# Patent

## Title
Nematic liquid crystal composition and liquid crystal display element using same

## Abstract

A liquid crystal composition in which deterioration of viscosity that is associated with an increase in Δn and an increase in Δ∈ is suppressed, and a liquid crystal display element having a markedly improved response speed by using the relevant liquid crystal composition. The liquid crystal composition has a large value of Δn and negative Δ∈, and have large absolute values thereof. Also, the liquid crystal composition has low η, has excellent liquid crystal properties, and exhibits a liquid crystal phase that is stable in a wide temperature range. Furthermore, since the liquid crystal composition is chemically stable to heat, light, water and the like, the liquid crystal composition is capable of low voltage driving, and is practically useful and highly reliable.

## Background
TECHNICAL FIELD
The present invention relates to a nematic liquid crystal composition having negative dielectric anisotropy (Δ∈), which is useful as an electro-optical liquid crystal display material, and a liquid crystal display element using this liquid crystal composition.
BACKGROUND ART
Vertical alignment type VA-LCD's using liquid crystal compositions having negative dielectric anisotropy (negative Δ∈) can express the black of coal-black, and therefore have an excellent display quality. Thus, as high contrast liquid crystal display devices, VA-LCD's have widely penetrated into the liquid crystal TV-centered market. Furthermore, recently, in addition to the active matrix driving systems that are represented by liquid crystal TV's and the like, even in the passive matrix driving systems that are used as display devices for in-vehicle applications or electric appliance applications, the employment of VA-LCD's is increasing. In regard to the liquid crystal TV applications, in order to realize smooth movie display performance, the gap between glass substrates tends to be narrowed, while the birefringence (Δn) of the liquid crystal material tends to increase. On the other hand, in regard to the in-vehicle display devices, in order to obtain satisfactory contrast even in high time-shared driving, namely high multiplex drive with a large display capacity, a liquid crystal composition having negative Δ∈ is required to have a large Δn that has not been conventionally found, and at the same time, the liquid crystal composition is also required to have a large absolute value of Δ∈ in order to cone with voltage lowering. Many liquid crystal compounds and liquid crystal compositions have been suggested as liquid crystal materials for VA-LCD's; however, in order to increase Δn, it is necessary to increase the content of a liquid crystal compound having a large Δn in the liquid crystal composition, and in order to increase the absolute value of Δ∈, it is necessary to increase the content of a liquid crystal compound having a large absolute value of Δ∈ in the liquid crystal composition. However, when the contents of these compounds are increased, viscosity (η) is deteriorated, and consequently, the response speed is deteriorated.
Liquid crystal compositions which exhibit negative values of Δ∈ and large values of Δn have been hitherto disclosed (Patent Literatures 1 to 4). However, the liquid crystal composition described in Patent Literature 1 contains a liquid crystal compound having positive Δ∈, and the absolute value of Δ∈ is small. Furthermore, the liquid crystal compositions described in Patent Literatures 2 to 4 are such that the absolute value of Δ∈ is large but the value of Δn is not sufficiently large. Also, the liquid crystal compositions have large values of η.
Therefore, there is a demand for a liquid crystal composition which has a large absolute value of Δ∈ and a large value of Δn but a small value of η.
CITATION LIST
Patent Literature


    Patent Literature 1: Japanese Patent Application Laid-Open (JP-A) No. 11-228966
    Patent Literature 2: JP-A No. 11-140447
    Patent Literature 3: JP-A No. 2001-354967
    Patent Literature 4: JP-A No. 2000-96058


SUMMARY OF INVENTION
Technical Problem
An object of the present invention is to provide a liquid crystal composition in which deterioration of viscosity associated with an increase in Δn and an increase in Δ∈ is suppressed, and to provide a liquid crystal display element having an improved response speed, by using the relevant liquid crystal composition.
Solution to Problem
The inventors of the present invention conducted a thorough investigation in order to solve the problems described above, and as a result, they found that the problems are solved by a combination of at least two or more kinds of particular compounds. That is, there are provided a liquid crystal composition containing, as a first component, one kind or two or more kinds of compounds selected from compounds represented by Formula (I):




wherein R11 and R12 each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, while these groups are each independently unsubstituted or have at least one halogen group as a substituent, and one or two or more of —CH2— present in these groups may be each independently substituted by —O—, —S—, —CO—, —COO—, —OCO— or —OCO—C— such that oxygen atoms are not directly bonded to each other;
A11 and A12 each independently represent a group selected from the group consisting of:
(a) a trans-1,4-cyclohexylene group (wherein one —CH2— or non-adjacent two or more of —CH2—, which are present in this group, may be substituted by —O— and/or —S—,
(b) a 1,4-phenylene group (wherein one —CH═ or non-adjacent two or more of —CH═ groups, which are present in this group, may be substituted by —N═), and
(c) 1,4-cyclohexenylene, 1,4-bicyclo(2.2.2) octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, or 1,2,3,4-tetrahydronaphthalene-2,6-diyl,
while the hydrogen atoms on the group (a), group (b) and group (c) may be each independently substituted by an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkenyloxy group having 1 to 3 carbon atoms, CN or halogen;
Z11 and Z12 each independently represent —COO—, —OCO—, —CH2O—, —OCH2—, —CF2O—, —OCF2—, —CH2CH2—, —CH═CH—, —C≡C—, —(CH2)4—, —CH═CH—CH2CH2—, —CH2—CH2—CH═CH—, or a single bond;
a11 and a12 each independently represent 0 or 1; and
as a second component, one kind or two or more kinds of compounds selected from compounds represented by Formulas (II) and (III):




