The present invention relates to a liquid crystal composition useful as a constituent member of a liquid crystal display device and the like, and a liquid crystal display element.
A liquid crystal display element has become used in watches, clocks, and electronic calculators, and also in various measurement instruments, automobile panels, word processors, electronic organizers, printers, computers, televisions, watches, clocks, advertisement billboards, etc. Typical liquid crystal display systems include a TN (twisted nematic) mode, an STN (super-twisted nematic) mode, a TFT (thin-film transistor)-using VA (hereinafter also referred to as vertical alignment) mode, an IPS (in-plane switching) mode, etc. The liquid crystal composition to be used in these liquid crystal display elements is required to be stable to external factors such as moisture, air, heat, light and the like, to express a liquid crystal phase in a broadest possible temperature range around room temperature as the center, to have a low viscosity and to have a low driving voltage. Furthermore, to make characteristic values of dielectric anisotropy (Δ∈), refractive index anisotropy (Δn) and the like be optimum values to the individual display elements, the liquid crystal composition is constituted of compounds of several kinds to several tens kinds.
For example, VA mode widely used in a liquid crystal TV and the like generally uses a liquid crystal composition having negative Δ∈, and TN mode used in PC monitor and the like and IPS mode widely used in a touch panel and the like generally use a liquid crystal composition having positive Δ∈. As a matter of course, a liquid crystal composition showing low voltage driving, high response and wide operating temperature range is required in not only those IPS and VA modes, but all of driving systems. To respond to the requirement, a liquid crystal composition having Δ∈ of large absolute value, small viscosity (η) and high nematic phase-isotropic liquid phase transition temperature (Tni) is required. Further, from the setting of Δn×d that is a product of Δn and a cell gap (d), it is necessary to adjust Δn of a liquid crystal composition to an appropriate range in conformity with a cell gap. In addition, in the case of applying a liquid crystal display element to a television and the like, high responsiveness is considered to be important, and therefore, a liquid crystal composition having small γ1 is required. In view of the above, to constitute a liquid crystal composition having small γ1, conventionally a compound having a bicyclohexane framework has been generally used as shown in, for example, PTL 1.
However, a bicyclohexane compound is effective to decrease γ1, but vapor pressure generally tends to be high, and particularly the tendency is remarkable in a compound having short alkyl chain length. Further, the bicyclohexane compound has the tendency showing low Tni, and therefore, the bicyclohexane compound generally uses a compound in which the total of a side chain length is 5 to 7 carbon atoms or more, in many cases.
For example, one of the technology in which a bicyclohexane framework is essential includes PTL 2. PTL 2 discloses a liquid crystal composition in which the formula (1) of a so-called tetracyclic framework in which four benzene rings or four cyclohexane rings are connected, and the formula (2) of a bicyclohexane framework are essential.
According to PTL 2, the compound (1) represented by the formula (1) of a tetracyclic framework plays a role of increasing an upper limit temperature and an absolute value of dielectric anisotropy, and the compound (2) represented by the formula (2) of a bicyclohexane framework plays a role of decreasing a viscosity (paragraph [0046]). For this reason, it is surely confirmed that when Examples of PTL 2 are examined, viscosity (η), dielectric anisotropy (Δ∈) or phase transition temperature (Tni) is improved as compared with Comparative Examples.
PTL 1: JP-T 2008-505235
PTL 2: JP-A 2011-144274
PTL 2 describes that in the characteristics of dielectric anisotropy (Δ∈) having large absolute value, small viscosity (η), upper limit (Nl) and lower limit (Tc) of a nematic phase, large specific resistance, high stability to ultraviolet rays, high stability to heat, and the like, at least one characteristic is satisfied. However, properties of a liquid crystal composition confirmed in all Examples of the PTL are any one of viscosity (η), dielectric anisotropy (Δ∈), phase transition temperatures (Nl and Tc) and voltage holding ratio (VHR). Thus, it is the present status that evaluations and investigations are not made at all on the items relating to reliability, such as large specific resistance, stability to ultraviolet rays and stability to heat. PTL 1 is the same in this regard, and characteristics relating to reliability are indispensable from the standpoint of maintaining display quality of a liquid crystal display element that is the use embodiment of a liquid crystal composition. Particularly, in the case of using the bicyclohexane compound and the liquid crystal compound of relatively low molecule described in PTLs 1 and 2 above, the problem of high volatility always remains, and additionally, when an alkenyl group, an alkoxy group or the like is bonded to the end of those compounds, new problem causes in reliability such as light resistance, heat resistance or burn-in.
In view of the above, the present invention has been made to solve the above problems, and has an object that in the liquid crystal composition of the present invention, a composition having excellent reliability such as light resistance, heat resistance or burn-in while maintaining high responsiveness is provided.
To solve the above problems, the present inventors have found that reliability such as light resistance, heat resistance or burn-in can be improved, and have reached to complete the present invention.
The present invention has an object to provide a liquid crystal composition containing, as a first component, at least one selected from the group of compounds represented by the following formula (1):
in General Formula (1), R1 and R2 each independently represent one group selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms and an alkoxy group having 1 to 15 carbon atoms, and
as a second component, at least one selected from the group consisting of compounds represented by the following General Formula (2):
in General Formula (2), R3 is selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms and an alkoxy group having 1 to 15 carbon atoms,
Z0 represents a single bond, —CH2O— or —OCH2—, and
R4 is selected from the group consisting of an alkyl group having 1 to 15 carbon atoms and an alkoxy group having 1 to 15 carbon atoms.
According to the present invention, the liability such as light resistance, heat resistance or burn-in of a liquid crystal composition can be improved.
The first aspect of the present invention is a liquid crystal composition containing, as a first component, at least one selected from the group of compounds represented by General Formula (1):
in General Formula (1), R1 and R2 each independently represent one group selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, and an alkoxy group having 1 to 15 carbon atoms, and
as a second component, at least one selected from the group of compounds represented by General Formula (2):
in General Formula (2), R3 is selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, and an alkoxy group having 1 to 15 carbon atoms,
Z0 represents a single bond, —CH2O— or —OCH2—, and
R4 is at least one group selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, and an alkoxy group having 1 to 15 carbon atoms.
Reliability such as light resistance, heat resistance or burn-in of the liquid crystal composition can be improved by the combination of General Formula (1) and General Formula (2).
The liquid crystal composition of the present invention contains the first component represented by General Formula (1) and the second component represented by General Formula (2) as essential components, and as necessary, may further contain a third component represented by General Formula (3), a fourth component represented by General Formula (4), a polymerizable monomer and at least one selected from the group consisting of other components such as additives. Specifically, the liquid crystal composition of the present invention contains the compounds represented by General Formulas (1) and (2) as essential components, and as necessary, can further contain at least one selected from the group consisting of the compounds of General Formulas (3) and (4) described hereinunder.
The total content of the compounds represented by General Formulas (1) and (2) contained in the liquid crystal composition is that, as the lower limit, 5 mass % is preferable, 10 mass % is preferable, 12 mass % is preferable, 15 mass % is preferable, 17 mass % is preferable, 20 mass % is preferable, 22 mass % is preferable, 24 mass % is preferable, 26 mass % is preferable, 28 mass % is preferable, and 30 mass % is preferable. As the upper limit, 50 mass % is preferable, 45 mass % is preferable, 43 mass % is preferable, 40 mass % is preferable, 38 mass % is preferable, 36 mass % is preferable, 30 mass % is preferable, 28 mass % is preferable, and 26 mass % is preferable.
The value of dielectric anisotropy Δ∈ of the liquid crystal composition of the present invention is, at 25° C., preferably −2.0 to −6.0, more preferably −2.5 to −5.0, and particularly preferably −2.5 to −4.0, and further in detail, the value of dielectric anisotropy Δ∈ falls within a range of −2.5 to −3.4 from the viewpoint of response speed.
The value of refractive index anisotropy (Δn) of the liquid crystal composition of the present invention is, at 25° C., preferably 0.08 to 0.13, more preferably 0.09 to 0.12. Further in detail, the value is preferably about 0.10 to 0.12 for a thin cell gap, and is preferably about 0.08 to 0.10 for a thick cell gap.
The upper limit of the rotational viscosity (γ1) of the liquid crystal composition of the present invention is preferably 150 (mPa·s) or less, more preferably 130 (mPa·s) or less, even more preferably 120 (mPa·s) or less. On the other hand, the lower limit of the rotational viscosity (γ1) is preferably 20 (mPa·s) or more, more preferably 30 (mPa·s) or more, even more preferably 40 (mPa·s) or more, still more preferably 50 (mPa·s) or more, further more preferably 60 (mPa·s) or more, and especially preferably 70 (mPa·s) or more.
Of the liquid crystal composition of the present invention, the function Z between the rotational viscosity and the refractive index anisotropy preferably indicates a specific value.
Z=γ1/(Δn)2 [Math. 1]
In the above numerical formula, γ1 represents a rotational viscosity, and Δn represents a refractive index anisotropy.
Z is preferably 13,000 or less, more preferably 12,000 or less, even more preferably 11,000 or less.
