(m, 8H), 2.12-2.20 (m, 2H), 4.10 (q, 2H), 6.63-6.67
(m, 1H), 6.94-6.97 (m, 1H) ¹⁹ F-NMR (δppm): -72.0--72.1 (t, 2F), -150.8--150.9
(m, 1F), -156.5--156.6 (m, 1F)

The following compounds No. 1 to No. 204 can be produced based on the description in Examples 1 to 4 and the detailed description of the invention. The compounds obtained in Examples 1 to 4 are also listed below.

[0131]

[Chemical formula 45]

[0132]

[Chemical formula 46]

[0133]

[Chemical 47]

[0134]

[Chemical 48]

[0135]

[Chemical 49]

[0136]

[Chemical 50]

[0137]

[Chemical 51]

[0138]

[Chemical 52]

[0139]

[Chemical 53]

[0140]

[Chemical 54]

[0141]

[Chemical 55]

[0142]

[Chemical 56]

[0143]

[Chemical 57]

[0144]

[Chemical 58]

[0145]

[Chemical 59]

[0146]

[Chemical 60]

[0147]

[Chemical formula 61]

[0148]

[Chemical formula 62]

[0149]

[Chemical formula 63]

[0150]

[Chemical 64]

[0151]

[Chemical 65]

[0152]

[Chemical formula 66]

[0153]

[Chemical formula 67]

[0154]

[Chemical 68]

[0155]

[Chemical 69]

[0156]

[Chemical 70]

Example 5 Nematic liquid crystal composition containing a cyanophenylcyclohexane type liquid crystal compound (hereinafter referred to as liquid crystal composition A): 4- (4-propylcyclohexyl) benzonitrile 24% 4- (4-pentylcyclohexyl) Benzonitrile 36% 4- (4-heptylcyclohexyl) benzonitrile 25% 4- (4- (4-pentylcyclohexyl) phenyl) benzonitrile 15% has the following properties:

Clearing point (TNI): 71.7 ° C., cell thickness 8.
Threshold voltage (Vth) at 8 μm: 1.78 V, Δ
ε: 11.0, Δn: 0.137, viscosity at 20 ° C. (η): 26.3 mPa · s. 85% by weight of this liquid crystal composition A and 1-obtained in Example 1
(3- (trans-4- (trans-4-pentylcyclohexyl) cyclohexyl) -1,1-difluoropropyleneoxy) -3,4,5-trifluorobenzene (Compound No. 40) 15 wt% liquid crystal A composition was prepared. The characteristics were as follows. Clearing point (TNI): 75.8 ° C., threshold voltage (Vth) at cell thickness 8.9 μm: 1.70 V, Δε: 11.4, Δ
n: 0.128, viscosity at 20 ° C (η): 28.4 m
Pa · s.

The compound No. was calculated by extrapolation from the physical properties of each liquid crystal composition and the mixing ratio of the compounds.
The physical property values of 40 were as follows. Clearing point (TNI): 99.0 ° C, Δε: 13.7, Δn:
Viscosity (η) at 0.077, 20 ° C: 31.8 mPas
・ S.

Example 6 85% by weight of the liquid crystal composition A shown in Example 4 and 1- (3
-(4'-propyl-3,5-difluorobiphenyl-
4-yl) -1,1-difluoropropyleneoxy)-
3,4,5-Trifluorobenzene (Compound No. 63)
A liquid crystal composition consisting of 15% by weight was prepared. The characteristics were as follows. Clearing point (TNI): 61.4 ° C., threshold voltage (Vth) at cell thickness of 8.9 μm: 1.50 V, Δε: 13.5, Δ
n: 0.133, viscosity at 20 ° C. (η): 30.0 m
Pa · s. The physical properties of the compound calculated by extrapolation from the physical properties of each liquid crystal composition and the mixing ratio of the compounds were as follows. Clearing point (TNI): 4.4 ° C, Δε: 24.3, Δn:
Viscosity (η) at 0.110 and 20 ° C: 45.3 mPas
・ S.

Example 7 Nematic liquid crystal composition (hereinafter referred to as liquid crystal composition B): 4-ethoxyphenyl = 4-propylcyclohexanecarboxylate 17.2% 4-butoxyphenyl = 4-propylcyclohexanecarboxylate 27.6 % 4-ethoxyphenyl = 4-butylcyclohexanecarboxylate 20.7% 4-methoxyphenyl = 4-pentylcyclohexanecarboxylate 20.7% 4-ethoxyphenyl = 4-pentylcyclohexanecarboxylate 13.8% has the following characteristics. Have.

Clearing point (T _NI ): 74.0 ° C., Δε: −1.
3, Δn: 0.087, viscosity at 20 ° C (η2
0): 18.9 mPa · s. 85% by weight of this liquid crystal composition B and 1-obtained in Example 3
(3- (trans-4- (trans-4-propylcyclohexyl) cyclohexyl) -1,1-difluoropropyleneoxy) -2,3-difluoro-4-ethoxybenzene (Compound No. 46) 15% by weight A liquid crystal composition was prepared. The characteristics were as follows. Clearing point (T _NI ): 84.9 ° C., Δε: -1.72, Δn:
Viscosity (η20) at 0.089, 20 ° C: 24.3 m
Pa · s. The physical properties of compound No. 46 calculated by extrapolation from the physical properties of each liquid crystal composition and the mixing ratio of the compounds were as follows. Clearing point (T _NI ): 143.3 ° C, Δε: -3.70, Δ
n: 0.100, viscosity at 20 ° C. (η20): 48.
1 mPa · s.

Example 8 According to Example 7, 85% by weight of the liquid crystal composition B and the compound of the present invention 1- (3- (2,3-difluoro-4-ethoxyphenyl) -1,1-difluoropropyleneoxy) -4-
A liquid crystal composition containing (trans-4-propylcyclohexyl) benzene (Compound No. 201) 15% by weight was prepared. The characteristics were as follows. Clearing point (T _NI ): 77.9 ° C, Δε: -1.88, Δn:
Viscosity (η20) at 0.092, 20 ° C: 24.2 m
Pa · s. The physical properties of compound No. 201 calculated by extrapolation from the physical properties of each liquid crystal composition and the mixing ratio of the compounds were as follows. Clearing point (T _NI ): 96.6 ° C., Δε: −4.88, Δn:
Viscosity (η20) at 0.120 and 20 ° C: 48.0m
Pa · s.

The compositions and physical properties of the nematic liquid crystal compositions of the present invention containing the compound of formula (1) synthesized according to the above method as the first component are shown in Examples 9 to 54 below.
In addition, each compound in the composition was represented according to the agreement shown in Table 2 below by associating the groups shown in the columns of the left terminal group, the bonding group, the ring structure and the right terminal group with the respective symbols.

[0165]

[Table 2]

The No. given to the compound in the composition is the same as that shown in the above-mentioned Examples, and the content of the compound means% by weight unless otherwise specified. The characteristic data of the composition examples are NI (nematic-isotropic liquid transition temperature or clearing point), η (viscosity: measurement temperature 20.0 ° C.),
Δn (refractive index anisotropy value: measurement temperature 25.0 ° C.), Δε
(Dielectric anisotropy value: measurement temperature 25.0 ° C.) and Vth
(Threshold voltage: measured temperature 25.0 ° C.).

Example 9 5-HH2ZB (F, F) -F (No.40) 8.0% 5-H2ZB (F, F) -C (No.11) 7.0% 1V2-BEB (F, F) -C 5.0% 3-HB-C 10.0% 1-BTB-3 5.0% 2-BTB-1 10.0% 3-HH-4 11.0% 3-HHB-1 11 0.0% 3-HHB-3 9.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB (F) TB-2 6. 0% 3-HB (F) TB-3 6.0% NI = 92.4 (° C) η = 16.6 (mPa · s) Δn = 0.154 Δε = 8.5 Vth = 1.99 (V ) The pitch when 0.8 part of CM33 was added to 100 parts of the above composition was 10.7 μm.