wherein R21, R22, R31 and R32 each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, while these groups are each independently unsubstituted or have at least one halogen group as a substituent, and one or two or more of —CH2— present in these groups may be each independently substituted by —O—, −S—, —CO—, —COO—, —OCO— or —OCO—O— such that oxygen atoms are not directly bonded to each other;
A21, A22, A23, A31, A32 and A33 each independently represent a group selected from the group consisting of:
(a) a trans-1,4-cyclohexylene group (wherein one —CH2— or non-adjacent two or more of —CH2—, which are present in this group, may be substituted by —O— and/or —S—,
(b) a 1,4-phenylene group (wherein one —CH═ or non-adjacent two or more of —CH═ groups, which are present in this group, may be substituted by —N═), and
(c) 1,4-cyclohexenylene, 1,4-bicyclo(2.2.2)octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, or 1,2,3,4-tetrahydronaphthalene-2,6-diyl,
while the hydrogen atoms on the group (a), group (b) and group (c) may be each independently substituted by an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkenyloxy group having 1 to 3 carbon atoms, CN or halogen;
Z21, Z22, Z23, Z31, Z32 and Z33 each independently represent —COO—, —OCO—, —CH2—, —OCH2—, —CF2O—, —OCF2—, —CH2CH2—, —CH═CH—, —C≡C—, —(CH2)4—, —CH═CH—CH2—CH2—, —CH2CH2—CH═CH—, or a single bond; and
a21, a22, a31 and a32 each independently represent 0 or 1,
and a liquid crystal display element including the relevant liquid crystal composition as a constituent member.
Advantageous Effects of Invention
The liquid crystal composition of the present invention has features of a large value of Δn, negative Δ∈, and large absolute values thereof. Also, the liquid crystal composition has low η, has excellent liquid crystal properties, and exhibits a liquid crystal phase that is stable in a wide temperature range. Furthermore, since the liquid crystal composition is chemically stable to heat, light, water and the like, it is a liquid crystal composition that is capable of low voltage driving, and is practically useful and highly reliable.


DESCRIPTION OF EMBODIMENTS
In regard to the compound represented by Formula (I) as a first component, R11 and R12 each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms; however, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms is preferred, and a linear group is preferred, a11 represents 0 or 1; however, in the case where a high response speed is considered important, 0 is preferred, while in the case where the nematic phase upper limit temperature is considered important, 1 is preferred. Also, in the case where having a large value of Δn is considered important, 1 is preferred. A11 and A12 each independently represent any one of:




and one or two or more hydrogen atoms present on the benzene rings may be substituted by halogen. However, a 1,4-phenylene group or a 1,4-cyclohexylene group are preferred, and the 1,4-phenylene group may be substituted with one or two or more fluorine atoms. A11, if present, is more preferably a 1,4-cyclohexylene group when viscosity is considered important, and A12 is more preferably a 1,4-phenylene group when refractive index anisotropy is considered important.
More specifically, the compound represented by Formula (I) is preferably a compound represented by any one of the following Formulas (I-1) to (I-3):




wherein R11 has the same meaning as R11 in Formula (I); and R12 has the same meaning as R12 in Formula (I)
In regard to the compounds represented by Formulas (II-1) and (II-2) as a second component, one kind or two or more kinds of compounds represented by Formula (II-1) only may be used, one kind or two or more kinds of compounds represented by Formula (II-2) may be used, or mixtures of one kind or two or more kinds of compounds represented by Formula (II-1) and one kind or two or more kinds of compounds represented by Formula (II-2) may also be used.
It is preferable that the compound represented by Formula (I) be contained in an amount of at least 2% by weight or more, but it is more preferable that the compound be contained in an amount of 2% by weight to 70% by weight, and even more preferably 2% by weight to 40% by weight.
Regarding the compounds represented by Formulas (II-1) and (II-2), R21, R22, R31 and R32 each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms. However, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms is preferred, and a linear group is preferred. a21, a22, a31 and a32 each independently represent 0 or 1; however, a21+a22 is preferably 0 or 1, and a21+a22 is preferably 0 in the case where a high response speed is considered important, while a21+a22 is preferably 1 in the case where the nematic phase upper limit temperature is considered important, a31+a32 is preferably 0 or 1, and a31+a32 is preferably 0 when a high response speed is considered important, while a31+a32 is preferably 1 when the nematic phase upper limit temperature is considered important. Z21, Z22, Z31 and Z32 each independently represent a single bond, —CH═CH—, —C≡C—, —CH2O—, —OCH2— or —CH2CH2—, but a single bond, —CH2O—, —OCH2— or —CH2CH2— is preferred. A21, A22, A23, A31, A32 and A33 each independently represent any one of the following:




but one or two or more hydrogen atoms present on the benzene ring may be substituted by halogen. However, a 1,4-phenylene group or a 1,4-cyclohexylene group is preferred, and the 1,4-phenylene group may be substituted with one or two or more fluorine atoms. If viscosity is considered important, a 1,4-cyclohexylene group is preferred.
More specifically, the compounds represented by Formulas (II) and (III) are preferably compounds represented by the following Formulas (II-1) to (III-3):