In the case where the liquid crystal composition of the present invention is used in an active matrix display element, it must have a specific resistivity of 1011 (Ω·m) or more, preferably 1012 (Ω·m) or more, more preferably 1013 (Ω·m) or more.
The liquid crystal composition of the present invention can be used in a broad nematic phase-isotropic liquid phase transition temperature (TNI) range, and the phase transition temperature (TNI) is preferably 60 to 120° C., more preferably 70 to 110° C., even more preferably 75 to 100° C.
The components that can be contained in the liquid crystal composition of the present invention are described in detail hereinunder.
The liquid crystal composition of the present invention contains, as the first component, the compound represented by the following General Formula (1):
in General Formula (1), R1 and R2 each independently represent one group selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, and an alkoxy group having 1 to 15 carbon atoms,
as the essential component.
Preferably, the liquid crystal composition contains the compound represented by General Formula (1) from the standpoint of the improvement of reliability, such as light resistance, heat resistance or burn-in. Particularly, when the compound represented by General Formula (1) is contained in the liquid crystal composition, the compound contributes to the increase of a transition temperature and Δn, but also increases a viscosity. For this reason, the compound may be disadvantageous to the liquid crystal composition that aims at high response. However, it has been confirmed that the increase of a viscosity can be suppressed to a certain extent by combining the compound with the compound represented by General Formula (2). The compound has an ester bond in a linking group. Therefore, solubility is excellent as compared with a compound in which tetracyclic structure is directly connected, but there a problem that the ester bond is easy to decompose and is easy to hold ions as impurities. However, as confirmed in the examples described hereinunder, it has been confirmed that a liquid crystal composition having excellent light resistance that is relatively difficult to be decomposed can be provided by combining with the compound represented by General Formula (2).
In General Formula (1), preferably, R1 and R2 each independently represent one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms.
The compound represented by General Formula (1) as the first component preferably contains at least one kind of the compounds represented by the following General Formula (1-1)
in General Formula (1-1), R2 each independently is one group selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms and an alkoxy group having 1 to 15 carbon atoms.
The liquid crystal composition preferably contains the compound represented by General Formula (3) from the standpoint of the improvement of reliability in light resistance, heat resistance or burn-in.
The compound represented by General Formula (1) is particularly preferably compounds represented by the formulae (1.1) to (1.5).
In the liquid crystal composition of the present invention, the lower limit of the content of the first component is, as one embodiment of the present invention, for example, preferably 1 mass %, preferably 3 mass %, preferably 5 mass %, preferably 7 mass %, preferably 9 mass %, preferably 10 mass %, preferably 12 mass %, preferably 15 mass %, preferably 16 mass %, preferably 18 mass %, preferably 20 mass %, preferably 22 mass %, preferably 24 mass %, preferably 26 mass %, preferably 28 mass %, preferably 30 mass %, preferably 32 mass %, preferably 35 mass %, and preferably 40 mass %, based on the total amount (100 mass %) of the liquid crystal composition of the present invention.
Further, in the liquid crystal composition of the present invention, the upper limit of the content of the first component is, as one embodiment of the present invention, for example, preferably 45 mass %, preferably 42 mass %, preferably 40 mass %, preferably 38 mass %, preferably 36 mass %, preferably 34 mass %, preferably 32 mass %, preferably 30 mass %, preferably 28 mass %, preferably 26 mass %, preferably 24 mass %, preferably 26 mass %, preferably 24 mass %, preferably 22 mass %, preferably 20 mass %, preferably 18 mass %, preferably 16 mass %, preferably 14 mass %, preferably 12 mass %, preferably 10 mass %, preferably 8 mass %, preferably 6 mass %, preferably 5 mass %, and preferably 4 mass %, based on the total amount (100 mass %) of the liquid crystal composition of the present invention.
In the first component in the present invention, kinds that can combine the compounds represented by General Formula (1) with each other are not particularly limited, and are used by appropriately combining depending on desired performances such as solubility at low temperature, a transition temperature, electrical reliability and a birefringence. For example, as one embodiment of the present invention, the kind of the compound of General Formula (1) used as the first component is that the first component is one kind of the compounds represented by General Formula (1). Alternatively, in other embodiment of the present invention, the first component is two kinds of the compounds represented by General Formula (1). In other embodiment of the present invention, the first component is three kinds of the compounds represented by General Formula (1). In other embodiment of the present invention, the first component is four kinds of the compounds represented by General Formula (1). In other embodiment of the present invention, the first component is five kinds of the compounds represented by General Formula (1). In other embodiment of the present invention, the first component is six kinds of the compounds represented by General Formula (1). In other embodiment of the present invention, the first component is seven kinds of the compounds represented by General Formula (1). In other embodiment of the present invention, the first component is eight kinds of the compounds represented by General Formula (1). In other embodiment of the present invention, the first component is nine kinds of the compounds represented by General Formula (1). In other embodiment of the present invention, the first component is a system containing ten or more kinds of the compounds represented by General Formula (1).
The liquid crystal composition of the present invention contains, as the second component, at least one selected from the group consisting of the compound represented by the following General Formula (2):
in General Formula (2), R3 is selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms and an alkoxy group having 1 to 15 carbon atoms,
Z0 represents a single bond, —CH2O— or —OCH2—, and
R4 is at least one group selected from the group consisting of an alkyl group having 1 to 15 carbon atoms and an alkoxy group having 1 to 15 carbon atoms, as the essential component.
The liquid crystal composition preferably contains the compound represented by General Formula (2) from the standpoint of the improvement of reliability in light resistance, heat resistance or burn-in. When Z0 is a single bond, the condition is preferably satisfied that R3 in General Formula (2) preferably satisfies the condition that R4 is an alkyl group in the case where R3 in General Formula (2) is an alkenyl group, from the standpoint of the improvement of reliability in light resistance, heat resistance or burn-in.
In General Formula (2), R3 is preferably selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, and R4 is preferably at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms.
The preferred embodiment of the compound represented by General Formula (2) is preferably one or more kinds selected from the group consisting of the following formulae (2.1) to (2.26).
Compounds represented by
are preferred, and the formulae (2.1) to (2.6), the formulae (2.13) to (2.21) and the formulae (2.25) to (2.26) are more preferred.
In the case of considering reliability of the liquid crystal composition of the present invention to be important, Z0 is preferably a single bond. On the other hand, in the case of using the liquid crystal composition of the present invention in a display element of low voltage driving, Z0 is preferably —CH2O— or —OCH2—, and is more preferably —CH2O— from the standpoint of dielectric anisotropy.
In the liquid crystal composition of the present invention, the lower limit of the content of the second component is, as one embodiment of the present invention, for example, preferably 1 mass %, preferably 3 mass %, preferably 5 mass %, preferably 7 mass %, preferably 9 mass %, preferably 10 mass %, preferably 12 mass %, preferably 15 mass %, preferably 16 mass %, preferably 18 mass %, preferably 20 mass %, preferably 22 mass %, preferably 24 mass %, preferably 26 mass %, preferably 28 mass %, preferably 30 mass %, preferably 32 mass %, preferably 35 mass %, and preferably 40 mass %, based on the total amount (100 mass %) of the liquid crystal composition of the present invention.
Further, in the liquid crystal composition of the present invention, the upper limit of the content of the second component is, as one embodiment of the present invention, for example, preferably 60 mass %, preferably 58 mass %, preferably 56 mass %, preferably 54 mass %, preferably 52 mass %, preferably 50 mass %, preferably 48 mass %, preferably 46 mass %, preferably 45 mass %, preferably 42 mass %, preferably 40 mass %, preferably 38 mass %, preferably 36 mass %, preferably 34 mass %, preferably 32 mass %, preferably 30 mass %, preferably 28 mass %, preferably 2 mass % preferably 24 mass %, preferably 26 mass %, preferably 24 mass % s, preferably 22 mass %, preferably 20 mass %, preferably 18 mass %, preferably 16 mass %, preferably 14 mass %, preferably 12 mass % and preferably 10 mass %, based on the total amount (100 mass %) of the liquid crystal composition of the present invention.
In the second component in the present invention, kinds that can combine the compounds represented by General Formula (2) with each other are not particularly limited, and are used by appropriately combining depending on desired performances such as solubility at low temperature, a transition temperature, electrical reliability and a birefringence. For example, as one embodiment of the present invention, the kind of the compound of General Formula (2) used as the second component is that the second component is one kind of the compound represented by General Formula (2). Alternatively, in other embodiment of the present invention, the second component is two kinds of the compounds represented by General Formula (2). In other embodiment of the present invention, the second component is three kinds of the compounds represented by General Formula (2). In other embodiment of the present invention, the second component is four kinds of the compounds represented by General Formula (2). In other embodiment of the present invention, the second component is five kinds of the compounds represented by General Formula (2) In other embodiment of the present invention, the second component is six kinds of the compounds represented by General Formula (2). In other embodiment of the present invention, the second component is seven kinds of the compounds represented by General Formula (2). In other embodiment of the present invention, the second component is eight kinds of the compounds represented by General Formula (2). In other embodiment of the present invention, the second component is nine kinds of the compounds represented by General Formula (2) In other embodiment of the present invention, the second component is a system containing ten or more kinds of the compounds represented by General Formula (2).