Example 10 3-HH2ZB (F) -OCF3 (No.36) 5.0% 5-HH2ZB (F) -OCF3 (No.37) 5.0% 3-H2ZB (F, F) B ( F) -F (No.99) 7.0% 5-H2ZB (F, F) B (F) -F (No.100) 6.0% 2O1-BEB (F) -C 5.0% 3O1- BEB (F) -C 15.0% 4O1-BEB (F) -C 8.0% 5O1-BEB (F) -C 8.0% 2-HHB (F) -C 9.0% 3-HHB ( F) -C 8.0% 3-HB (F) TB-2 4.0% 3-HB (F) TB-3 4.0% 3-HB (F) TB-4 4.0% 3-HHB -1 8.0% 3-HHB-O1 4.0% NI = 87.6 (° C) η = 79.0 (mPa · s) Δn = 0.141 Δε = 29.9 Vth = 0.89 (V )

Example 11 5-H2ZB (F, F) -F (No.5) 2.0% 5-H2ZB (F) -OCF3 (No.7) 2.0% 5-H2ZB (F) B ( F, F) -F (No.102) 3.0% 5-H2ZB (F, F) -C (No.11) 2.0% 5-PyB-F 2.0% 3-PyB (F)- F 2.0% 2-BB-C 3.0% 4-BB-C 3.0% 5-BB-C 3.0% 2-PyB-2 2.0% 3-PyB-2 2.0% 4-PyB-2 2.0% 6-PyB-O5 3.0% 6-PyB-O6 3.0% 6-PyB-O7 3.0% 6-PyB-O8 3.0% 3-PyBB-F 6.0% 4-PyBB-F 6.0% 5-PyBB-F 6.0% 3-HHB-1 6.0% 3-HHB-3 8.0% 2-H2BTB-2 4.0% 2 -H2BTB-3 4.0% 2-H2BTB- 5.0% 3-H2BTB-2 5.0% 3-H2BTB-3 5.0% 3-H2BTB-4 5.0% NI = 93.5 (° C.) η = 35.6 (mPa · s) Δn = 0.193 Δε = 6.6 Vth = 2.26 (V)

Example 12 3-HH2ZB (F, F) -F (No.39) 4.0% 3-H2ZB (F, F) -F (No.4) 3.0% 3-H2ZB (F) -OCF3 (No. 6) 4.0% 3-GB-C 6.0% 4-GB-C 6.0% 2-BEB-C 12.0% 3-BEB-C 4.0% 3-PyB (F) -F 3.0% 3-HEB-O4 8.0% 4-HEB-O2 6.0% 5-HEB-O1 6.0% 3-HEB-O2 5.0% 5-HEB-O2 4.0% 5-HEB-5 5.0% 4-HEB-5 5.0% 1O-BEB-2 4.0% 3-HHB-1 6.0% 3-HHEBB-C 3.0% 3 -HBEBB-C 3.0% 5-HBEBB-C 3.0% NI = 68.7 (° C) η = 36.7 (mPa · s) Δn = 0.112 Δε = 10.8 Vth = 1.34 (V)

Example 13 3-H2ZB (F, F) -F (No.4) 4.0% 5-H2ZB (F, F) -F (No.5) 4.0% 3-HH2ZB (F) -OCF3 (No.6) 9.0% 3-H2ZB (F, F) B (F) -F (No.99) 3.0% 3-HB-C 8.0% 7-HB-C 3. 0% 1O1-HB-C 5.0% 3-HB (F) -C 5.0% 2-PyB-2 2.0% 3-PyB-2 2.0% 4-PyB-2 2.0% 1O1-HH-3 7.0% 2-BTB-O1 7.0% 3-HHB-1 7.0% 3-HHB-F 4.0% 3-HHB-O1 4.0% 3-HHB-3 8.0% 3-H2BTB-2 3.0% 3-H2BTB-3 3.0% 2-PyBH-3 4.0% 3-PyBH-3 3.0% 3-PyBB-2 3.0% NI = 79.5 (° C) η = 16.4 (mPa · s ) Δn = 0.126 Δε = 7.7 Vth = 1.80 (V)

Example 14 3-HH2ZB (F, F) -F (No.39) 3.0% 5-HH2ZB (F) -OCF3 (No.37) 6.0% 3-H2ZB (F, F) -C (No.10) 9.0% 2-BEB (F) -C 5.0% 3-BEB (F) -C 4.0% 4-BEB (F) -C 4.0% 1V2-BEB (F, F) -C 6.0% 3-HH-EMe 10.0% 3-HB-O2 18.0% 7-HEB-F 2.0% 3-HHEB-F 2.0% 5-HHEB -F 2.0% 3-HBEB-F 4.0% 2O1-HBEB (F) -C 2.0% 3-HB (F) EB (F) -C 2.0% 3-HBEB (F, F ) -C 2.0% 3-HHB-F 4.0% 3-HHB-O1 4.0% 3-HHB-3 7.0% 3-HEBEB-F 2.0% 3-HEBEB-1 2. 0% NI = 78.2 (℃ η = 33.6 (mPa · s) Δn = 0.109 Δε = 23.7 Vth = 0.90 (V)

Example 15 3-H2ZB (F, F) -C (No.10) 9.0% 5-H2ZB (F, F) -C (No.11) 8.0% 2-BEB (F) -C 5.0% 3-BEB (F) -C 4.0% 4-BEB (F) -C 4.0% 1V2-BEB (F, F) -C 7.0% 3-HB-O2 10 0.0% 3-HH-4 3.0% 3-HHB-F 3.0% 3-HHB-1 8.0% 3-HHB-O1 4.0% 3-HBEB-F 4.0% 3- HHEB-F 7.0% 5-HHEB-F 7.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB (F) TB -5.0% NI = 87.5 (° C.) η = 35.8 (mPa · s) Δn = 0.131 Δε = 24.9 Vth = 1.15 (V)

Example 16 5-HH2ZB (F, F) -F (No.40) 4.0% 5-H2ZB (F, F) -F (No.5) 3.0% 3-HH2ZB (F) -OCF3 (No.36) 3.0% 5-HH2ZB (F) -OCF3 (No.37) 4.0% 3-H2ZB (F, F) B (F) -F (No.99) 3.0 % 3-H2ZB (F) B (F, F) -F (No.101) 7.0% 5-H2ZB (F) B (F, F) -F (No.102) 7.0% 3-H2ZB (F, F) -C (No. 10) 4.0% 2-BEB-C 4.0% 3-BEB-C 3.0% 4-BEB-C 3.0% 3-HB-C 5. 0% 3-HEB-O4 12.0% 4-HEB-O2 8.0% 5-HEB-O1 8.0% 3-HEB-O2 6.0% 5-HEB-O2 5.0% 3-HHB -1 7.0% 3-HHB-O1 .0% NI = 63.4 (℃) η = 29.9 (mPa · s) Δn = 0.092 Δε = 10.2 Vth = 1.34 (V)

Example 17 3-H2ZB (F, F) B (F) -F (No.99) 5.0% 5-H2ZBB (F, F) B-2 (No.182) 6.0% 5 -H2ZBB (F, F) B-F (No.184) 6.0% 2-BEB-C 10.0% 5-BB-C 7.0% 7-BB-C 7.0% 1-BTB- 3 7.0% 2-BTB-1 10.0% 1O-BEB-2 7.0% 1O-BEB-5 9.0% 2-HHB-1 4.0% 3-HHB-F 4.0% 3-HHB-1 7.0% 3-HHB-O1 4.0% 3-HHB-3 7.0%

Example 18 3-HH2ZB (F) -OCF3 (No.36) 3.0% 5-HH2ZB (F) -OCF3 (No.37) 3.0% 2-HB-C 5.0% 3 -HB-C 12.0% 3-HB-O2 15.0% 2-BTB-1 3.0% 3-HHB-1 8.0% 3-HHB-F 4.0% 3-HHB-O1 5 0.0% 3-HHB-3 14.0% 3-HHEB-F 4.0% 5-HHEB-F 4.0% 2-HHB (F) -F 5.0% 3-HHB (F) -F 5.0% 5-HHB (F) -F 5.0% 3-HHB (F, F) -F 5.0% NI = 101.3 (° C) η = 18.3 (mPa · s) Δn = 0.100 Δε = 5.1 Vth = 2.49 (V)