wherein R21 has the same meaning as R21 in formula (II); R22 has the same meaning as R22 in Formula (II); R31 has the same meaning as R31 in Formula (III); and R32 has the same meaning as R32 in Formula (III).
Furthermore, in the compounds represented by Formulas (II-1) and (II-3), R21 is preferably an alkyl group or an alkenyl group, R22 is preferably an alkyl group or an alkenyl group. Furthermore, in the compound represented by Formula (II-1), R21 is preferably an alkenyl group, and R22 is preferably an alkyl group. In the compound represented by Formula (II-3), R21 is preferably an alkenyl group, and R22 is preferably an alkyl group. In the compounds represented by Formulas (II-2), (II-4) and (II-5), R21 is preferably an alkyl group or an alkenyl group, and R22 is preferably an alkoxy group or an alkenyloxy group. Furthermore, in the compound represented by Formula (II-2), R21 is preferably an alkenyl group, and R22 is preferably an alkenyloxy group. In the compound represented by Formula (I-1-4), R21 is preferably an alkyl group, and R22 is preferably an alkoxy group. In the compound represented by Formula (II-5), R21 is preferably an alkyl group, and R22 is preferably an alkoxy group. In the compounds represented by Formulas (III-1), (III-2) and (III-3), R31 is preferably an alkyl group or an alkenyl group, and R32 is preferably an alkoxy group or an alkenyloxy group. Furthermore, R31 is preferably an alkyl group, and R32 is preferably an alkoxy group.
At least one or more kinds of compounds selected from the compounds represented by Formulas (II) and (III) are used. However, it is more preferable to use two or more kinds, and it is even more preferable to use three or more kinds.
The compound represented by Formula (IV), which is a third component, is a compound having a value of Δ∈ close to zero, and may have an electron-withdrawing group in the molecule. However, it is preferable that the number of the electron-withdrawing group be 2 or less, and preferably one or less, and it is more preferable that the compound contain no electron-withdrawing group.




R41 and R42 each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms. However, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms is preferred, and a linear group is preferred.
A41, A42 and A43 each independently represent any one of the following:




but a 1,4-phenylene group or a 1,4-cyclohexylene group is preferred, and the 1,4-phenylene group may be substituted with one or two or more fluorine atoms or methyl groups. A41, A42 and A43 are not intended to represent a 2,3-dihalo-1,4-phenylene group.
Z41 and Z42 each independently represent a single bond, —C≡C—, —C═N—N═C—, —CH═CH—, —CF═CF—, —CF2O—, —OCF2—, —COO— or —OCO—; however, a single bond, —CH2CH2—, —C≡C—, —COO— or —OCO— is preferred, and a single bond or —C≡C— is preferred. a41 represents 0, 1 or 2, but 0 or 1 is preferred. When plural A42's are present, they may be identical or different from each other, and when plural Z42's are present, they may be or different from each other.
More specifically, the compound represented by Formula (IV) is preferably a compound represented by any one of the following formulas (IV-1) to (IV-10):




wherein R41 has the same meaning as R41 in Formula (IV) and R42 has the same meaning as R42 in Formula (IV).
Regarding the compound represented by Formula (IV), it is preferable that one kind to ten kinds of such compounds be contained, and it is particularly preferable that two kinds to eight kinds of such compounds be contained. The lower limit of the content of the compound represented by Formula (IV) is preferably 5% by mass, more preferably 10% by mass, even more preferably 20% by mass, and particularly preferably 30% by mass. The upper limit is preferably 80% by mass, more preferably 70% by mass, and even more preferably 60% by mass.
When the present invention is used in an active matrix-driven liquid crystal display element, the nematic phase-isotropic liquid phase transition temperature (Tni) is preferably 60° C. to 120° C., and the lower limit is more preferably 65° C., and particularly preferably 70° C. The upper limit is more preferably 90° C., and particularly preferably 80° C. It is preferable that Δ∈ at 25° C. be from −2.0 to −6.0, and Δ∈ is more preferably from −2.5 to −5.0, and particularly preferably from −2.5 to −3.5. Δn at 25° C. is preferably 0.08 to 0.13, but more preferably 0.09 to 0.12. To be more specific, in the case of dealing with a small cell gap, Δn is preferably 0.10 to 0.12, and in the case of dealing with a large cell gap, Δn is preferably 0.08 to 0.10. The viscosity at 20° C. is preferably 10 mPa·s to 30 mPa·s, but the viscosity is more preferably 10 mPa·s to 25 mPa·s, and particularly preferably 10 mPa·s to 20 mPa·s.
Furthermore, when the present invention is used in a passive matrix-driven liquid crystal display element, for consumer use applications, Tni is preferably from 60° C. to 120° C., and the lower limit is more preferably 65° C., and particularly preferably 70° C. The upper limit is more preferably 90° C., and particularly preferably 80° C. For in-vehicle applications and the like, the lower limit is more preferably 90° C., and particularly preferably 100° C. The upper limit is more preferably 115° C., and particularly preferably 105° C. Δn at 25° C. is preferably from 0.08 to 0.13 for low duty driving, and particularly preferably from 0.08 to 0.11. Furthermore, Δn at 25° C. is preferably from 0.13 to 0.20 for high duty driving, and particularly preferably from 0.15 to 0.18. Δ∈ at 25° C. is preferably from −2.0 to −7.0 in low duty driving, and particularly preferably from −2.5 to −5.5. The viscosity at 20° C. is preferably from 10 mPa·s to 40 mPa·s, but the viscosity is more preferably from 10 mPa·s to 30 mPa·s, and particularly preferably from 10 mPa·s to 25 mPa·s.
The nematic liquid crystal composition of the present invention may also contain, in addition to the compounds described above, a conventional nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, an oxidation inhibitor, an ultraviolet absorber, a polymerizable monomer, and the like.
The nematic liquid crystal composition of the present invention is useful for liquid crystal display elements, is useful for liquid crystal display elements for active matrix driving and liquid crystal display elements for passive matrix driving, and is particularly useful for liquid crystal display elements for passive matrix driving. Furthermore, the nematic liquid crystal composition of the present invention can be used in liquid crystal display elements for the VA mode, PSVA mode, IPS mod or ECB mode.
EXAMPLES
Hereinafter, the present invention will be described in more detail by way of Examples, but the present invention is not intended to be limited to these Examples. Furthermore, the unit “percent (%)” for the compositions of the following Examples and Comparative Examples means “percent (%) by mass”.
Examples of the present invention will be introduced below, but the present invention is not intended to be limited to these.
Terms used in the Examples will be described below.
TNI: Nematic-isotropic transition temperature [° C.]
Δn: Refractive index anisotropy (589 nm, 25° C.)
Δ∈: Dielectric anisotropy (1 KHz, 25° C.)
η: Bulk flow viscosity [mPa·s](20° C.)
Response speed: Injected into a vertical alignment cell with a gap of 3.5 μm and a pretilt angle of 89°, and measured with square waves at 5 V and 100 Hz
τon: Time taken for the change from transmittance 0%transmittance 90% [ms]
τoff: Time taken for the change from transmittance 100% to transmittance 10% [ms]
The brevity codes described below will be used for the description of compounds in the Examples.
Brevity codes for side chains will be shown blow.
-n (number): —CnH2n+1 (the alkyl side chain will be expressed as a number, and a representative will be expressed as R).
-On: —OCnH2+1 
-ndm: —(CnH2n+1—C═C—(CH2)m-1)
ndm-: CnH2n+1—C═C— (CH2)m-1—
-nOm: —(CH2)nOCmH2m+1 
nOm-: CnH2n+1O(CH2)m—
-Od(m)n: —O(CHnH2n+1—C═C—(CH2)m-2)
d(m)nO-: CnH2n+1—C═C—(CH2)m-2O—
-Brevity codes for linking groups will be shown below.
-V-: —CO—
-VO-: —COO— (-E- is also possible)
-OV-: —OCO—
-1N-: —C═N—
-N1-: —N═C—
-T-: —C≡C—
-2-: —CH2CH2—
-3-: —CH2CH2CH2—
-4-: —CH2CH2CH2CH2—
-1O-: —CH2—O—
-O1-: —O—CH2—
-Z-: —CH═N—N═CH—
-G-: —CF═CF—
-D-: —CH═CH—
-2D-: —CH2CH2CH═CH—
-D2-: —CH═CHCH2CH2—
Brevity codes for substituents will be shown below.
-CN: —C≡N
-F: —F
-Cl: —Cl
OCFFF: OCF3 
CFFF: CF3 
OCFF: OCHF2 
O1CFFF: OCH2CF3 
Brevity codes for rings will be shown below.