Preferably, the liquid crystal composition of the present invention further contains, as the third component, at least one compound selected from the group consisting of compounds represented by the following General Formula (3):
(in General Formula (3), RL1 and RL2 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or non-adjacent two or more (—CH2—)'s in the alkyl group may be each independently substituted with —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
OL indicates 0, 1, 2 or 3,
BL1, BL2 and BL3 each independently represent a group selected from the following (a) and (b):
(a) a 1,4-cyclohexylene group (one —CH2— or non-adjacent 2 or more (—CH2—)'s existing in this group may be substituted with —O—),
(b) a 1,4-phenylene group (one —CH═ or non-adjacent two or more (—CH═)'s existing in this group may be substituted with —N═),
wherein the hydrogen atom contained in the group represented by the above (a) and the above (b) may be each independently substituted with a cyano group, a chlorine atom or a fluorine atom,
LL1 and LL2 each independently represent a single bond, —CH2CH2—, —(CH2)4—, —OCH2—, —CH2O—, —COO—, —OCO—, —OCF2—, —CF2O—, —CH═N—N═CH—, —CH═CH—, —CF═CF— or —C≡C—,
when OL is 2 or 3 and plural LL2's are present, they may be the same or different, and when OL is 2 or 3 and plural BL3's are present, they may be the same or different,
with the proviso that compounds represented by General Formula (1) and compounds represented by General Formula (2) are excluded.)
In General Formula (5) where the cyclic structure bonding thereto is a phenyl group (aromatic), RL1 and RL2 each are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 (or more) carbon atoms, or an alkenyl group having 4 to 5 carbon atoms, and where the cyclic structure bonding thereto is a cyclohexane, a pyran, a dioxane or the like saturated cyclic structure, they each are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 (or more) carbon atoms, or a linear alkenyl group having 2 to 5 carbon atoms.
In the case where the liquid crystal composition of the present invention is required to have chemical stability, it is desirable that the compound represented by General Formula (3) to be therein does not have a chlorine atom in the molecule thereof. With respect to the compound represented by General Formula (3) according to the present invention, it is preferred that the number of a halogen atom present in one molecule is zero or 1.
Adding such a compound represented by General Formula (3) to the liquid crystal composition is especially preferred in the point that the viscosity, Δn and the transition point of the liquid crystal composition can be changed arbitrarily while minimizing the driving voltage change for liquid crystal display elements.
The content of the third component in the liquid crystal composition of the present invention is, like that of the above-mentioned other components, suitably selected in relation to not only the use mode and the use object of the liquid crystal composition but also to the other components, and therefore a preferred range of the content of the third component contained in the liquid crystal composition is preferably differently and independently defined.
In the liquid crystal composition of the present invention, the lower limit of the content of the third component is, as one embodiment of the present invention, for example, preferably 1 mass % based on the total amount (100 mass %) of the liquid crystal composition of the present invention. Alternatively, in another embodiment of the present invention, the lower limit is preferably 10 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 20 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 30 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 40 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 50 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 55 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 60 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 65 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 70 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 75 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 80 mass %.
Further, in the liquid crystal composition of the present invention, the upper limit of the content of the third component is, for example, preferably 95 mass % based on the total amount (100 mass %) of the liquid crystal composition of the present invention in one embodiment of the present invention. Further, the upper limit is preferably 85 mass % in another embodiment of the present invention. Further, the upper limit is preferably 75 mass % in another embodiment of the present invention. Further, the upper limit is preferably 65 mass % in another embodiment of the present invention. Further, the upper limit is preferably 55 mass % in another embodiment of the present invention. Further, the upper limit is preferably 45 mass % in another embodiment of the present invention. Further, the upper limit is preferably 35 mass % in another embodiment of the present invention. Further, the lower limit is preferably 25 mass % in another embodiment of the present invention.
In the liquid crystal composition of the present invention, the content of the compound represented by General Formula (3) is required to be appropriately adjusted depending on required performances such as solubility at low temperature, a transition temperature, electrical reliability, a birefringence, process adaptability and drop marks described hereinunder, burn-in and dielectric anisotropy.
In the case where a liquid crystal composition maintaining a viscosity of the liquid crystal composition of the present invention low and having high response speed is required, it is preferred that the lower limit is high and the upper limit is high. Further, in the case where a liquid crystal composition maintaining Tni of the liquid crystal composition of the present invention high and having good temperature stability is required, it is preferred that the lower limit is high and the upper limit is high. When dielectric anisotropy is desired to be increased in order to maintain driving voltage low, it is preferred that the lower limit is low and the upper limit is low.
In the third component in the present invention, kinds that can combine the compounds represented by General Formula (3) with each other are not particularly limited, and are used by appropriately combining those depending on desired performances such as solubility at low temperature, a transition temperature, electrical reliability and a birefringence. For example, as one embodiment of the present invention, the kind of the compound of General Formula (3) used as the third component is that the third component is one kind of the compound represented by General Formula (3). Alternatively, in other embodiment of the present invention, the third component is two kinds of the compounds represented by General Formula (3). Further, in other embodiment of the present invention, the third component is three kinds of the compounds represented by General Formula (3). In other embodiment of the present invention, the third component is four kinds of the compounds represented by General Formula (3). In other embodiment of the present invention, the third component is five kinds of the compounds represented by General Formula (3). In other embodiment of the present invention, the third component is six kinds of the compounds represented by General Formula (3). In other embodiment of the present invention, the third component is seven kinds of the compounds represented by General Formula (3). In other embodiment of the present invention, the third component is eight kinds of the compounds represented by General Formula (3). In other embodiment of the present invention, the third component is nine kinds of the compounds represented by General Formula (3). In other embodiment of the present invention, the third component is a system containing ten or more kinds of the compounds represented by General Formula (3).
The total content of the compounds represented by General Formulas (1), (2) and (3) contained in the liquid crystal composition of the present invention is that, as the lower limit, 16 mass % is preferable, 18 mass % is preferable, 20 mass % is preferable, 23 mass % is preferable, 25 mass % is preferable, 28 mass % is preferable, 30 mass % is preferable, 32 mass % is preferable, 35 mass % is preferable, 38 mass % is preferable, 40 mass % is preferable, 42 mass % is preferable, 45 mass % is preferable, 47 mass % is preferable, and 50 mass % is preferable. As the upper limit, 35 mass % is preferable, 38 mass % is preferable, 40 mass % is preferable, 42 mass % is preferable, 45 mass % is preferable, 47 mass % is preferable, 50 mass % is preferable, 53 mass % is preferable, 55 mass % is preferable, 57 mass % is preferable, 60 mass % is preferable, 62 mass % is preferable, 65 mass % is preferable, 68 mass % is preferable, 70 mass % is preferable, 72 mass % is preferable, 75 mass % is preferable, 78 mass t is preferable, 80 mass % is preferable, 82 mass % is preferable, 85 mass % is preferable, 88 mass % is preferable, 90 mass % is preferable, 92 mass % is preferable, 95 mass % is preferable, 97 mass % is preferable, 98 mass % is preferable, 99 mass % is preferable, and 100 mass % is preferable.
The lower limit of the dielectric anisotropy (Δ∈) of the compound represented by General Formula (3) of the present invention is −1 in one embodiment, and −0.5 in another embodiment. Further, the value is 0 in another embodiment, and 0.5 in still another embodiment. Further, the value is 1 in another embodiment and −0.3 in still another embodiment. On the other hand, the upper limit of the dielectric anisotropy (Δ∈) of a liquid crystal composition including the compound represented by General Formula (3) is +1 in one embodiment, and +0.5 in another embodiment. Further, the value is 0 in another embodiment, and −0.5 in still another embodiment. Further, the value is +0.3 in another embodiment, and −0.7 in still another embodiment.
The compound represented by General Formula (3) in the present invention is preferably at least one kind of a compound selected from the group of the compounds represented by General Formulas (V-a) to (V-g).
In General Formulas (V-a) to (V-f), R500 to RS11 each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and L is a divalent linking group; and, in General Formula (V-g), RS1 and R52 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, A51 and AS2 each independently represent a 1,4-cyclohexylene group or a 1,4-phenylene group, Q5 represents a single bond or COO—, X51 and X52 each independently represent a fluorine atom or a hydrogen atom, and mS0 is an integer of 0 or 1, but excluding the condition that General Formula (V-g) has the same structure as General Formulas (V-b) to (V-e). Further, it is preferred to exclude that X51 and X52 are simultaneously a fluorine atom in General Formula (V-g), and this is the same as that the compound represented by General Formula (3) in the present invention does not contain a halogen in the same ring structure.
In General Formulas (V-a) to (V-f), R500 to RS11 each independently preferably represent an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and more preferably represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 2 to 5 carbon atoms. Further, the divalent linking group (L) in General Formula (V-f) preferably represents a single bond, —CF2O— or COO—.