Example 19 5-H2ZB (F, F) B (F) -F (No.100) 3.0% 3-H2ZB (F) B (F, F) -F (No.101) 3. 0% 3-H2ZB (F, F) -C (No. 10) 2.0% 3-BEB (F) -C 4.0% 3-HB-C 4.0% V-HB-C 8.0 % 1V-HB-C 8.0% 3-HB-O2 3.0% 3-HH-2V 14.0% 3-HH-2V1 7.0% V2-HHB-1 15.0% 3-HHB- 1 5.0% 3-HHEB-F 7.0% 3-H2BTB-2 6.0% 3-H2BTB-3 6.0% 3-H2BTB-4 5.0% NI = 98.8 (° C) η = 17.3 (mPa · s) Δn = 0.129 Δε = 8.0 Vth = 2.24 (V)

Example 20 3-HH2ZB (F, F) -F (No.39) 7.0% 5-HH2ZB (F, F) -F (No.40) 7.0% 3-H2ZB (F) B (F, F) -F (No.101) 3.0% 5-H2ZB (F) B (F, F) -F (No.102) 3.0% 3-H2ZB (F, F) -C (No.10) 6.0% 5-H2ZB (F, F) -C (No.11) 5.0% V2-HB-C 6.0% 1V2-HB-C 6.0% 3-HB- C 5.0% 3-HB (F) -C 5.0% 2-BTB-1 2.0% 3-HH-4 8.0% 3-HH-VFF 6.0% 2-HHB-C3 0.0% 3-HHB-C 6.0% 3-HB (F) TB-2 8.0% 3-H2BTB-2 5.0% 3-H2BTB-3 5.0% 3-H2BTB-4 4. 0% NI = 87.8 (° C.) η = 21.4 (mPa · s) Δ n = 0.137 Δε = 11.6 Vth = 1.73 (V)

Example 21 5-HH2ZB (F) -OCF3 (No.37) 3.0% 3-H2ZB (F, F) -C (No.10) 3.0% 5-BEB (F) -C 5.0% V-HB-C 5.0% 5-PyB-C 6.0% 4-BB-3 11.0% 3-HH-2V 10.0% 5-HH-V 11.0% V -HHB-1 7.0% V2-HHB-1 15.0% 3-HHB-1 9.0% 1V2-HBB-2 10.0% 3-HHEBH-3 5.0% NI = 92.9 ( ℃) η = 16.1 (mPa · s) Δn = 0.112 Δε = 5.5 Vth = 2.28 (V)

Example 22 5-H2ZB (F, F) -F (No.5) 2.0% 3-H2ZB (F) -OCF3 (No.6) 3.0% 3-HH2ZB (F) -OCF3 (No.36) 7.0% 5-H2ZB (F) B (F, F) -F (No.102) 3.0% 1V2-BEB (F, F) -C 3.0% 3-HB- C 7.0% V2V-HB-C 7.0% V2V-HH-3 19.0% 3-HB-O2 4.0% 3-HHB-1 10.0% 3-HHB-3 15.0% 3-HB (F) TB-2 4.0% 3-HB (F) TB-3 4.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4 0.0% NI = 101.3 (° C.) η = 15.2 (mPa · s) Δn = 0.117 Δε = 5.6 Vth = 2.30 (V)

Example 23 3-HH2ZB (F, F) -F (No.39) 3.0% 3-H2ZB (F, F) B (F) -F (No.99) 4.0% 5- H2ZB (F, F) B (F) -F (No.100) 4.0% V2-HB-TC 10.0% 3-HB-TC 10.0% 3-HB-C 3.0% 5- HB-C 3.0% 5-BB-C 3.0% 2-BTB-1 10.0% 2-BTB-O1 5.0% 3-HH-4 5.0% 3-HHB-1 10. 0% 3-HHB-3 11.0% 3-H2BTB-2 3.0% 3-H2BTB-3 3.0% 3-HB (F) TB-2 3.0% 5-BTB (F) TB- 3 10.0% NI = 101.2 (° C) η = 16.7 (mPa · s) Δn = 0.202 Δε = 7.5 Vth = 2.15 (V)

Example 24 3-H2ZB (F, F) -C (No.10) 8.0% 5-H2ZB (F, F) -C (No.11) 8.0% 1V2-BEB (F, F) -C 3.0% 3-HB-C 5.0% 2-BTB-1 10.0% 5-HH-VFF 30.0% 1-BHH-VFF 8.0% 1-BHH-2VFF 11 0.0% 3-H2BTB-2 5.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HHB-1 4.0% NI = 74.8 (° C) η = 13 .5 (mPa · s) Δn = 0.120 Δε = 8.1 Vth = 1.75 (V)

Example 25 3-H2ZB (F, F) -C (No.10) 8.0% 5-H2ZB (F, F) -C (No.11) 7.0% 5-HBZB (F, F) -C 3.0% 3-HB (F, F) ZB (F, F) -C 3.0% 3-HB-C 3.0% 2-BTB-1 10.0% 5-HH- VFF 30.0% 1-BHH-VFF 8.0% 1-BHH-2 VFF 11.0% 3-H2BTB-2 5.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HHB-1 4.0% NI = 76.6 (° C.) η = 14.5 (mPa · s) Δn = 0.120 Δε = 7.5 Vth = 1.81 (V)

Example 26 3-HH2ZB (F, F) -F (No.39) 4.0% 3-HH2ZB (F) -OCF3 (No.36) 3.0% 5-H2ZB (F, F) B (F) -F (No.100) 3.0% 5-H2ZB (F) B (F, F) -F (No.102) 5.0% 2-HHB (F) -F 5.0% 3-HHB (F) -F 14.0% 5-HHB (F) -F 16.0% 2-H2HB (F) -F 10.0% 3-H2HB (F) -F 5.0% 5- H2HB (F) -F 10.0% 2-HBB (F) -F 6.0% 3-HBB (F) -F 6.0% 5-HBB (F) -F 13.0% NI = 97. 9 (° C) η = 27.3 (mPa · s) Δn = 0.096 Δε = 6.4 Vth = 2.01 (V) When 0.3 part of CN is added to 100 parts of the above composition, the pitch is It was 77.5 μm.

Example 27 5-HH2ZB (F, F) -F (No.40) 7.0% 5-HH2ZB (F) -OCF3 (No.37) 6.0% 5-H2ZBB (F, F) B-2 (No.182) 5.0% 5-H2ZBB (F, F) B-F (No.184) 4.0% 7-HB (F, F) -F 3.0% 3-HB- O2 7.0% 2-HHB (F) -F 8.0% 3-HHB (F) -F 8.0% 5-HHB (F) -F 8.0% 2-HBB (F) -F6 0.0% 3-HBB (F) -F 6.0% 5-HBB (F) -F 6.0% 2-HBB-F 4.0% 3-HBB-F 4.0% 5-HBB-F 3.0% 3-HBB (F, F) -F 5.0% 5-HBB (F, F) -F 10.0%

Example 28 3-HH2ZB (F, F) -F (No.39) 3.0% 3-H2ZB (F, F) -F (No.4) 3.0% 3-H2ZB (F) -OCF3 (No.6) 3.0% 3-HH2ZB (F) -OCF3 (No.36) 4.0% 5-HH2ZB (F) -OCF3 (No.37) 4.0% 3-H2ZB (F) , F) B (F) -F (No.99) 3.0% 5-HB-CL 4.0% 3-HH-4 12.0% 3-HH-5 4.0% 3-HHB-F 4.0% 3-HHB-CL 3.0% 4-HHB-CL 4.0% 3-HHB (F) -F 7.0% 4-HHB (F) -F 7.0% 5-HHB ( F) -F 7.0% 7-HHB (F) -F 7.0% 5-HBB (F) -F 4.0% 5-HBBH-1O1 3.0% 3-HHBB (F, F)- F 2.0% 4-HHBB (F, F) F 3.0% 5-HHBB (F, F) -F 3.0% 3-HH2BB (F, F) -F 3.0% 4-HH2BB (F, F) -F 3.0% NI = 115 .8 (° C.) η = 23.0 (mPa · s) Δn = 0.087 Δε = 5.5 Vth = 2.42 (V)