Examples 1 and 2
Nematic liquid crystal composition examples and the results for the measurement of property values will be described below.
Examples 1 and 2, and Comparative Example 1
Examples 1 and 2 are liquid crystal compositions containing compounds represented by Formula (I) and Formula (II-1), and Comparative Example 1 is a liquid crystal composition in which the compound represented by Formula (I) that is contained in Example 1 is replaced with a tolane derivative which is not substituted with fluorine atoms (3-Ph-T-Ph-O2 or the like). As compared with Comparative Example 1, Example 1 had a slight increase in viscosity, but the absolute value of Δ∈ became larger. Therefore, even if the content of the compound represented by Formula (II-1) is decreased, and the content of the so-called viscosity-reducing agent (although having a small absolute value of Δ∈, capable of lowering the viscosity of a liquid crystal composition when added thereto) is increased, a liquid crystal composition which exhibits a value of Δ∈ to the same extent as that of Comparative Example 1 can be prepared. In the liquid crystal composition described in this Example 2, the viscosity could be decreased to a large extent as compared with Comparative Example 1.











TABLE 1







Comparative





Example 1
Example 1
Example 2



















TNI
95.8
96.6
96.1


Δn
0.120
0.121
0.120


Δε
−2.7
−4.8
−2.8


η
44.5
48.7
26.2


0d1-Cy-Cy-5


7


0d1-Cy-Cy-3
12
12
20


3-Ph-T-Ph-O2
5


5-Ph-T-Ph-O1
5


3-Cy-Ph-T-Ph-2
5


4-Cy-Ph-T-Ph-1
5


0d1-Cy-Cy-Ph-1
11
11
10


0d3-Cy-Cy-Ph-1
11
11
14


0d1-Cy-1O-Ph5-O1-Cy-2
10
10
3


0d1-Cy-1O-Ph5-O1-Cy-3
10
10
3


0d1-Cy-1O-Ph5-O1-Cy-5
10
10
3


3-Ph-T-Ph5-O2

4
4


5-Ph-T-Ph5-O2

4
4


3-Cy-Ph-T-Ph5-O2

6
8


5-Cy-Ph-T-Ph5-O2

6
8


3-Cy-1O-Ph5-O1
8
8
8


3-Cy-1O-Ph5-O2
8
8
8









Examples 3 and 4, and Comparative Example 2
Examples 3 and 4 are liquid crystal compositions containing compounds represented by Formulas (I), (II-1) and (II-2), and Comparative Example 2 is a liquid crystal composition in which the compound represented by Formula (I) that is contained in Example 3 is replaced with a tolane derivative which is not substituted with fluorine atoms (3-Ph-T-Ph-O2 or the like). Similarly to the case of Examples 1 and 2 and Comparative Example 1, it was found that the viscosity was decreased to a large extent.