In the case of indicating an alkenyl group in General Formulas (V-a) to (V-g), the same alkenyl groups described above are preferably exemplified, and the formulae (i) to (iv) are more preferably exemplified.
R500 and RS09 may be the same or different, but preferably represent different substituents.
In the case of using the compound selected from the group of seven compounds represented by General Formulas (V-a) to (V-g) as the third component, one to ten kinds of compounds are preferably contained in the third component, one to eight kinds of compounds are more preferably contained in the third component, one to five kinds of compounds are even more preferably contained in the third component, and two to four kinds of compounds are particularly preferably contained in the third component. In this case, the total content of the third component in the liquid crystal composition of the present invention is preferably 5 to 50%, more preferably 5 to 40 mass %, and even more preferably 5 to 35 mass %, and particularly preferably 7 to 30 mass %.
The lower limit of the preferred content of General Formula (V-a) is 1%, 2%, 3%, 5%, 7%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% and 55%, based on the total amount of the composition of the present invention. The upper limit of the preferred content is 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30% and 25%, based on the total amount of the composition of the present invention.
The compound represented by General Formula (V-a) in the present invention is preferably a compound selected from the group of compounds represented by General Formula (V-a-1).
In General Formula (V-a-1), R5a and RSb each independently represent an alkyl group having 1 to 5 carbon atoms.
More specifically, the compound represented by General Formula (V-a-1) is preferably any of the following compounds.
Compounds represented by General Formula (5.1), General Formula (5.3) and the formula (5.4) are more preferred.
For producing a high-response liquid crystal display element having a small viscosity, using a larger amount of the formula (5.1) is preferred, but for producing a liquid crystal display element having a high Tni and stable even at high temperatures, increasing the content of the compound represented by the formula (5.3) or the formula (5.4) is preferred.
The compound represented by General Formula (V-a) in the present invention is preferably a compound selected from the group of compounds represented by General Formula (V-a-2).
In General Formula (V-a-2), R5c′ and R5c each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
More specifically, the compound represented by General Formula (V-a-2) is preferably any of the following compounds.
The compound represented by the above formula (5.6) or (5.7) is preferred and the compound represented by the formula (5.7) is more preferred.
The lower limit of the preferred total content of the compounds of General Formula (V-a-2) is 1%, 2%, 3%, 5%, 7%, 10%, 13%, 15%, 18%, 20%, 23%, 25%, 27%, 30%, 33% and 35%, based on the total amount of the composition of the present invention, and the upper limit is 80%, 70%, 60%, 50%, 45%, 40%, 37%, 35%, 33%, 30%, 28%, 25%, 23% and 20%, based on the total amount of the composition of the present invention.
Further, the compound represented by General Formula (V-a) is preferably a compound selected from the group of compounds represented by General Formula (V-a-3).
In General Formula (V-a-3), R5d represents an alkyl group having 1 to 5 carbon atoms, and R5e represents an alkoxy group having 1 to 4 carbon atoms.
More specifically, the compound represented by General Formula (V-a-3) is preferably any of the following compounds.
The compound of the above formula (5.16), the compound of the formula (5.18) and the compound of the formula (5.23) are preferred.
The liquid crystal composition of the present invention may further contain a compound of the formula (5.24) having a structure similar to that of the compound represented by General Formula (V-a).
Further, the compound represented by General Formula (V-a) is preferably a compound selected from the group of compounds represented by General Formula (V-a-4).
In General Formula (V-a-4), RSf and R5g each independently represent an alkenyl group having 2 to 5 carbon atoms.
Further, the compound represented by General Formula (V-a-4) is preferably a compound selected from the group of compounds represented by the formulae (5.25) to (5.34), more preferably a compound represented by the formula (5.26), the formula (5.28) or the formula (5.31).
The lower limit of the preferred content of the compound represented by General Formula (V-b) is 1%, 2%, 3%, 5%, 7% and 10%, based on the total amount of the composition of the present invention. The upper limit of the preferred content is 20%, 15%, 13%, 10%, 8%, 7%, 6%, 5% and 3%, based on the total amount of the composition of the present invention.
Further, the compound represented by General Formula (V-b) is preferably a compound selected from the group of compounds represented by General Formula (V-b-1).
In General Formula (V-b-1), R5h represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, R5i represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
More specifically, the compound represented by General Formula (V-b-1) is preferably any of the following compounds.
The compounds represented by the formula (5.36) and the formula (5.43) are preferred.
Further, the liquid crystal composition of the present invention may contain a compound selected from the group of compounds represented by General Formula (V-b-2) having a structure similar to that of the compound represented by General Formula (V-b-1).
In General Formula (V-b-2), R5j and RSk each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, XS0 each independently represents a fluorine atom or a chlorine atom.
Further, the compound represented by General Formula (V-b-2) is preferably a compound represented by the formula (5.44).
The lower limit of the preferred content of the compound represented by General Formula (V-c) is 1%, 2%, 3%, 5%, 7% and 10%, based on the total amount of the composition of the present invention. The upper limit of the preferred content is 20%, 15%, 13%, 10%, 8%, 7%, 6%, 5% and 3%, based on the total amount of the composition of the present invention.
Further, the compound represented by General Formula (V-c) is preferably a compound selected from the group of compounds represented by General Formula (V-c-1).
In General Formula (V-c-1), R5l and RSm each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
More specifically, the compound represented by General Formula (V-c-1) is preferably any of the following compounds.
Compounds represented by the formula (5.53), the formula (5.54) and the formula (5.58) are preferred.
Further, the composition may contain a compound selected from the group of compounds represented by General Formula (V-c-2) having a structure similar to that of the compound represented by General Formula (V-c-1).
In General Formula (V-c-2), R5n and RSo each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and X51 and X52 each independently represent a fluorine atom or a hydrogen atom, provided that any one of X51 and X52 is a fluorine atom.
Further, the compound represented by General Formula (V-c-2) is preferably a compound represented by the formula (5.59).
The lower limit of the preferred content of the compound represented by General Formula (V-d) is 1%, 2%, 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35% and 40%, based on the total amount of the composition of the present invention. The upper limit of the preferred content of the compound represented by General Formula (V-d) is 50%, 40%, 35%, 30%, 20%, 15%, 10% and 5%, based on the total amount of the composition of the present invention.
Further, the compound represented by General Formula (V-d) is, for example, preferably a compound selected from the group of compounds represented by General Formula (V-d-1).
In General Formula (V-d-1), R5p represents an alkyl group having 1 to 5 carbon atoms, and R5q represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
More specifically, the compound represented by General Formula (V-d-1) is preferably any of the following compounds.
The compound represented by General Formula (V-d-1) is more preferably a compound represented by the formula (5.60).
Further, the compound represented by General Formula (V-d) is, for example, preferably a compound selected from the group of compounds represented by General Formula (V-d-2).
In General Formula (V-d-2), R5r represents an alkyl group having 1 to 5 carbon atoms, and R5s represents an alkoxy group having 1 to 4 carbon atoms.
Further, the compound represented by General Formula (V-d-1) is, for example, preferably any of compounds represented by the formulae (5.62) to (5.65), and among these, the compound represented by the formula (5.65) is more preferred.
The compound represented by General Formula (V-d) in the present invention is, for example, preferably a compound selected from the group of compounds represented by General Formula (V-d-3).
(In General Formula (V-d-3), R5t represents an alkenyl group having 2 to 5 carbon atoms, and R5u represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.)
Further, the compound represented by General Formula (V-d-3) is, for example, preferably any of compounds represented by the formulae (5.66) to (5.68).
The lower limit of the preferred content of the compound represented by General Formula (V-e) is 1%, 2%, 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35% and 40%, based on the total amount of the composition of the present invention. The upper limit of the preferred content of the compound represented by General Formula (V-e) is 50%, 40%, 35%, 30%, 20%, 15%, 10% and 5%, based on the total amount of the composition of the present invention.
The compound represented by General Formula (V-e) in the present invention is preferably a compound selected from the group of compounds represented by General Formula (V-e-1).
In General Formula (V-e-1), R5v and R5w each independently represent an alkenyl group having 2 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
More specifically, the compound represented by General Formula (V-e-1) is preferably any of the following compounds.
The compound represented by General Formula (V-e) in the present invention is more preferably a compound selected from the group of compounds represented by General Formula (V-e-2).
In General Formula (V-e-2), R5x represents an alkenyl group having 2 to 5 carbon atoms, and R5y each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
The compound represented by General Formula (V-e-2) is, for example, preferably a compound represented by the formula (5.72) or the formula (5.73).
The compound represented by General Formula (V-e) in the present invention is preferably a compound selected from the group of compounds represented by General Formula (V-e-3).
In General Formula (V-e-3), Ra1 represents an alkyl having 1 to 5 carbon atoms, and Rb1 represents an alkoxy group having 1 to 4 carbon atoms.
Further, the compound represented by General Formula (V-e-3) is, for example, preferably a compound selected from the group of compounds represented by the formula (5.74) to the formula (5.76), and is especially preferably a compound represented by the formula (5.76).