Example 29 3-HH2ZB (F, F) -F (No.39) 3.0% 5-HH2ZB (F, F) -F (No.40) 4.0% 5-H2ZB (F, F) -F (No.5) 3.0% 5-H2ZB (F) -OCF3 (No.7) 3.0% 3-HH2ZB (F) -OCF3 (No.36) 6.0% 5-HH2ZB (F) -OCF3 (No.37) 6.0% 3-H2ZB (F, F) B (F) -F (No.99) 3.0% 5-H2ZB (F, F) B (F)- F (No.100) 4.0% 3-H2ZB (F) B (F, F) -F (No.101) 3.0% 5-H2ZB (F) B (F, F) -F (No. 102) 4.0% 3-HHB (F, F) -F 9.0% 3-H2HB (F, F) -F 4.0% 4-H2HB (F, F) -F 4.0% 5- H2HB (F, F) -F 4.0% 3-HBB (F, F ) -F 10.0% 5-HBB (F, F) -F 10.0% 3-H2BB (F, F) -F 4.0% 5-HHBB (F, F) -F 3.0% 5 -HHEBB-F 2.0% 3-HH2BB (F, F) -F 3.0% 4-HBBH-1O1 4.0% 5-HBBH-1O1 4.0% NI = 97.6 (° C.) η = 34.2 (mPa · s) Δn = 0.106 Δε = 10.9 Vth = 1.56 (V)

Example 30 3-HH2ZB (F) -OCF3 (No.36) 3.0% 5-H2ZB (F) B (F, F) -F (No.102) 3.0% 5-HB- F 12.0% 6-HB-F 9.0% 7-HB-F 7.0% 2-HHB-OCF3 7.0% 3-HHB-OCF3 7.0% 4-HHB-OCF3 7.0% 5-HHB-OCF3 5.0% 3-HH2B-OCF3 4.0% 5-HH2B-OCF3 4.0% 3-HHB (F, F) -OCF3 5.0% 3-HBB (F) -F7 0.0% 5-HBB (F) -F 7.0% 3-HH2B (F) -F 3.0% 3-HB (F) BH-3 3.0% 5-HBBH-3 3.0% 3 -HHB (F, F) -OCF2H 4.0% NI = 84.6 (° C) η = 15.5 (mPa · s) Δn = 0.089 Δε = 5.0 Vth = 2.30 (V)

Example 31 3-HH2ZB (F) -OCF3 (No.36) 6.0% 5-HH2ZB (F) -OCF3 (No.37) 6.0% 3-H2ZB (F, F) B ( F) -F (No.99) 4.0% 5-H2ZB (F, F) B (F) -F (No.100) 4.0% 3-H2ZB (F) B (F, F) -F (No.101) 8.0% 5-H2ZB (F) B (F, F) -F (No.102) 8.0% 2-HHB (F) -F 3.0% 2-HBB (F) -F 3.0% 3-HBB (F) -F 7.0% 4-HBB (F) -F 2.0% 5-HBB (F) -F 7.0% 2-H2BB (F) -F 6.0% 3-H2BB (F) -F 6.0% 3-HBB (F, F) -F 6.0% 5-HBB (F, F) -F 6.0% 2-HHB (F, F) -F 5.0% 3-HHB (F, F) -F 5.0% 4- HB (F, F) -F 5.0% 3-HHB-F 3.0% NI = 96.0 (° C) η = 37.8 (mPa · s) Δn = 0.127 Δε = 10.2 Vth = 1.58 (V)

Example 32 3-H2ZB (F, F) -F (No.4) 3.0% 3-H2ZB (F, F) B (F) -F (No.99) 5.0% 3- H2ZB (F) B (F, F) -F (No.101) 5.0% 5-H2ZB (F) B (F, F) -F (No.102) 5.0% 5-HB-CL 3 0.0% 3-HH-4 8.0% 3-HBB (F, F) -F 15.0% 5-HBB (F, F) -F 10.0% 3-HHB (F, F) -F 8.0% 3-HHEB (F, F) -F 10.0% 4-HHEB (F, F) -F 3.0% 5-HHEB (F, F) -F 3.0% 2-HBEB ( F, F) -F 3.0% 3-HBEB (F, F) -F 5.0% 5-HBEB (F, F) -F 3.0% 3-HHBB (F, F) -F 6. 0% 3-HHB-1 5.0% NI = 78.5 (° C.) η = 26.6 (mPa · s) Δn = .102 Δε = 10.2 Vth = 1.42 (V)

Example 33 3-HH2ZB (F, F) -F (No.39) 5.0% 5-HH2ZB (F, F) -F (No.40) 5.0% 3-HH2ZB (F) -OCF3 (No. 36) 5.0% 7-HB (F) -F 6.0% 5-H2B (F) -F 6.0% 3-HB-O2 4.0% 3-HH-4 12 0.0% 2-HHB (F) -F 6.0% 3-HHB (F) -F 6.0% 5-HHB (F) -F 6.0% 2-HBB (F) -F 2.0 % 3-HBB (F) -F 2.0% 5-HBB (F) -F 4.0% 3-HBB (F, F) -F 3.0% 2-HHBB (F, F) -F 4 0.0% 3-HHBB (F, F) -F 5.0% 3-HHEB-F 4.0% 5-HHEB-F 4.0% 3-HHB-1 7.0% 3-HHB-34 0.0% NI = 100.5 (° C) η = 20.4 (mPa · s) Δ = 0.087 Δε = 5.7 Vth = 2.12 (V)

Example 34 3-HH2ZB (F, F) -F (No.39) 6.0% 5-HH2ZB (F, F) -F (No.40) 6.0% 5-HH2ZB (F) -OCF3 (No.37) 3.0% 3-H2ZB (F, F) B (F) -F (No.99) 6.0% 5-H2ZB (F, F) B (F) -F (No .100) 6.0% 3-H2ZB (F) B (F, F) -F (No.101) 13.0% 5-H2ZB (F) B (F, F) -F (No.102) 12 0.0% 3-HH-4 4.0% 3-H2HB (F, F) -F 6.0% 4-H2HB (F, F) -F 6.0% 5-H2HB (F, F) -F 4.0% 3-HBB (F, F) -F 13.0% 5-HBB (F, F) -F 12.0% 3-HHBB (F, F) -F 3.0% NI = 64. 2 (° C) η = 33.9 (mPa · s) Δn = 0.103 Δε = 1 2.2 Vth = 1.34 (V)

Example 35 3-H2ZB (F) -OCF3 (No.6) 2.0% 5-HH2ZB (F) -OCF3 (No.37) 5.0% 3-H2ZB (F, F) B ( F) -F (No.99) 5.0% 7-HB (F, F) -F 3.0% 3-H2HB (F, F) -F 12.0% 4-H2HB (F, F)- F 10.0% 3-HHB (F, F) -F 10.0% 4-HHB (F, F) -F 5.0% 3-HBB (F, F) -F 10.0% 3-HHEB (F, F) -F 10.0% 4-HHEB (F, F) -F 3.0% 5-HHEB (F, F) -F 3.0% 2-HBEB (F, F) -F 3 0.0% 3-HBEB (F, F) -F 5.0% 5-HBEB (F, F) -F 3.0% 3-HGB (F, F) -F 5.0% 3-HHBB (F , F) -F 6.0% NI = 77.5 (° C.) η = 34.8 (mPa · s ) Δn = 0.086 Δε = 13.4 Vth = 1.36 (V)