TABLE 2







Comparative





Example 2
Example 3
Example 4



















TNI
105.9
104.0
102.7


Δn
0.123
0.124
0.123


Δε
−3.1
−4.8
−3.2


η
40.8
43.4
27.5


0d1-Cy-Cy-5


6


0d1-Cy-Cy-3
20
20
20


3-Ph-T-Ph-O2
4


5-Ph-T-Ph-O1
4


3-Cy-Ph-T-Ph-2
4


4-Cy-Ph-T-Ph-1
4


0d1-Cy-Cy-Ph-1
12
12
14


0d3-Cy-Cy-Ph-1
15
15
15


3-Cy-1O-Nd4-O4
5
5
3


5-Cy-1O-Nd4-O2
5
5
3


5-Cy-1O-Nd4-O3
5
5
3


3-Cy-2-Cy-1O-Nd4-O2
5
5
3


2-Cy-Cy-1O-Nd4-O2
5
5
3


3-Ph-T-Ph5-O2

4
5


5-Ph-T-Ph5-O2

4
5


3-Cy-Ph-T-Ph5-O2

4
5


5-Cy-Ph-T-Ph5-O2

4
5


3-Cy-1O-Ph5-O1
6
6
5


3-Cy-1O-Ph5-O2
6
6
5









Examples 5 and 6, and Comparative Example 3
Examples 5 and 6 are liquid crystal compositions containing compounds represented by Formulas (I) and (II-1), and Comparative Example 1 is a liquid crystal composition in which the compound represented by Formula (II-1) that is contained in Example 1 is replaced with a compound which does not have a linking group in the molecule (3-Cy-Ph5-O2 or the like). As compared with Comparative Example 3, Example 5 had a slight increase in viscosity, but the absolute value of Δ∈ became larger. Therefore, even if the content of the compound represented by Formula (II-1) is decreased, and the content of the so-called viscosity-reducing agent (although having a small absolute value of Δ∈, capable of lowering the viscosity of a liquid crystal composition when added thereto) is increased, a liquid crystal composition which exhibits a value of Δ∈ to the same extent as that of Comparative Example 1 can be prepared. In the liquid crystal composition described in this Example 6, the viscosity could be decreased to a large extent as compared with Comparative Example 1.











TABLE 3







Comparative





Example 3
Example 5
Example 6



















TNI
107.1
106.9
106.8


Δn
0.129
0.126
0.127


Δε
−2.5
−3.0
−2.5


η
15.6
21.3
14.3


0d1-Cy-Cy-5


7


0d1-Cy-Cy-3
22
22
22


0d1-Cy-Cy-Ph-1
12
12
10


0d3-Cy-Cy-Ph-1
15
15
15


2-Cy-Cy-1O-Ph5-O2

9
8


3-Cy-Cy-1O-Ph5-O2

9
8


3-Cy-1O-Ph5-O1

9
4


3-Ph-T-Ph5-O2
6
6
7


5-Ph-T-Ph5-O2
6
6
7


3-Cy-Ph-T-Ph5-O2
6
6
6


5-Cy-Ph-T-Ph5-O2
6
6
6


3-Cy-Ph5-O2
9


2-Cy-Cy-Ph5-O2
9


3-Cy-Cy-Ph5-O2
9









Examples 7 and 8, and Comparative Example 4
Examples 7 and 8 are liquid crystal compositions containing compounds represented by Formulas (I) and (II-1) and Comparative Example 4 is a liquid crystal composition in which the compound represented by Formula (II-1) that is contained in Example 7 is replaced with a compound which does not have a linking group in the molecule (3-Cy-Ph5-O2 or the like). Similar to the case of Examples 5 and 6 and Comparative Example 3, it was found that the viscosity was decreased to a large extent.











TABLE 4







Comparative





Example 4
Example 7
Example 8



















TNI
113.8
114.3
109.3


Δn
0.126
0.125
0.126


Δε
−2.30
−2.66
−2.27


η
15.0
15.4
13.7


0d1-Cy-Cy-5


4


0d1-Cy-Cy-3
24
24
24


0d1-Cy-Cy-Ph-1
15
15
15


0d3-Cy-Cy-Ph-1
15
15
15


2-Cy-Cy-1O-Ph5-O2

12
9


3-Cy-Cy-1O-Ph5-O2

12
9


3-Ph-T-Ph5-O2
7
7
8


5-Ph-T-Ph5-O2
7
7
8


3-Cy-Ph-T-Ph5-O2
4
4
4


5-Cy-Ph-T-Ph5-O2
4
4
4


2-Cy-Cy-Ph5-O2
12


3-Cy-Cy-Ph5-O2
12









Examples 9 and 10, and Comparative Example 5
Examples 9 and 10 are liquid crystal compositions containing compounds represented by Formulas (I) and (II-2), and Comparative Example 5 is a liquid crystal composition in which the compound represented by Formula (I) that is contained in Example 9 is replaced with a tolane derivative which is not substituted with fluorine atoms (3-Ph-T-Ph-O2 or the like), and the compound represented by Formula (II-2) is replaced with a compound which does not have a linking group in the molecule (3-Cy-Ph5-O2 or the like). As compared with Comparative Example 5, Example 9 had a slight increase in viscosity, but the absolute value of Δ∈ became larger. Therefore, it was found that even if the contents of the compounds represented by Formulas (I) and (II-2) are decreased, and the content of the so-called viscosity-reducing agent (although having a small absolute value of Δ∈, capable of lowering the viscosity of a liquid crystal composition when added thereto) is increased, a liquid crystal composition which exhibits a larger absolute value of Δ∈ and a viscosity that is lower to a large extent as compared with Comparative Example 1 can be prepared, as is the case with the liquid crystal composition disclosed in Example 10.