The lower limit of the preferred content of the compound represented by General Formula (V-f) is 1%, 2%, 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26% and 30%, based on the total amount of the composition of the present invention. The upper limit of the preferred content of the compound represented by General Formula (V-f) is 40%, 35%, 30%, 20%, 15%, 10% and 5%, based on the total amount of the composition of the present invention.
The compound represented by General Formula (V-f) in the present invention is, for example, preferably a compound selected from the group of compounds represented by General Formula (V-f-1).
In General Formula (V-f-1), Rc1 and Rd1 each independently represent an alkenyl group having 2 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
Further, the compound represented by General Formula (V-f-1) is, for example, preferably a compound of the formula (5.77).
The compound represented by General Formula (V-f) in the present invention is, for example, preferably a compound selected from the group of compounds represented by General Formula (V-f-2).
In General Formula (V-f-2), Re1 and Rf1 each independently represent an alkenyl group having 2 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
Further, the compound represented by General Formula (V-f-2) is, for example, preferably a compound represented by any of the formulae (5.78) to (5.82), and is especially preferably a compound represented by the formula (5.79) and/or the formula (5.82).
The compound represented by General Formula (V-f-2) is preferable from the standpoint of the improvement in a transition temperature, but an ester group of three-ring structure is relatively easy to decompose, and is easy to hold ions. Therefore, there is a possibility that the compound is poor in the standpoint of reliability.
The lower limit of the preferred content of the compound represented by General Formula (V-g) is 1%, 2%, 3%, 5%, 7%, 10%, 14%, 16% and 20%, based on the total amount of the composition of the present invention. The upper limit of the preferred content of the compound represented by General Formula (V-g) is 30%, 25%, 23%, 20%, 18%, 15%, 10% and 5%, based on the total amount of the composition of the present invention.
The compound represented by General Formula (V-g) in the present invention is preferably a compound represented by General Formula (V-g-1).
In General Formula (V-g-1), R51 and RS2 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and X51 and X52 each independently represent a fluorine atom or a hydrogen atom.
The compound represented by General Formula (V-g) in the present invention is preferably a compound represented by General Formula (V-g-2).
In General Formula (V-g-2), RS1 and R52 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
Further, the compound represented by General Formula (V-g-2) is preferably a compound of any of the formulae (5.83) to (5.86), and is preferably a compound of the formula (5.84).
Further, the compound represented by General Formula (V-g) is preferably the compound represented by General Formula (V-g-2).
In General Formula (V-g-3), RS1 and R52 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
Further, the compound represented by General Formula (V-g-3) is preferably compounds represented by the formulae (5.87) to (5.89), and more preferably the compound represented by the formula (5.87).
The compound represented by General Formula (V-g) in the present invention is preferably a compound represented by General Formula (V-g-4).
In General Formula (V-g-4), RS1 and R52 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
Further, the compound represented by General Formula (V-g-4) is compounds represented by the formulae (5.85) to (5.87), and preferably the compound represented by the formula (5.85).
The compound represented by General Formula (V-g) of the present invention is preferably a compound represented by General Formula (V-g-5).
In General Formula (V-g-5), RS1 and R52 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and X51 and X52 each independently represent a fluorine atom or a hydrogen atom.
The compound represented by General Formula (V-g) in the present invention is preferably a compound represented by General Formula (V-g-6).
In General Formula (V-g-6), RS1 and R52 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
Further, the compound represented by General Formula (V-g-6) is preferably compounds represented by the formulae (5.88) to (5.4), and more preferably compounds represented by the formula (5.88) and/or the formula (5.91).
The compound represented by General Formula (V-g) in the present invention is preferably a compound represented by General Formula (V-g-7).
In General Formula (V-g-7), R51 and RS2 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
Further, the compound represented by General Formula (V-g-7) is preferably compounds represented by the formulae (5.92) to (5.95), and more preferably compounds represented by the formula (5.92) and/or the formula (5.93).
The compound represented by General Formula (V-g) in the present invention is preferably a compound represented by General Formula (V-g-9).
In General Formula (V-g-9), R51 and RS2 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and XS1 to XS6 each independently represent a fluorine atom or a hydrogen atom.
Further, in General Formula (V-g-9), with respect to each of the combinations of X51 and X52, X53 and X54, and X55 and X56, it is preferred that at least one of the two groups is a fluorine atom.
The lower limit of the preferred content of the compound of General Formula (V-g-9) is 1%, 2%, 3%, 5% and 7%, based on the total amount of the composition of the present invention. The upper limit of the preferred content of those compounds is 25%, 20%, 15%, 13%, 10% and 9%.
The compound represented by General Formula (V-g) in the present invention is preferably compounds represented by General Formulas (V-g-10) to (V-g-13).
In General Formulas (V-g-10) to (V-g-13), R51 and R52 each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
The lower limit of the preferred content of the compound of General Formula (V-g-10) is 1%, 2%, 3%, 5% and 7%, based on the total amount of the composition of the present invention. The upper limit of the preferred content of those compounds is 25%, 20%, 15%, 13%, 10% and 9%.
Further, the compound represented by General Formula (V-g) is preferably a compound represented by General Formula (V-g-10). Preferred examples of the compound represented by General Formula (V-g-10) are compounds of the following formulae (5.100) to (5.116).
The lower limit of the content of the third component represented by General Formulas (V-a) to (V-g) is preferably 20 mass %, 25 mass %, 30 mass %, 35 mass %, 40 mass %, 45 mass % and 50 mass %, in this order. Further, the upper limit of the content of the third component represented by General Formulas (V-a) to (V-g) is preferably 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass % and 30 mass %, in this order.
The particularly preferred embodiment of the third component of the present invention is that in the compounds represented by General Formulas (5.100) to (5.108) and the formulae (5.109) to (5.114), one to three different kinds of compounds are mixed. In such a case, the mass ratio of the whole third component in the present invention is particularly preferably 32 to 40 mass % based on the whole liquid crystal composition.
The liquid crystal composition of the present invention preferably further contains, as the fourth component, at least one selected from the groups of compounds represented by the following General Formula (4):
In General Formula (4), RX1 and RX2 each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and one methylene group or two or more non-adjacent methylene groups existing in these groups may be substituted with —O— or —S—, and one or more hydrogen atoms exiting in these groups may be substituted with a chlorine atom and/or a fluorine atom,
u and v each independently indicate 0, 1 or 2, and u+v is 2 or less,
MX1, MX2 and MX3 each independently represent a group selected from the following (a) and (b):
(a) a trans-1,4-cyclohexylene group (one methylene group or two or more non-adjacent methylene groups existing in this group may be substituted with —O— or —S—),
(b) a 1,4-phenylene group (one —CH═ or two or more non-adjacent (—CH═)'s existing in this group may be substituted with —N═),
the hydrogen atom contained in the group of the above (a) or the above (b) may be substituted with a group selected from a cyano group, a fluorine atom, a trifluoromethyl group and a trifluoromethoxy group, and plural MX2's and/or MX3's, if any, may be the same or different,
LX1, LX2 and LX3 each independently represent a single bond, —COO—, —OCO—, —CH2CH2—, —(CH2)4—, —OCH2—, —CH2O—, —OCF2—, —CF2O—, —CH═CH— or —C≡C—, and plural LX1's and/or LX3 s, if any, may be the same or different, and
XX1 and XX2 each independently represent a trifluoromethyl group, a trifluoromethoxy group or a fluorine atom, provided that any one of XX1 and XX2 represents a fluorine atom, with the proviso that the compounds represented by General Formula (1) to General Formula (4) are excluded.
In the case where the cyclic structure bonding thereto is a phenyl group (aromatic), Rx1 and Rx2 each are preferably a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 (or more) carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, more preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 (or more) carbon atoms, or an alkenyl group having 4 to 5 carbon atoms. On the other hand where the cyclic structure bonding thereto is a cyclohexane, a pyran, a dioxane or the like saturated cyclic structure, Rx1 and Rx2 each are preferably a linear or branched alkyl group having 1 to 10 carbon atoms, a linear alkoxy group having 1 to 10 (or more) carbon atoms, or a linear alkenyl group having 2 to 10 carbon atoms, more preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 (or more) carbon atoms, or a linear alkenyl group having 2 to 5 carbon atoms.
In the case where improving the response speed of a display element is considered to be important, an alkenyl group is preferred in General Formula (4) in the present invention, but where reliability such as a voltage holding ratio or the like is considered to be important, an alkyl group is preferred.
The alkyl group and alkoxy group in General Formula (4) are preferably the same alkyl group and/or alkoxy group as in the first to third components. Further, the alkenyl group in General Formula (4) is preferably the same alkenyl group as in the third component, and more preferably the above formulae (i) to (iv).
Addition of the compound represented by General Formula (4) to the liquid crystal composition is particularly preferred in the standpoint that it changes a driving voltage of a liquid crystal display element.