Example 36 3-HH2ZB (F, F) -F (No.39) 4.0% 5-HH2ZB (F, F) -F (No.40) 4.0% 5-H4HB (F, F) -F 7.0% 5-H4HB-OCF3 15.0% 3-H4HB (F, F) -CF3 8.0% 5-H4HB (F, F) -CF3 10.0% 3-HB-CL 6.0% 5-HB-CL 4.0% 2-H2BB (F) -F 5.0% 3-H2BB (F) -F 5.0% 5-H2HB (F, F) -F 4.0 % 3-HHB-OCF3 5.0% 3-H2HB-OCF3 5.0% V-HHB (F) -F 5.0% 3-HHB (F) -F 4.0% 5-HHB (F)- F 4.0% 3-HBEB (F, F) -F 5.0% NI = 70.5 (° C.) η = 25.4 (mPa · s) Δn = 0.094 Δε = 8.9 Vth = 1 .64 (V)

Example 37 3-HH2ZB (F) -OCF3 (No.36) 5.0% 5-HH2ZB (F) -OCF3 (No.37) 4.0% 3-H2ZB (F, F) -C (No.10) 6.0% 5-H2ZB (F, F) -C (No.11) 6.0% 5-HB-CL 5.0% 7-HB (F, F) -F 3.0 % 3-HH-4 10.0% 3-HH-5 5.0% 3-HB-O2 15.0% 3-H2HB (F, F) -F 5.0% 4-H2HB (F, F) -F 5.0% 3-HHB (F, F) -F 6.0% 2-HHB (F) -F 4.0% 3-HHB (F) -F 4.0% 5-HHB (F) -F 4.0% 3-HHB-1 8.0% 3-HHB-O1 5.0% NI = 71.6 (° C) η = 19.3 (mPa · s) Δn = 0.074 Δε = 6 .7 Vth = 1.75 (V)

Example 38 5-HH2ZB (F, F) -F (No.40) 4.0% 5-H2ZB (F, F) -F (No.5) 3.0% 5-H2ZB (F) -OCF3 (No.7) 4.0% 3-HH2ZB (F) -OCF3 (No.36) 3.0% 5-HH2ZB (F) -OCF3 (No.37) 3.0% 5-HB-CL 4.0% 4-HHB (F) -F 10.0% 5-HHB (F) -F 9.0% 7-HHB (F) -F 9.0% 3-HHB (F, F) -F 8.0% 4-HHB (F, F) -F 3.0% 3-H2HB (F, F) -F 12.0% 3-HBB (F, F) -F 13.0% 2-HHBB ( F, F) -F 6.0% 3-GHB (F, F) -F 3.0% 4-GHB (F, F) -F 3.0% 5-GHB (F, F) -F 3.0. 0% NI = 79.9 (° C.) η = 26.6 (mPa · s) Δn 0.082 Δε = 8.0 Vth = 1.65 (V)

Example 39 3-HH2ZB (F, F) -F (No.39) 5.0% 5-H2ZB (F, F) B (F) -F (No.100) 3.0% 3- H2ZB (F) B (F, F) -F (No.101) 3.0% 3-H2ZB (F, F) -C (No.10) 5.0% 2-HHB (F) -F 7. 0% 3-HHB (F) -F 8.0% 5-HHB (F) -F 7.0% 3-HHB (F, F) -F 8.0% 3-HBB (F, F) -F 11.0% 3-H2HB (F, F) -F 10.0% 3-HHEB (F, F) -F 10.0% 4-HHEB (F, F) -F 3.0% 2-HBEB ( F, F) -F 2.0% 3-HBEB (F, F) -F 3.0% 3-GHB (F, F) -F 3.0% 4-GHB (F, F) -F 4. 0% 5-GHB (F, F) -F 4.0% 3-HHBB (F, F) -F 4.0% NI = 79.4 (° C) η = 35.5 (mPa · s) Δn = 0.089 Δε = 11.8 Vth = 1.40 (V)

Example 40 3-H2ZB (F) -OCF3 (No.6) 4.0% 3-H2ZB (F, F) B (F) -F (No.99) 4.0% 7-HB ( F) -F 3.0% 5-HB-CL 3.0% 3-HH-4 9.0% 3-HH-EMe 23.0% 3-HHEB (F, F) -F 10.0% 4 -HHEB (F, F) -F 5.0% 3-HHEB-F 8.0% 5-HHEB-F 8.0% 4-HGB (F, F) -F 5.0% 5-HGB (F , F) -F 6.0% 2-H2GB (F, F) -F 4.0% 3-H2GB (F, F) -F 5.0% 5-GHB (F, F) -F 3.0 % NI = 79.1 (° C.) η = 19.5 (mPa · s) Δn = 0.065 Δε = 5.8 Vth = 1.79 (V)

Example 41 3-H2ZB (F, F) B (F) -F (No.99) 4.0% 5-H2ZB (F, F) B (F) -F (No.100) 5. 0% 3-H2ZB (F) B (F, F) -F (No.101) 7.0% 5-H2ZB (F) B (F, F) -F (No.102) 8.0% 3- H2HB (F, F) -F 5.0% 5-H2HB (F, F) -F 5.0% 3-HBB (F, F) -F 20.0% 5-HBB (F, F) -F 16.0% 5-HBB (F) B-2 10.0% 5-HBB (F) B-3 10.0% 3-BB (F) B (F, F) -F 5.0% 5- B2B (F, F) B (F) -F 5.0% NI = 100.8 (° C.) η = 53.6 (mPa · s) Δn = 0.149 Δε = 11.8 Vth = 1.50 ( V)

Example 42 3-HH2ZB (F, F) -F (No.39) 4.0% 3-H2ZB (F, F) -F (No.4) 4.0% 3-H2ZB (F) -OCF3 (No.6) 4.0% 5-H2ZB (F) -OCF3 (No.7) 3.0% 3-HH2ZB (F) -OCF3 (No.36) 3.0% 5-H2ZB (F ) B (F, F) -F (No. 102) 3.0% 3-HB (F, F) ZB (F, F) -F 5.0% 5-HB (F, F) ZB (F, F) -F 5.0% 5-HB-CL 3.0% 3-HH-4 14.0% 2-HH-5 4.0% 3-HHB-1 4.0% 3-HHEB-F 6 0.0% 5-HHEB-F 6.0% 3-HHB (F, F) -F 6.0% 4-HHB (F, F) -F 3.0% 3-HHEB (F, F) -F 3.0% 4-HHEB (F, F) -F 3.0% 5-HHEB ( , F) -F 2.0% 2-HBEB (F, F) -F 3.0% 3-HBEB (F, F) -F 3.0% 5-HBEB (F, F) -F 3.0 % 2-HHBB (F, F) -F 3.0% 3-HHBB (F, F) -F 3.0% NI = 79.0 (° C.) η = 18.6 (mPa · s) Δn = 0 0.072 Δε = 7.6 Vth = 1.69 (V)

Example 43 3-HH2ZB (F, F) -F (No.39) 3.0% 5-HH2ZB (F, F) -F (No.40) 3.0% 3-H2ZB (F, F) -F (No.4) 4.0% 5-H2ZB (F, F) -F (No.5) 3.0% 3-H2ZB (F) -OCF3 (No.6) 4.0% 5 -H2ZB (F) -OCF3 (No.7) 3.0% 3-HH2ZB (F) -OCF3 (No.36) 3.0% 5-HH2ZB (F) -OCF3 (No.37) 3.0% 3-H2ZB (F, F) B (F) -F (No.99) 3.0% 5-H2ZB (F, F) B (F) -F (No.100) 2.0% 3-H2ZB ( F) B (F, F) -F (No.101) 4.0% 5-H2ZB (F) B (F, F) -F (No.102) 3.0% 3-BB (F, F) ZB (F, F) -F 10.0% 3-HH-4 0.0% 3-HHB (F, F) -F 6.0% 3-H2HB (F, F) -F 9.0% 3-HBB (F, F) -F 6.0% 2-HHBB (F , F) -F 3.0% 3-HHBB (F, F) -F 3.0% 3-HH2BB (F, F) -F 4.0% 3-HHB-1 6.0% 5-HBBH- 1O1 7.0% NI = 83.2 (° C) η = 24.1 (mPa · s) Δn = 0.095 Δε = 9.3 Vth = 1.59 (V)