TABLE 5







Comparative





Example 5
Example 9
Example 10



















TNI
120.1
115.5
114.5


Δn
0.120
0.136
0.124


Δε
−1.72
−5.81
−1.88


η
17.8
49.2
13.8


0d1-Cy-Cy-5


16


0d1-Cy-Cy-3
20
20
22


3-Ph-T-Ph-O2
6


5-Ph-T-Ph-O1
6


3-Cy-Ph-T-Ph-2
5


0d1-Cy-Cy-Ph-1
10
10
14


0d3-Cy-Cy-Ph-1
13
13
15


3-Cy-1O-Nd4-O4

7


5-Cy-1O-Nd4-O2

7
3


5-Cy-1O-Nd4-O3

7
2


3-Cy-2-Cy-1O-Nd4-O2

7
2


3-Cy-2-Cy-1O-Nd4-O3

6


2-Cy-Cy-1O-Nd4-O2

6
2


3-Ph-T-Ph5-O2

6
4


5-Ph-T-Ph5-O2

6
4


3-Cy-Ph-T-Ph5-O2

5
8


5-Cy-Ph-T-Ph5-O2


8


2-Cy-Cy-Ph5-O2
10


3-Cy-Cy-Ph5-O1
10


3-Cy-Cy-Ph5-O2
10


3-Cy-Cy-Ph5-O4
10









Examples 11 and 12, and Comparative Example 6
Examples 11 and 12 are liquid crystal compositions containing compounds represented by Formulas (I) and (II-1), and Comparative Example 6 is a liquid crystal composition in which the compound represented by Formula (II-1) that is contained in Example 11 is replaced with a compound which does not have a linking group in the molecule (2-Cy-Cy-Ph5-O2 or the like). Similarly to the case of Examples 9 and 10 and Comparative Example 5, it was found that the viscosity was decreased to a large extent.











TABLE 6







Comparative





Example 6
Example 11
Example 12



















TNI
112.8
111.5
113.3


Δn
0.119
0.115
0.118


Δε
−1.84
−3.67
−1.98


η
16.9
28.1
14.8


0d1-Cy-Cy-5


9


0d1-Cy-Cy-3
18
18
24


3-Ph-T-Ph-O2
5


5-Ph-T-Ph-O1
5


3-Ph-T-Ph-1
6


0d1-Cy-Cy-Ph-1
11
11
14


0d3-Cy-Cy-Ph-1
15
15
15


0d1-Cy-1O-Ph5-O1-Cy-2

14
6


0d1-Cy-1O-Ph5-O1-Cy-3

13
5


0d1-Cy-1O-Ph5-O1-Cy-5

13
5


3-Ph-T-Ph5-O2

3
3


5-Ph-T-Ph5-O2

3
3


3-Cy-Ph-T-Ph5-O2

5
8


5-Cy-Ph-T-Ph5-O2

5
8


2-Cy-Cy-Ph5-O2
10


3-Cy-Cy-Ph5-O1
10


3-Cy-Cy-Ph5-O2
10


3-Cy-Cy-Ph5-O4
10









Example 13 and Comparative Example 7
Example 13 is a liquid crystal composition containing compounds represented by Formula (I), Formula (II-1) and Formula (II-2), and Comparative Example 7 is a liquid crystal composition in which the compound represented by Formula (I) that is contained in Example 13 is replaced with a tolane derivative which is not substituted with fluorine atoms (3-Ph-T-Ph-1 or the like). These liquid crystal compositions have the values of TNI, Δn and Δ∈ matched. It was found that Example 13 had its viscosity greatly improved.










TABLE 7







Comparative




Example 7
Example 13




















TNI
102
102



Δn
0.180
0.180



Δε
−2.64
−22.70



η
31.0
22.3



0d1-Cy-Cy-5
4
14



1d3-Ph-T-Ph-1d3
17
10



3-Ph-T-Ph-1
10
6



0d1-Cy-Cy-Ph-1
10
14



0d3-Cy-Cy-Ph-1
7
10



3-Cy-Ph-T-Ph-2
6



4-Cy-Ph-T-Ph-1
6



3-Cy-Ph-T-Pa2-1
3



3-Cy-VO-Ph-T-Ph-1
2



3-Cy-1O-Nd4-O4
4
4



5-Cy-1O-Nd4-O2
4
3



5-Cy-1O-Nd4-O3
3
3



3-Cy-2-Cy-1O-Nd4-O2
3



2-Cy-Cy-1O-Nd4-O2
3



0d1-Cy-1O-Ph5-O1-Cy-2
9



0d1-Cy-1O-Ph5-O1-Cy-3
9
5



3-Ph-T-Ph5-O2

7



5-Ph-T-Ph5-O2

8



3-Cy-Ph-T-Ph5-O2

8



5-Cy-Ph-T-Ph5-O2

8










Example 14 and Comparative Example 8
Example 14 is a liquid crystal composition containing compounds represented by Formula (I), Formula (II-1) and Formula (II-2), and Comparative Example 8 is a liquid crystal composition in which the compound represented by Formula (I) that is contained in Example 14 is replaced with a tolane derivative which is not substituted with fluorine atoms (3-Ph-T-Ph-1 or the like). These liquid crystal compositions have the values of TNI, Δn and Δ∈ matched. It was found that Example 14 had its viscosity greatly improved.










TABLE 8







Comparative




Example 8
Example 14




















TNI
101.9
101.2



Δn
0.200
0.200



Δε
−2.72
−2.81



η
33.5
24.1



0d1-Cy-Cy-5

13



1d3-Ph-T-Ph-1d3
16
12



3-Ph-T-Ph-1
14
8



4-Ph-T-Ph-O2
3



0d1-Cy-Cy-Ph-1
12
8



1d3-Cy-Cy-Ph-1

4



3-Cy-Ph-T-Ph-2
6
4



4-Cy-Ph-T-Ph-1
6
4



3-Cy-Ph-T-Pa2-1
3



3-Cy-VO-Ph-T-Ph-1
6



3-Cy-1O-Nd4-O4
4
4



5-Cy-1O-Nd4-O2
4
4



5-Cy-1O-Nd4-O3
4
4



3-Cy-2-Cy-1O-Nd4-O2
3



2-Cy-Cy-1O-Nd4-O2
3



0d1-Cy-1O-Ph5-O1-Cy-2
8



0d1-Cy-1O-Ph5-O1-Cy-3
8
5



3-Ph-T-Ph5-O2

7



5-Ph-T-Ph5-O2

7



3-Cy-Ph-T-Ph5-O2

8



5-Cy-Ph-T-Ph5-O2

8










Examples 15 and 16
Example 15 is a liquid crystal composition having the value of Δn adjusted to be as low as 0.089, and Example 16 is a liquid crystal composition having the value of Δn adjusted to be as high as 0.200. Furthermore, liquid crystal compositions having large absolute values of Δ∈ in which the absolute values of Δ∈ were as large as 5.9 to 5.6, and voltage reduction could be achieved in a wide range of Δn, could be prepared. It was found that the liquid crystal compositions of the present invention can have the values of Δn and Δ∈ adjusted in accordance with various requirement characteristics, and low viscosity can be realized.