The content of the fourth component in the liquid crystal composition of the present invention is appropriately selected by not only use embodiment and use purpose of a liquid crystal composition, but the relationship with other components, similar to the above-described first component and second component that are essential components. Therefore, the preferred range of the content of the fourth component contained in the liquid crystal composition is preferably individually independent depending on the embodiments, respectively.
In the liquid crystal composition of the present invention, the lower limit of the content of the fourth component is, as one embodiment of the present invention, for example, preferably 1 mass % based on the total amount (100 mass %) of the liquid crystal composition of the present invention. Alternatively, in another embodiment of the present invention, the lower limit is preferably 10 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 20 mass %. In another embodiment of the present invention, the lower limit is preferably 30 mass %. In another embodiment of the present invention, the lower limit is preferably 40 mass %. In another embodiment of the present invention, the lower limit is preferably 50 mass %. In another embodiment of the present invention, the lower limit is preferably 55 mass %. In another embodiment of the present invention, the lower limit is preferably 60 mass %. In another embodiment of the present invention, the lower limit is preferably 65 mass %. In another embodiment of the present invention, the lower limit is preferably 70 mass %. In another embodiment of the present invention, the lower limit is preferably 75 mass %. In another embodiment of the present invention, the lower limit is preferably 80 mass %.
Further, in the liquid crystal composition of the present invention, the upper limit of the content of the fourth component is, as one embodiment of the present invention, for example, preferably 95 mass % based on the total amount (100 mass %) of the liquid crystal composition of the present invention. Further, in another embodiment of the present invention, the upper limit is preferably 85 mass %. In another embodiment of the present invention, the upper limit is preferably 75 mass %. In another embodiment of the present invention, the upper limit is preferably 65 mass %. In another embodiment of the present invention, the upper limit is preferably 55 mass %. In another embodiment of the present invention, the upper limit is preferably 45 mass %. In another embodiment of the present invention, the upper limit is preferably 35 mass %. In another embodiment of the present invention, the upper limit is preferably 25 mass %.
In the liquid crystal composition of the present invention, the content of the compound represented by General Formula (4) is required to be appropriately adjusted depending on required performances such as solubility at low temperature, a transition temperature, electrical reliability, a birefringence, process adaptability and drop marks described hereinunder, burn-in and dielectric anisotropy.
In the case where a liquid crystal composition maintaining a viscosity of the liquid crystal composition of the present invention low and having high response speed is required, it is preferred that the lower limit is high and the upper limit is high. Further, in the case where a liquid crystal composition maintaining Tni of the liquid crystal composition of the present invention high and having good temperature stability is required, it is preferred that the lower limit is high and the upper limit is high. When dielectric anisotropy is desired to be increased in order to maintain driving voltage low, it is preferred that the lower limit is low and the upper limit is low.
In the fourth component in the present invention, kinds that can combine the compounds represented by General Formula (4) with each other are not particularly limited, and are used by appropriately combining those depending on desired performances such as solubility at low temperature, a transition temperature, electrical reliability and a birefringence. For example, as one embodiment of the present invention, the kind of the compound of General Formula (4) used as the fourth component is that the fourth component is one kind of the compound represented by General Formula (4). Alternatively, in another embodiment of the present invention, the fourth component is two kinds of the compounds represented by General Formula (4). Further, in another embodiment of the present invention, the fourth component is three kinds of the compounds represented by General Formula (4). In another embodiment of the present invention, the fourth component is four kinds of the compounds represented by General Formula (4). In another embodiment of the present invention, the fourth component is five kinds of the compounds represented by General Formula (4). In another embodiment of the present invention, the fourth component is six kinds of the compounds represented by General Formula (4). In another embodiment of the present invention, the fourth component is seven kinds of the compounds represented by General Formula (4). In another embodiment of the present invention, the fourth component is eight kinds of the compounds represented by General Formula (4). In another embodiment of the present invention, the fourth component is nine kinds of the compounds represented by General Formula (4). In another embodiment of the present invention, the fourth component is a system containing ten or more kinds of the compounds represented by General Formula (4).
The total content of the compounds represented by General Formulas (1), (2) and (4) contained in the liquid crystal composition of the present invention is that as the lower limit, 16 mass % is preferable, 18 mass % is preferable, 20 mass % is preferable, 23 mass % is preferable, 25 mass % is preferable, 28 mass % is preferable, 30 mass % is preferable, 32 mass % is preferable, 35 mass % is preferable, 38 mass % is preferable, 40 mass % is preferable, 42 mass % is preferable, 45 mass % is preferable, 47 mass % is preferable, and 50 mass % is preferable. As the upper limit, 35 mass % is preferable, 38 mass % is preferable, 40 mass % is preferable, 42 mass % is preferable, 45 mass % is preferable, 47 mass % is preferable, 50 mass % is preferable, 53 mass % is preferable, 55 mass % is preferable, 57 mass % is preferable, 60 mass % is preferable, 62 mass % is preferable, 65 mass % is preferable, 68 mass % is preferable, 70 mass % is preferable, 72 mass % is preferable, 75 mass % is preferable, 78 mass % is preferable, 80 mass % is preferable, 82 mass % is preferable, 85 mass % is preferable, 88 mass % is preferable, and 90 mass % is preferable.
The lower limit of the dielectric anisotropy (Δ∈) of the compound represented by General Formula (4) of the present invention is −20 in one embodiment, and −15 in another embodiment. Further, the value is −13 in another embodiment, and −12 in still another embodiment. Further, the value is −10 in other embodiment, and −8 in still another embodiment. On the other hand, the upper limit of the dielectric anisotropy (Δ∈) of a liquid crystal composition including the compound represented by General Formula (4) is 0 in one embodiment, and −1 in other embodiment. Further, the upper limit is −2 in another embodiment, and −3 in still another embodiment. Further, the upper limit is −4 in another embodiment, and −5 in still another embodiment.
The compound represented by General Formula (4) in the present invention is preferably at least one kind selected from the group of the compounds represented by General Formulas (VI-a), (VI-b), (VI-c) and (VI-e):
In General Formula (VI-a), R6a and R6b each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, at least one hydrogen atom in the alkyl group, alkenyl group, alkoxy group and/or alkenyloxy group may be substituted with a fluorine atom, and a methylene group in the alkyl group, alkenyl group, alkoxy group and/or alkenyloxy group may be substituted with an oxygen atom so long as the oxygen atom does not continuously bond, and may be substituted with a carbonyl group so long as the carbonyl group does not continuously bond.
A1 represents a 1,4-phenylene group or a tetrahydropyran-2,5-diyl group, and when A1 represents a 1,4-phenylene group, at least one hydrogen atom in the 1,4-phenylene group may be substituted with a fluorine atom.
In General Formula (VI-b), R6c and R6d each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, at least one hydrogen atom in the alkyl group, alkenyl group, alkoxy group and/or alkenyloxy group may be substituted with a fluorine atom, and a methylene group in the alkyl group, alkenyl group, alkoxy group and/or alkenyloxy group may be substituted with an oxygen atom so long as the oxygen atom does not continuously bond, or may be substituted with a carbonyl group so long as the carbonyl group does not continuously bond.
In General Formula (VI-c), R6e and R6f each independently represent an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms or an alkoxy group having 1 to 15 carbon atoms.
In General Formula (VI-d), R6g and R6h each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, at least one hydrogen atom in the alkyl group, alkenyl group, alkoxy group and/or alkenyloxy group may be substituted with a fluorine atom, and a methylene group in the alkyl group, alkenyl group, alkoxy group and/or alkenyloxy group may be substituted with an oxygen atom so long as the oxygen atom does not continuously bond, or may be substituted with a carbonyl group so long as the carbonyl group does not continuously bond.
A2 represents a 1,4-cyclohexylene group, a 1,4-phenylene group or a tetrahydropyran-2,5-diyl group, and when A represents a 1,4-phenylene group, at least one hydrogen atom in the 1,4-phenylene group may be substituted with a fluorine atom,
Z1 represents a single bond, —OCH2—, —OCF2—, —CH2O— or CF2O—,
n is 0 or 1, and
X61 to X66 each independently represents a hydrogen atom or a fluorine atom, and at least two of X61 to X66 represent a fluorine atom.
In General Formula (VI-e), R6i and R6j each independently represent an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms or an alkoxy group having 1 to 15 carbon atoms.
The compounds represented by General Formulas (VI-a) to (VI-e) are described in detail hereinunder.
The compound represented by General Formula (4) in the present invention is preferably a compound represented by General Formula (VI-a).
In General Formula (VI-a), R6a and R6b each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, and one or more hydrogen atoms in the alkyl group, the alkenyl group, the alkoxy group and/or the alkenyloxy group may be substituted with a fluorine atom, and the methylene group in the alkyl group, the alkenyl group, the alkoxy group and/or the alkenyloxy group may be substituted with an oxygen atom so far as oxygen atoms do not bond continuously, and may be substituted with a carbonyl group so far as carbonyl groups do not bond continuously, and
A1 represents a 1,4-cyclohexylene group, a 1,4-phenylene group or a tetrahydropyrane-2,5-diyl group, and when A1 represents a 1,4-phenylene group, one or more hydrogen atoms in the 1,4-phenylene group may be substituted with a fluorine atom.