Example 44 5-H2ZB (2F, 3F) -O2 (No.14) 11.0% 3-H2ZB (2F, 3F) B (2F, 3F) -O2 (No.106) 11.0% 5-H2ZBB (F, F) B-2 (No.182) 6.0% 5-H2ZBB (F, F) B-F (No.184) 6.0% 3-HEB-O4 17.0% 4 -HEB-O2 15.0% 5-HEB-O1 14.0% 3-HEB-O2 12.0% 5-HEB-O2 8.0%

Example 45 3-H2ZB (2F, 3F) -O2 (No. 13) 7.0% 3-HH2ZB (2F, 3F) -O2 (No.46) 6.0% 5-HH2ZB (2F, 3F) -O2 (No.47) 7.0% 3-H2ZB (2F, 3F) B (2F, 3F) -O2 (No.106) 10.0% 3-HH-2 5.0% 3-HH -4 6.0% 3-HH-O1 4.0% 3-HH-O3 5.0% 5-HH-O1 4.0% 3-HB (2F, 3F) -O2 8.0% 5-HB (2F, 3F) -O2 8.0% 3-HHB (2F, 3F) -O2 8.0% 5-HHB (2F, 3F) -O2 8.0% 3-HHB (2F, 3F) -2 14 0.0% NI = 89.2 (° C) Δn = 0.085 Δε = -3.7

Example 46 5-H2ZB (2F, 3F) -O2 (No.14) 5.0% 3-HH2ZB (2F, 3F) -O2 (No.46) 6.0% 3-HH-55 0.0% 3-HH-4 5.0% 3-HH-O1 6.0% 3-HH-O3 6.0% 3-HB-O1 5.0% 3-HB-O2 5.0% 3- HB (2F, 3F) -O2 8.0% 5-HB (2F, 3F) -O2 7.0% 3-HHB (2F, 3F) -O2 9.0% 5-HHB (2F, 3F) -O2 10.0% 3-HHB (2F, 3F) -2 4.0% 2-HHB (2F, 3F) -1 4.0% 3-HHEH-3 5.0% 3-HHEH-5 5.0% 4-HHEH-3 5.0% NI = 87.4 (° C.) Δn = 0.078 Δε = −3.1

Example 47 5-H2ZB (2F, 3F) -O2 (No.14) 3.0% 5-HH2ZB (2F, 3F) -O2 (No.47) 6.0% 3-BB (2F, 3F) -O2 9.0% 3-BB (2F, 3F) -O4 10.0% 5-BB (2F, 3F) -O4 10.0% 2-BB (2F, 3F) B-3 19.0. % 3-BB (2F, 3F) B-5 13.0% 5-BB (2F, 3F) B-5 14.0% 5-BB (2F, 3F) B-7 16.0% NI = 78. 9 (° C) Δn = 0.195 Δε = -3.5

Example 48 3-H2ZB (2F, 3F) -O2 (No.13) 3.0% 3-H2ZB (2F, 3F) B (2F, 3F) -O2 (No.106) 4.0% 3-HB-O1 15.0% 3-HB-O2 6.0% 3-HEB (2F, 3F) -O2 8.0% 4-HEB (2F, 3F) -O2 8.0% 5-HEB ( 2F, 3F) -O2 8.0% 2-BB2B-O2 6.0% 3-BB2B-O2 6.0% 5-BB2B-O1 6.0% 5-BB2B-O2 6.0% 1-B2BB ( 2F) -5 7.0% 3-B2BB (2F) -5 7.0% 5-B (F) BB-O2 7.0% 3-BB (2F, 3F) B-3 3.0% NI = 79.3 (° C) η = 23.4 (mPa · s) Δn = 0.161

Example 49 3-H2ZB (2F, 3F) -O2 (No.13) 11.0% 5-HH2ZB (2F, 3F) -O2 (No.47) 6.0% 3-H2ZB (2F, No. 3F) B (2F, 3F) -O2 (No.106) 3.0% 3-HH-O1 8.0% 5-HH-O1 4.0% 3-HH-4 5.0% 3-HB ( 2F, 3F) -O2 10.0% 5-HB (2F, 3F) -O2 16.0% 2-HHB (2F, 3F) -1 4.0% 3-HHB (2F, 3F) -1 5. 0% 3-HHB (2F, 3F) -02 14.0% 5-HHB (2F, 3F) -O2 14.0% NI = 65.0 (° C) η = 24.9 (mPa · s) Δn = 0.079 Δε = −3.9

Example 50 3-HH2ZB (2F, 3F) -O2 (No.46) 9.0% 5-HH2ZB (2F, 3F) -O2 (No.47) 9.0% 3-H2ZB (2F, No. 3F) B (2F, 3F) -O2 (No.106) 14.0% 3-HB-O1 15.0% 3-HH-4 5.0% 3-HB (2F, 3F) -O2 12.0 % 5-HB (2F, 3F) -O2 12.0% 2-HHB (2F, 3F) -1 5.0% 3-HHB (2F, 3F) -1 5.0% 3-HHB (2F, 3F) ) -O2 4.0% 5-HHB (2F, 3F) -O2 4.0% 3-HHB-1 6.0% NI = 87.5 (° C) η = 41.7 (mPa · s) Δn = 0.095 Δε = −3.2

Example 51 3-H2ZB (2F, 3F) -O2 (No. 13) 6.0% 5-H2ZB (2F, 3F) -O2 (No.14) 6.0% 3-HH2ZB (2F, 3F) -O2 (No.46) 7.0% 5-HH2ZB (2F, 3F) -O2 (No.47) 7.0% 3-H2ZB (2F, 3F) B (2F, 3F) -O2 (No .106) 10.0% 3-HB-O1 15.0% 3-HH-4 5.0% 3-HB (2F, 3F) -O2 6.0% 5-HB (2F, 3F) -O2 6 0.0% 2-HHB (2F, 3F) -1 7.0% 3-HHB (2F, 3F) -1 7.0% 3-HHB (2F, 3F) -O2 6.0% 5-HHB (2F , 3F) -O2 6.0% 6-HEB (2F, 3F) -O2 6.0% NI = 85.9 (° C) η = 39.3 (mPa · s) Δn = 0.09 Δε = -3 .3

Example 52 3-H2ZB (2F, 3F) -O2 (No.13) 5.0% 3-HH2ZB (2F, 3F) -O2 (No.46) 3.0% 5-HH2ZB (2F, 3F) -O2 (No. 47) 3.0% 3-HB-O2 20.0% 1O1-HH-3 6.0% 1O1-HH-5 5.0% 3-HH-EMe 7.0% 4 -HEB-O1 9.0% 4-HEB-O2 7.0% 5-HEB-O1 8.0% 3-HHB-1 3.0% 3-HHB-3 3.0% 4-HEB (2CN, 3CN) -O4 3.0% 6-HEB (2CN, 3CN) -O4 3.0% 3-HEB (2CN, 3CN) -O5 4.0% 4-HEB (2CN, 3CN) -O5 3.0% 5-HEB (2CN, 3CN) -O5 2.0% 2-HBEB (2CN, 3CN) -O2 2.0% 4-HBEB (2CN, 3CN) O4 4.0% NI = 62.3 (℃) η = 41.1 (mPa · s) Δn = 0.076 Δε = -6.0

Example 53 3-HH2ZB (2F, 3F) -O2 (No.46) 4.0% 2O-B (2F, 3F) 2ZBH-3 (No.201) 4.0% 3-HEB-O4 28.0% 4-HEB-O2 20.0% 5-HEB-O1 20.0% 3-HEB-O2 18.0% 5-HEB-O2 10.0% NI = 76.2 (° C) η = 22.0 (mPa · s) Δn = 0.089

Example 54 2O-B (2F, 3F) 2ZBH-3 (No.201) 14.0% 3-HH-2 5.0% 3-HH-4 6.0% 3-HH-O1 4 0.0% 3-HH-O3 5.0% 5-HH-O1 4.0% 3-HB (2F, 3F) -O2 12.0% 5-HB (2F, 3F) -O2 11.0% 5 -HHB (2F, 3F) -O2 15.0% 3-HHB (2F, 3F) -2 24.0% NI = 78.6 (° C) Δn = 0.080 Δε = -3.9

[0213]

INDUSTRIAL APPLICABILITY The present invention provides a liquid crystal compound having excellent compatibility with other liquid crystal compounds, low viscosity and low threshold voltage. In addition, the present invention provides a novel liquid crystal compound having the characteristics of the above-mentioned embodiment having desired physical properties by appropriately selecting a ring, a substituent, a bonding group, etc. constituting the compound using the liquid crystal compound as a component. Providing a liquid crystal composition,
Further provided is a liquid crystal display device using this liquid crystal composition.