TABLE 9







Example 15
Example 16




















TNI
93.5
101.5



Δn
0.089
0.200



Δε
−5.90
−5.60



η
28.9
65.6



1d1-Cy-Cy-3
20



1d3-Ph-T-Ph-1d3

10



3-Ph-T-Ph-1

5



0d1-Cy-Cy-Ph-1
5



0d3-Cy-Cy-Ph-1
5



3-Cy-Ph-T-Ph-2

4



4-Cy-Ph-T-Ph-1

4



3-Cy-1O-Nd4-O4

5



5-Cy-1O-Nd4-O2

5



5-Cy-1O-Nd4-O3

5



0d1-Cy-1O-Ph5-O1-Cy-2
6
10



0d1-Cy-1O-Ph5-O1-Cy-3
15
11



0d1-Cy-1O-Ph5-O1-Cy-5

11



3-Ph-T-Ph5-O2

7



5-Ph-T-Ph5-O2

7



3-Cy-Ph-T-Ph5-O2
3
8



5-Cy-Ph-T-Ph5-O2

8



3-Cy-Cy-VO-Ph5-O2
10



3-Cy-1O-Ph5-O1
8



3-Cy-1O-Ph5-O2
10



2-Cy-Cy-1O-Ph5-O2
8



3-Cy-Cy-1O-Ph5-O2
10










Examples 17 to 19
Examples 17 to 19 are liquid crystal compositions in which TNI is as high as 104° C., and the values of Δn and Δ∈ are also respectively set to be high. It is usually difficult to obtain a liquid crystal composition which satisfies such requirement characteristics, but the present invention enables this. Furthermore, an increase in viscosity could also be suppressed.











TABLE 10







Example 17
Example 18
Example 19



















TNI
104.1
106.0
107.3


Δn
0.247
0.232
0.231


Δε
−6.9
−7.6
−7.7


η
48.8
51.1
41.2


1d3-Ph-T-Ph-1d3
5
3


3-Ph-T-Ph-1
5
2
6


0d1-Cy-Cy-Ph-1
5


3-Cy-1O-Nd4-O4
5


5-Cy-1O-Nd4-O2
5


5-Cy-1O-Nd4-O3
5


0d1-Cy-1O-Ph5-O1-Cy-2

10


0d1-Cy-1O-Ph5-O1-Cy-3

10


0d1-Cy-1O-Ph5-O1-Cy-5

5


3-Cy-1O-Ph5-O2


10


2-Cy-Cy-1O-Ph5-O2


6


3-Cy-Cy-1O-Ph5-O2


10


3-Ph-T-Ph5-O2
20
20
18


5-Ph-T-Ph5-O2
20
20
18


3-Cy-Ph-T-Ph5-O2
15
15
16


5-Cy-Ph-T-Ph5-O2
15
15
16

## Claims

1. A liquid crystal composition comprising:
as a first component, one or more compounds selected from compounds represented by Formula (I):




wherein R11 and R12 each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, while these groups are each independently unsubstituted or have at least one halogen group as a substituent, and one or more of —CH2— present in these groups may be each independently substituted by —O—, —S—, —CO—, —COO—, —OCO— or —OCO—O— such that oxygen atoms are not directly bonded to each other;
A11 and A12 each independently represent a group selected from the group consisting of:
(a) a trans-1,4-cyclohexylene group (wherein one —CH2— or non-adjacent two or more of —CH2—, which are present in this group, may be substituted by —O— and/or —S—,
(b) a 1,4-phenylene group (wherein one —CH═ or non-adjacent two or more of —CH═ groups, which are present in this group, may be substituted by —N═), and
(c) 1,4-bicyclo(2.2.2)octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, or 1,2,3,4-tetrahydronaphthalene-2,6-diyl,
while the hydrogen atoms on the group (a), group (b) and group (c) may be each independently substituted by an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkenyloxy group having 1 to 3 carbon atoms, CN or halogen;
Z11 and Z12 each independently represent —COO—, —OCO—, —CH2O—, —OCH2—, —CF2O—, —OCF2—, —CH2CH2—, —CH═CH—, —C≡C—, —(CH2)4—, —CH═CH—CH2CH2—, —CH2CH2—CH═CH—, or a single bond;
a11 and a12 each independently represent 0 or 1; and
as a second component, one or more compounds selected from compounds represented by Formulas (II) and (III):