In General Formula (VI-a), R6a is preferably an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, even more preferably an alkyl group having 1 to 8 carbon atoms, and further more preferably an alkyl group having 3 to 5 carbon atoms.
In General Formula (VI-a), R6b is preferably an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, even more preferably an alkyl group having 3 to 5 carbon atoms or an alkoxy group having 2 to 4 carbon atoms, and further more preferably an alkyl group having 3 or 5 carbon atoms or an alkoxy group having 2 or 4 carbon atoms.
In General Formula (VI-a), A1 represents a 1,4-cyclohexylene group, a 1,4-phenylene group or a tetrahydropyrane-2,5-diyl group, and when A1 is a 1,4-phenylene group, one or more hydrogen atoms in the 1,4-phenylene group may be substituted with a fluorine atom, but A1 is preferably a 1,4-cyclohexylene group or a 1,4-phenylene group. More specifically, in the liquid crystal element and the liquid crystal display produced using the liquid crystal composition of the present invention, when the response speed is considered to be important, A1 is preferably a 1,4-phenylene group, but when the operation temperature range is considered to be important, that is, the element and the display require a high operation temperature range (high Tni), A1 is preferably a 1,4-cyclohexylene group. In the case where A1 is a 1,4-phenylene group, one or more hydrogen atoms in the benzene ring may be substituted with a fluorine atom, but preferably the group is unsubstituted or mono-substituted or di-substituted. More preferably, the group is unsubstituted. As the di-substituted group, a 2,3-difluoro-1,4-phenylene group is preferred.
Specifically, the compound represented by General Formula (VI-a) is preferably a compound selected from the group of the following General Formula (VI-a-1).
In General Formula (VI-a-1), R6a and R6b each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, and one or more hydrogen atoms in the alkyl group, the alkenyl group, the alkoxy group and/or the alkenyloxy group may be substituted with a fluorine atom, and the methylene group in the alkyl group, the alkenyl group, the alkoxy group and/or the alkenyloxy group may be substituted with an oxygen atom so far as oxygen atoms do not bond continuously, and may be substituted with a carbonyl group so far as carbonyl groups do not bond continuously.
More preferably, R6a and R6b each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms, and in the case where R6a and R6b each are an alkenyl group, the carbon number thereof is preferably 4 to 5.
The lower limit of the preferred content of the compound represented by General Formula (VI-a) is 3%, 5%, 7%, 10%, 13%, 15%, 17% and 20%, based on the total amount of the composition of the present invention. The upper limit of the preferred content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 11%, 10% and 8%, based on the total amount of the composition of the present invention.
Specifically the compound represented by General Formula (VI-a) in the present invention is preferably compounds represented by the following formulae (6.13) to (6.21):
but the compounds represented by the formulae (6.13) to (6.20) are more preferred, and the compounds represented by the formulae (6.13) to 6.15) and the formulae (6.19) to (6.21) are even more preferred.
In the case where the compound represented by General Formula (VI-a) in the present invention has an alkenyl group, specifically, a compound selected from the group of the following formulae (6.22) to (6.27) is preferred:
In the above formulae, R6b each independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
The compound represented by the formula (4) in the present invention is preferably a compound selected from the group of General Formula (VI-b).
In General Formula (VI-b), R6c and R6d each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, one or more hydrogen atoms in the alkyl group, the alkenyl group, the alkoxy group and/or the alkenyloxy group may be substituted with a fluorine atom, and a methylene group in the alkyl group, the alkenyl group, the alkoxy group and/or the alkenyloxy group may be substituted with an oxygen atom so long as the oxygen atom does not bond continuously, or may be substituted with a carbonyl group so long as the carbonyl group does not bond continuously.
In General Formula (VI-b), R6c represents preferably an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, even more preferably an alkyl group having 1 to 8 carbon atoms, and further more preferably an alkyl group having 3 to 5 carbon atoms.
In General Formula (VI-b), R6d represents preferably an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, even more preferably an alkyl group having 3 to 5 carbon atoms or an alkoxy group having 2 to 4 carbon atoms, and further more preferably an alkyl group having 3 or 5 carbon atoms or an alkoxy group having 2 or 4 carbon atoms.
The lower limit of the preferred content of the compound represented by General Formula (VI-b) is 5%, 7%, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 37%, 40% and 42%, based on the total amount of the composition of the present invention. The upper limit of the preferred content is 50%, 48%, 45%, 43%, 40%, 38%, 35%, 33%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% and 5%, based on the total amount of the composition of the present invention.
Specifically the compound represented by General Formula (VI-b) is preferably compounds represented by the following formulae (6.28) to (6.35):
but the compounds represented by the formulae (6.28) to (6.29) and the formulae (6.31) to (6.35) are more preferred.
In the case where the compound represented by General Formula (VI-b) in the present invention has an alkenyl group, specifically, compounds represented by the following formulae (6.36) to (6.39) are preferred:
In the above formulae, R6d represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
The compound represented by the formula (4) in the present invention is preferably a compound represented by General Formula (VI-c).
In General Formula (VI-c), R6e and R6f each independently represent an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms or an alkoxy group having 1 to 15 carbon atoms.
In the compound represented by General Formula (VI-c), more preferably, R6e is an alkyl group having 1 to 10 carbon atoms and R6f is an alkoxy group having 1 to 10 carbon atoms, and particularly preferably, R6e is an alkyl group having 1 to 5 carbon atoms and R6f is an alkoxy group having 1 to 5 carbon atoms.
The lower limit of the preferred content of the compound represented by General Formula (VI-c) is 5%, 10%, 13%, 15%, 17% and 20%, based on the total amount of the composition of the present invention. The upper limit of the preferred content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15% and 13%, based on the total amount of the composition of the present invention.
Further, as the compound represented by General Formula (VI-c) in the present invention, a compound selected from the group of the following formulae (6.40) to (6.45):
is preferable.
The compound represented by General Formula (4) in the present invention is preferably a compound represented by General Formula (VI-d).
(In General Formula (VI-d), R6g and R6h each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, and one or more hydrogen atoms in the alkyl group, the alkenyl group, the alkoxy group and/or the alkenyloxy group may be substituted with a fluorine atom, and the methylene group in the alkyl group, the alkenyl group, the alkoxy group and/or the alkenyloxy group may be substituted with an oxygen atom so far as oxygen atoms do not bond continuously, and may be substituted with a carbonyl group so far as carbonyl groups do not bond continuously,
A2 represents a 1,4-cyclohexylene group, a 1,4-phenylene group or a tetrahydropyrane-2,5-diyl group, and when A2 is a 1,4-phenylene group, one or more hydrogen atoms in the 1,4-phenylene group may be substituted with a fluorine atom,
Z1 represents a single bond, —OCH2—, —OCF2—, —CH2O—, or CF2O—,
n indicates 0 or 1, and
X61 to X66 each independently represent a hydrogen atom or a fluorine atom, provided that at least two of X61 to X66 are fluorine atoms.)
The 1,4-cyclohexyl group in the present application is preferably a trans-1,4-cyclohexyl group.
In the case where the liquid crystal composition of the present invention contains a compound represented by General Formula (2) as the second component and where the compound represented by General Formula (VI-d) is the same as the compound represented by General Formula (2), preferably, the compound represented by General Formula (VI-d) is not contained in the fourth component.
In General Formula (VI-d), R6g preferably represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, even more preferably an alkyl group having 1 to 8 carbon atoms, and further more preferably an alkyl group having 3 to 5 carbon atoms.
In General Formula (VI-d), R6h preferably represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, even more preferably an alkyl group having 3 to 5 carbon atoms or an alkoxy group having 2 to 4 carbon atoms, further more preferably an alkyl group having 3 or 5 carbon atoms. Also preferably, Re and Rf differ from each other in point of the number of carbon atoms.
In General Formula (VI-d), preferably, X61 to X66 each are independently a hydrogen atom or a fluorine atom, and preferably, two to five of them are fluorine atoms, more preferably two to four are fluorine atoms, even more preferably, two to three are fluorine atoms, further more preferably two are fluorine atoms, and most preferably two are fluorine atoms.
In this case, when the formula has one fluorine atom, preferably any two of X63 to X66 are fluorine atoms, more preferably X63 or X64 is a fluorine atom. When the formula has two fluorine atoms, preferably any two of X63 to X66 are fluorine atoms, more preferably X63 and X64 are fluorine atoms or X65 and X66 are fluorine atoms, and even more preferably X63 and X64 are fluorine atoms. When the formula has three or more fluorine atoms, preferably at least X63 and X64 are fluorine atoms or at least X65 and X66 are fluorine atoms, and even more preferably at least X63 and X64 are fluorine atoms.