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[Procedure amendment]

[Submission date] May 20, 2002 (2002.5.2)
0)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Chemical 71] (In the formula, R ¹ and R ² are each independently hydrogen, halogen,
A cyano group or an alkyl group having 1 to 20 carbon atoms, one or more -CH ₂ in the alkyl group - is -CH = CH
-, -C≡C-, -O- or -S- may be substituted, but -O- is not continuous, and 1 in the group
One or more hydrogens may be replaced by halogens; Ring A
¹ to ring A ⁵ are each independently one or more non-adjacent -C.
H ₂ — may be substituted with —O— or —S— 1,
4-cyclohexylene group, 1,4-cyclohexenylene group, or one or more = CH- may be substituted with = N-, or hydrogen on the ring may be substituted with halogen 1. , 4-phenylene group; Z ^{1 to} Z ⁴ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —O.
_{CH 2 -, - COO -,} - OCO -, - CH = CH-,
-C≡C-, -CF ₂ O-, or -OCF _2- ;
Y ¹ , Y ² , Y ³ and Y ⁴ are each independently hydrogen or fluorine; k, l, m and n are each independently 0 or 1).

[Chemical 72] (In the formula, R ¹ , R ² , rings A ^{1 to} A ⁵ , Z ^{1 to} Z ⁴ and Y ^{1 to} Y ⁴
Represents the same meaning as described above), and the liquid crystal compound according to claim 1.

[Chemical formula 73] (In the formula, R ³ is an alkyl group having 1 to 10 carbon atoms, and any —CH ₂ — which is not adjacent to each other in this group may be substituted with —O— or —CH═CH—. any hydrogen in this group may be substituted by fluorine; X ¹ is fluorine, _{chlorine, -OCF 3, -OCF 2 H,} -CF 3, -CF 2
_{H, -CFH 2, -OCF 2 CF} 2 H or -OCF ₂ CF
HCF ₃ ; L ¹ and L ² are each independently hydrogen or fluorine; Z ⁵ and Z ⁶ are independently-(C
_{H 2) 2 -, - (} CH 2) 4 -, - COO -, - CF 2 O -, -
OCF ₂ —, —CH═CH— or a single bond; ring A and ring B are each independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, or hydrogen is replaced by fluorine. 1,4-phenylene, which may be optionally substituted, and ring C is 1,4-cyclohexylene or 1,4-phenylene in which hydrogen may be replaced by fluorine). A liquid crystal composition containing at least one kind.

[Chemical 74] (In the formula, R ⁴ and R ⁵ are each independently an alkyl group having 1 to 10 carbon atoms, and any —C which is not adjacent to each other in this group.
H ₂ — may be substituted with —O— or —CH═CH—, and any hydrogen in this group may be substituted with fluorine; X ² is —CN or —C≡C—CN. Ring D is 1,4-cyclohexylene, 1,4-phenylene,
1,3-dioxane-2,5-diyl or pyrimidine-
2,5-diyl; ring E is 1,4-cyclohexylene, 1,4-phenylene in which hydrogen may be replaced by fluorine, or pyrimidine-2,5-diyl; ring F is 1,4 - it is cyclohexylene or 1,4-phenylene; Z ⁷ is _{- (CH 2) 2 -,} - COO -, - CF 2 O -, -
OCF ₂ — or a single bond; L ³ , L ⁴ and L ⁵ are each independently hydrogen or fluorine; b, c and d are each independently 0 or 1.

[Chemical 75] (In the formula, R ⁶ and R ⁷ are each independently an alkyl group having 1 to 10 carbon atoms, and any —C which is not adjacent to each other in this group.
H ₂ — may be substituted with —O— or —CH═CH—, and any hydrogen in this group may be substituted with fluorine; ring G and ring I are each independently 1 , 4-cyclohexylene or 1,4-phenylene; L ⁶ and L ⁷ are each independently hydrogen or fluorine, but L ⁶ and L ⁷ are not hydrogen at the same time; Z ⁸ and Z ⁹ are each independently _{- (CH 2) 2 -,} - COO- or a single bond. )

[Chemical 76] (In the formula, R ⁸ and R ⁹ are each independently an alkyl group having 1 to 10 carbon atoms, and any —C which is not adjacent to each other in this group.
H ₂ — may be substituted with —O— or —CH═CH—, and any hydrogen in this group may be substituted with fluorine; ring J, ring K and ring M are each independently , 1,4
- cyclohexylene, pyrimidine-2,5-diyl or hydrogen is to be or 1,4-phenylene substituted by fluorine,; Z ^{1 0} and Z ¹¹ are each independently, -C≡C
-, - COO -, - ( CH 2) 2 -, - is CH = CH- or a single bond. )

[Chemical 77]

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07D 319/06 C07D 319/06 339/08 339/08 C09K 19/12 C09K 19/12 19/14 19/14 19 / 20 19/20 19/30 19/30 19/34 19/34 G02F 1/13 500 G02F 1/13 500 (72) Inventor Yasuyuki Sasada 1-5-5 Goikaigan, Ichihara-shi, Chiba Chisso Petrochemical Co., Ltd. Functional materials In-house (72) Inventor Kazutoshi Miyazawa 1 at 5 Goi Kaigan, Ichihara, Chiba Chisso Petrochemical Co., Ltd. Functional Materials Research Institute (72) Inventor Hiroyuki Takeuchi 1 Chisso Petrochemical Co., Ltd., Ichihara, Chiba 5 Company Functional Materials Laboratory (72) Inventor Katsuyuki Kono 1-5, Goi Kaigan, Ichihara, Chiba Chisso Petrochemical Co., Ltd. Functional Materials Laboratory (72) Inventor Yasuhiro Kubo 1-5, Goi Kaigan, Ichihara, Chiba Chisso Oil Co., Ltd. (72) Inventor, Etsuko Nakagawa, Ichihara City, Chiba Prefecture 1 in Chisso Petrochemical Co., Ltd. Functional Materials Research Laboratory (72) Inventor Mayumi Furuya 1 in 5 Chisso Petrochemicals Co., Ltd. Functional Materials Research Laboratory F-term (reference) 4C022 GA03 GA04 4C023 PA03 4C055 AA01 BA02 BA13 BA16 BB04 BB07 BB08 CA02 CA05 CA08 CB02 DA01 4H006 AA01 AA03 AB64 GP03 GP10 GP30 4H027 BA01 BB03 BB04 BC05 BD01 BD03 BD05 BD07 BD09 BD04 CN05 CM04 CM04 CG04 CL05 CG01 CM04 CE04 CE05 CE04 CE05 CP04 CR03 CR04 CR05 CS04 CS05 CT01 CT02 CT03 CT04 CU02 CU03 CU04 CU05 CW01 CW02 CW03 DE01 DE04 DF01 DF04 DH04 DH05

Claims (20)