wherein R21, R22, R31 and R32 each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, while these groups are each independently unsubstituted or have at least one halogen group as a substituent, and one or two or more of —CH2— present in these groups may be each independently substituted by —O—, —S—, —CO—, —COO—, —OCO— or —OCO—O— such that oxygen atoms are not directly bonded to each other;
A21, A22, A23 each independently represent a group selected from the group consisting of:
(a) a trans-1,4-cyclohexylene group (wherein one —CH2— or non-adjacent two or more of —CH2—, which are present in this group, may be substituted by —O— and/or —S—,
(b) a 1,4-phenylene group (wherein one —CH═ or non-adjacent two or more of —CH═groups, which are present in this group, may be substituted by —N═), and
(c) 1,4-bicyclo(2.2.2)octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, or 1,2,3,4-tetrahydronaphthalene-2,6-diyl,
while the hydrogen atoms on the group (a), group (b) and group (c) may be each independently substituted by an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkenyloxy group having 1 to 3 carbon atoms, CN or halogen;
Z21, and Z23 each independently represent —COO—, —OCO—, —CH2O—, —OCH2—, —CF2O—, —OCF2—, —CH2CH2—, —CH═CH—, —C≡C—, —(CH2)4—, —CH═CH—CH2CH2—, —CH2CH2—CH═CH—, or a single bond;
Z22 represents —COO—, —OCO—, —CH2O—, —OCH2—, —OCF2—, —CH2CH2—, —CH═CH—, —C≡C—, —(CH2)4—, —CH═CH—CH2CH2—, —CH2CH2—CH═CH—, or a single bond;
A31, A32 and A33 each independently represent a group selected from the group consisting of:
(a) a trans-1,4-cyclohexylene group (wherein one —CH2— or non-adjacent two or more of —CH2—, which are present in this group, may be substituted by —O— and/or —S—;
(b) a 1,4-phenylene group (wherein one —CH═ or non-adjacent two or more of —CH═ groups, which are present in this group, may be substituted by —N═) and
(c) 1,4-cyclohexenylene, 1,4-bicyclo(2.2.2)octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, or 1,2,3,4-tetrahydronaphthalene-2,6-diyl,
while the hydrogen atoms on the group (a), group (b) and group (c) may be each independently substituted by an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkenyloxy group having 1 to 3 carbon atoms, CN or halogen;
Z31, Z32 and Z33 each independently represent —COO—, —OCO—, —CH2O—, —OCH2—, —CF2O—, —OCF2—, —CH2CH2—, —CH═CH—, —C≡C—, —(CH2)4—, —CH═CH—CH2CH2—, —CH2CH2—CH═CH—, or a single bond; and
a21, a22, a31 and a32 each independently represent 0 or 1,
the liquid crystal composition comprising at least one compound represented by Formula (II) in which Z22 represents —CH2O—, or at least one compound represented by Formula (III) in which Z32 represents —CH2O— or —CF2O—.

2. The liquid crystal composition according to claim 1, comprising, as a third component, one or more compounds selected from compounds represented by Formula (IV):


[Chemical Formula 3]



R41-A41Z41A42-Z42a41-A43-R42  (IV)

wherein R41 and R42 each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms, while these groups are each independently unsubstituted or have at least one halogen group as a substituent, and one or two or more of —CH2— present in these groups may be each independently substituted by —O—, —S—, —CO—, —COO—, —OCO— or —OCO—O— such that oxygen atoms are not directly bonded to each other;
A41, A42 and A43 each independently represent a group selected from the group consisting of:
(a) a trans-1,4-cyclohexylene group (wherein one —CH2— or non-adjacent two or more of —CH2—, which are present in this group, may be substituted by —O— and/or —S—,
(b) a 1,4-phenylene group (wherein one —CH═ or non-adjacent two or more of —CH═ groups, which are present in this group, may be substituted by —N═), and
(c) 1,4-cyclohexenylene, 1,4-bicyclo(2.2.2)octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, or 1,2,3,4-tetrahydronaphthalene-2,6-diyl,
while the hydrogen atoms on the group (a), group (b) and group (c) may be each independently substituted by an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkenyloxy group having 1 to 3 carbon atoms, CN or halogen, but A41, A42 and A43 are not intended to represent a 2,3-dihalo-1,4-phenylene group;
Z41 and Z42 each independently represent —COO—, —OCO—, —CH2O—, —OCH2—, —CF2O—, —CF2—, —CH2CH2—, —CH═N—N═CH—, —CH═CH—, —C≡C—, —(CH2)4—, —CH═CH—CH2CH2—, —CH2CH2—CH═CH—, or a single bond; and
A41 represents 0, 1 or 2, but when a41 represents 2, the two A42's that are present may be identical or different from each other, and when a41 represents 2, the two Z42's that are present may be identical or different from each other.

3. The liquid crystal composition according to claim 2, wherein the second component is one or more compounds selected from compounds represented by Formula (II).

4. The liquid crystal composition according to claim 1, wherein the second component is one or more compounds selected from compounds represented by Formula (III).

5. The liquid crystal composition according to claim 1, wherein the second component is one or more compounds represented by Formula (II) in which Z22 represents —CH2O—.

6. The liquid crystal composition according to claim 1, wherein the second component is one or more compounds represented by Formula (III) in which Z32 represents —CH2O— or —CF2O—.

7. The liquid crystal composition according to claim 2, wherein the third component is one or more compounds in which a41 is 0; A41 and A43 are trans-1,4-cyclohexylene groups; and Z41 is a single bond.

8. The liquid crystal composition according to claim 1, wherein the total amount of the first component and the second component is from 10% by mass to 80% by mass.

9. The liquid crystal composition according to claim 1, wherein the nematic-isotropic transition temperature is 70° C. to 120° C., the dielectric anisotropy is −1.5 to −8.0, and the birefringence is 0.080 to 0.250.

10. The liquid crystal composition according to claim 9, comprising a photopolymerizable monomer in an amount of 500 ppm to 5000 ppm.

11. A liquid crystal display element using the liquid crystal composition according to claim 10.

12. The liquid crystal display element according to claim 11, wherein the pretilt angle is 80° to 90°.

13. The liquid crystal display element according to claim 11, being an active matrix-driven type element.

14. The liquid crystal display element according to claim 11, being a passive matrix-driven type element.