[Claims] 1. Formula (1): (In the formula, R ¹ and R ² are each independently hydrogen, halogen,
A cyano group or an alkyl group having 1 to 20 carbon atoms, one or more -CH ₂ in the alkyl group - is -CH = CH
-, -C≡C-, -O- or -S- may be substituted, but -O- is not continuous, and 1 in the group
One or more hydrogens may be replaced by halogens; Ring A
¹ to ring A ⁵ are each independently one or more non-adjacent -C.
H ₂ — may be substituted with —O— or —S— 1,
4-cyclohexylene group, 1,4-cyclohexenylene group, or one or more = CH- may be substituted with = N-, or hydrogen on the ring may be substituted with halogen 1. , 4-phenylene group; Z ^{1 to} Z ⁴ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —O.
_{CH 2 -, - COO -,} - OCO -, - CH = CH-,
-C≡C-, -CF ₂ O-, or -OCF _2- ;
Y ¹ , Y ² , Y ³ and Y ⁴ are each independently hydrogen or fluorine; k, l, m and n are each independently 0 or 1). 2. Formulas (1-1) to (1-6): (In the formula, R ¹ , R ² , rings A ^{1 to} A ⁵ , Z ^{1 to} Z ⁴ and Y ^{1 to} Y ⁴
Represents the same meaning as described above), and the liquid crystal compound according to claim 1. 3. The liquid crystal compound according to claim 1, wherein ring A ³ in the formula (1) is a 1,4-cyclohexylene group. 4. The liquid crystal compound according to claim 1, wherein in the formula (1), Y ¹ and Y ³ are both fluorine and Y ² and Y ⁴ are both hydrogen atoms. 5. The liquid crystal compound according to claim 1, wherein both Y ¹ and Y ² in the formula (1) are hydrogen. 6. The liquid crystallinity according to claim 2, wherein in the formula (1-1), ring A ³ is a 1,4-cyclohexylene group, Y ¹ and Y ³ are both fluorine, and Y ² and Y ⁴ are both hydrogen. Compound. 7. The ring A ³ in the formula (1-1) is a 1,4-cyclohexylene group, and both Y ¹ and Y ² are hydrogen.
The liquid crystal compound described. 8. A ring A ² and a ring A ³ in the formula (1-2).
^3. The liquid crystalline compound according to claim 2, wherein both are 1,4-cyclohexylene groups, Y ¹ and Y ³ are both fluorine, and Y ² and Y ⁴ are both hydrogen. 9. A ring A ² and a ring A ³ in the formula (1-2).
3. The liquid crystalline compound according to claim 2, wherein both are 1,4-cyclohexylene groups, and both Y ¹ and Y ² are hydrogen. 10. The ring A ³ in the formula (1-3) is 2,3-
The liquid crystalline compound according to claim 2, which is a difluoro-1,4-phenylene group. 11. A liquid crystal composition containing at least one compound of any one of claims 1 to 10. 12. A compound comprising at least one compound according to claim 1 as a first component,
As the second component, formulas (2), (3) and (4) (In the formula, R ³ is an alkyl group having 1 to 10 carbon atoms, and any —CH ₂ — which is not adjacent to each other in this group may be substituted with —O— or —CH═CH—. any hydrogen in this group may be substituted by fluorine; X ¹ is fluorine, _{chlorine, -OCF 3, -OCF 2 H,} -CF 3, -CF 2
_{H, -CFH 2, -OCF 2 CF} 2 H or -OCF ₂ CF
HCF ₃ ; L ¹ and L ² are each independently hydrogen or fluorine; Z ⁵ and Z ⁶ are independently-(C
_{H 2) 2 -, - (} CH 2) 4 -, - COO -, - CF 2 O -, -
OCF ₂ —, —CH═CH— or a single bond; ring A and ring B are each independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, or hydrogen is replaced by fluorine. 1,4-phenylene, which may be optionally substituted, and ring C is 1,4-cyclohexylene or 1,4-phenylene in which hydrogen may be replaced by fluorine). A liquid crystal composition containing at least one kind. 13. A compound containing at least one compound according to any one of claims 1 to 10 as a first component, and selected from the compound group consisting of formulas (5) and (6) as a second component. Liquid crystal composition containing at least one compound described above. [Chemical 4] (In the formula, R ⁴ and R ⁵ are each independently an alkyl group having 1 to 10 carbon atoms, and any —C which is not adjacent to each other in this group.
H ₂ — may be substituted with —O— or —CH═CH—, and any hydrogen in this group may be substituted with fluorine; X ² is —CN or —C≡C—CN. Ring D is 1,4-cyclohexylene, 1,4-phenylene,
1,3-dioxane-2,5-diyl or pyrimidine-
2,5-diyl; ring E is 1,4-cyclohexylene, 1,4-phenylene in which hydrogen may be replaced by fluorine, or pyrimidine-2,5-diyl; ring F is 1,4 - it is cyclohexylene or 1,4-phenylene; Z ⁷ is _{- (CH 2) 2 -,} - COO -, - CF 2 O -, -
OCF ₂ — or a single bond; L ³ , L ⁴ and L ⁵ are each independently hydrogen or fluorine; b, c and d are each independently 0 or 1. 14. A first component containing at least one compound according to any one of claims 1 to 10, and a second component consisting of formulas (7), (8) and (9). A liquid crystal composition containing at least one compound selected from the compound group. [Chemical 5] (In the formula, R ⁶ and R ⁷ are each independently an alkyl group having 1 to 10 carbon atoms, and any —C which is not adjacent to each other in this group.
H ₂ — may be substituted with —O— or —CH═CH—, and any hydrogen in this group may be substituted with fluorine; ring G and ring I are each independently 1 , 4-cyclohexylene or 1,4-phenylene; L ⁶ and L ⁷ are each independently hydrogen or fluorine, but L ⁶ and L ⁷ are not hydrogen at the same time; Z ⁸ and Z ⁹ are each independently _{- (CH 2) 2 -,} - COO- or a single bond. ) 15. A compound containing at least one compound according to any one of claims 1 to 10 as a first component, and as a second component from the above formulas (2), (3) and (4). A liquid crystal composition containing at least one compound selected from the group consisting of compounds represented by formulas (10), (11) and (12) as a third component. . [Chemical 6] (In the formula, R ⁸ and R ⁹ are each independently an alkyl group having 1 to 10 carbon atoms, and any —C which is not adjacent to each other in this group.
H ₂ — may be substituted with —O— or —CH═CH—, and any hydrogen in this group may be substituted with fluorine; ring J, ring K and ring M are each independently , 1,4
- cyclohexylene, pyrimidine-2,5-diyl or hydrogen is to be or 1,4-phenylene substituted by fluorine,; Z ^{1 0} and Z ¹¹ are each independently, -C≡C
-, - COO -, - ( CH 2) 2 -, - is CH = CH- or a single bond. ) 16. A compound containing at least one compound according to any one of claims 1 to 10 as a first component, and a compound consisting of the formulas (5) and (6) as a second component. At least one selected compound is contained, and as the third component, the above formulas (10), (11) and (1
A liquid crystal composition containing at least one compound selected from the compound group consisting of 2). 17. A compound comprising at least one compound according to any one of claims 1 to 10 as a first component, and as a second component from the above formulas (7), (8) and (9). A liquid crystal composition containing at least one compound selected from the group consisting of compounds and containing, as a third component, at least one compound selected from the group consisting of the formulas (10), (11) and (12). . 18. A compound containing at least one compound according to any one of claims 1 to 10 as a first component, and as a second component from the above formulas (2), (3) and (4). Containing at least one compound selected from the compound group consisting of, as a third component, containing at least one compound selected from the compound group consisting of the formulas (5) and (6), as a fourth component, A liquid crystal composition containing at least one compound selected from the compound group consisting of the formulas (10), (11) and (12). 19. A liquid crystal composition comprising the liquid crystal composition according to claim 11 and at least one optically active compound. 20. A liquid crystal display device using the liquid crystal composition according to claim 11.