In General Formula (VI-d), A2 is preferably a 1,4-cyclohexylene group, a 1,4-phenylene group or a tetrahydropyrane-2,5-diyl group, and in the case where response speed is considered to be important for display elements and liquid crystal displays produced using the liquid crystal composition, the group is preferably a 1,4-phenylene group or a tetrahydropyrane-2,5-diyl group, and more preferably a 1,4-phenylene group. In the case where a driving voltage is considered to be important, the group is preferably a 1,4-phenylene group or a tetrahydropyrane-2,5-diyl group, and more preferably a tetrahydropyrane-2, 5-diyl group. In the case where an operation temperature range is considered to be important, that is, where a high operation temperature range is needed, the group is preferably a 1,4-cyclohexylene group or a tetrahydropyrane-2,5-diyl group, and more preferably a 1,4-cycloyexylene group. When the group is a 1,4-phenylene group, one or more hydrogen atoms in the benzene ring may be substituted with a fluorine atom, and the group is preferably unsubstituted, monosubstituted or disubstituted, and when it is disubstituted, the group is preferably 2,3-difluorobenzene.
In General Formula (VI-d), Z1 represents a single bond, —OCH2—, —OCF2—, —CH2O—, or —CF2O—, and is preferably a single bond, —OCF2— or —CF2O—, more preferably a single bond.
In General Formula (VI-c), n indicates 0 or 1, and in the case where rapid response is considered to be important, n is preferably 0, but where an operation temperature range is considered to be important, that is, where a high operation temperature range is needed, n is preferably 1.
In General Formulas (VI-a) to (VI-d), R6a to R6h correspond to RX1 and RX2 in General Formula (4), and therefore it is needless to say that the alkyl group, the alkenyl group, the alkoxy group and the alkenyloxy group each are preferably linear or branched and more preferably linear.
The lower limit of the preferred content of the compound represented by General Formula (VI-d) is 5%, 8%, 10%, 13%, 15%, 17% and 20%, based on the total amount of the composition of the present invention. The upper limit of the preferred content is 35%, 33%, 30%, 28%, 25%, 23%, 20%, 18%, 15% and 13%, based on the total amount of the composition of the present invention.
Specifically, the compound represented by General Formula (VI-d) in the present invention is preferably any of compounds represented by the following General Formulas (VI-d-1) to (VI-d-12):
In the above formulae, R6g has the same meaning as that of R6g in General Formula (VI-d), and R6h has the same meaning as that of R6h in General Formula (VI-d).
The General Formula (VI-d-1), General Formulas (VI-d-3) to (VI-d-9) and General Formulas (VI-d-12) to (VI-d-15) are more preferred, General Formula (VI-d-1), General Formula (VI-d-3), General Formula (VI-d-5), General Formula (VI-d-6), General Formula (VI-d-9), General Formula (VI-d-12), General Formula (VI-d-13) and General Formula (VI-d-15) are even more preferred, General Formula (VI-d-1), General Formula (VI-d-5) and General Formula (VI-d-6) are especially preferred, and General Formula (VI-d-5) is most preferred.
In General Formula (VI-d) (including General Formulas (VI-d-1) to (VI-d-12)) in the present invention, R6g and R6h each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, more preferably an alkyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms, most preferably an alkyl group having 2 to 5 carbon atoms, and these groups are preferably linear. In the case where R6g and R6h are both alkyl groups, preferably, they differ from each other in point of the number of carbon atoms.
More precisely, the compound where R6g is a propyl group and R6h is an ethyl group, or the compound where R6g is a butyl group and R6h is an ethyl group is preferred.
Specifically, the compound represented by General Formula (VI-d-1) in the present invention is preferably any of compounds of the formulae (6.46) to (6.57).
Of the compound represented by General Formula (4) in the present invention, a compound selected from the group of the compounds represented by the formulae (VI-d-1) and (VI-d-2) and the compounds represented by the formulae (6.46), (6.47), (6.48), (6.49) and (6.50) are more preferred.
The particularly preferred embodiment of the fourth component in the present invention is that 1 to 3 kinds of different compounds in compounds selected from the group of the compounds represented by the formulae (VI-d-1) and (VI-d-2) and the compounds represented by the formulae (6.46), (6.47), (6.48), (6.49) and (6.50) are mixed. Further, in such a case, a mass ratio of the whole fourth component in the present invention is particularly preferably 20 to 32 mass % based on the whole liquid crystal composition.
The compound represented by General Formula (4) in the present invention is preferably the compound represented by General Formula (VI-e).
In General Formula (VI-e), R6i and R6j each independently represent an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms or an alkoxy group having 1 to 15 carbon atoms.
In General Formula (VI-e) in the present invention, R6i represents preferably an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, even more preferably an alkyl group having 1 to 8 carbon atoms, and further more preferably an alkyl group having 3 to 5 carbon atoms.
In General Formula (VI-e), R6j represents preferably an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, even more preferably an alkyl group having 3 to 5 carbon atoms or an alkoxy group having 2 to 4 carbon atoms, and further more preferably an alkyl group having 3 or 5 carbon atoms.
When the liquid crystal composition contains the compound represented by General Formula (VI-e), an absolute value of dielectric anisotropy is increased, and as a result, the effect of enabling low voltage driving is exhibited. Further, when the compound represented by General Formula (VI-e) is combined with the compound (Z0═—CH2O—) of General Formula (2), an absolute value of dielectric anisotropy is further increased, and as a result, the effect of enabling low voltage driving is exhibited.
The lower limit of the preferred content of the compound represented by General Formula (VI-e) is 5%, 10%, 13%, 15%, 17% and 20%, based on the total amount of the composition of the present invention. The upper limit of the preferred content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15% and 13%, based on the total amount of the composition of the present invention.
Specifically, the compound represented by General Formula (VI-e) in the present invention is preferably the compounds represented by the formulae (9.1) to (9.8).
The total content of the compounds represented by General Formulas (1), (2) and (VI-e) contained in the liquid crystal composition is that, as the lower limit, 10 mass % is preferable, 12 mass % is preferable, 15 mass % is preferable, 18 mass % is preferable, 20 mass % is preferable, 22 mass % is preferable, 26 mass % is preferable, 28 mass % is preferable, and 30 mass % is preferable. As the upper limit, 60 mass % is preferable, 55 mass % is preferable, 50 mass % is preferable, 45 mass % is preferable, 40 mass % is preferable, 36 mass % is preferable, 33 mass % is preferable, 32 mass % is preferable, and 30 mass % is preferable.
The liquid crystal composition of the present invention may further contain, as a fifth component, at least one kind of the compounds represented by the following General Formulas (6a) and (6b).
In General Formula (6a), R31 and R32 each independently represent a straight chain alkyl group having 1 to 10 carbon atoms, a straight chain alkoxy group having 1 to 10 carbon atoms or a straight chain alkenyl group having 2 to 10 carbon atoms.
In General Formula (6b), R41 and R42 each independently represent a straight chain alkyl group having 1 to 10 carbon atoms, a straight chain alkoxy group having 1 to 10 carbon atoms or a straight chain alkenyl group having 4 to 10 carbon atoms.
Addition of the compounds represented by General Formulas (6a) and (6b) to the liquid crystal composition is particularly preferred from the standpoint that a liquid crystal composition having low viscosity is particularly obtained.
The content of the fifth component in the liquid crystal composition of the present invention is appropriately selected by not only use embodiment and use purpose of a liquid crystal composition, but the relationship with other components, similar to the above-described first component and second component that are essential components. Therefore, the preferred range of the content of the fourth component contained in the liquid crystal composition is preferably individually independent depending on the respective embodiments.
In the liquid crystal composition of the present invention, the lower limit of the content of the fifth component is, for example, as one embodiment of the present invention, preferably 1 mass % based on the total amount (100 mass %) of the liquid crystal composition of the present invention. Alternatively, in another embodiment of the present invention, the lower limit is preferably 10 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 20 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 30 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 40 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 50 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 55 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 60 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 65 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 70 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 75 mass %. Further, in another embodiment of the present invention, the lower limit is preferably 80 mass %.
In the liquid crystal composition of the present invention, the upper limit of the content of the fifth component is, for example, in one embodiment of the present invention, preferably 95 mass % based on the total amount (100 mass %) of the liquid crystal composition of the present invention. Further, in another embodiment of the present invention, the upper limit is preferably 85 mass %. Further, in another embodiment of the present invention, the upper limit is preferably 75 mass %. Further, in another embodiment of the present invention, the upper limit is preferably 65 mass %. Further, in another embodiment of the present invention, the upper limit is preferably 55 mass %. Further, in another embodiment of the present invention, the upper limit is preferably 45 mass %. Further, in another embodiment of the present invention, the upper limit is preferably 35 mass %. Further, in another embodiment of the present invention, the upper limit is preferably 25 mass %.
In the liquid crystal composition of the present invention, the content of the compound represented by General Formula (6a) or (6b) must be appropriately adjusted depending on required performances such as solubility at low temperature, a transition temperature, electrical reliability, a birefringence, process adaptability and drop marks described hereinunder, burn-in and dielectric anisotropy.
In the case where a liquid crystal composition maintaining a viscosity of the liquid crystal composition of the present invention low and having high response speed is required, it is preferred that the lower limit is high and the upper limit is high. Further, in the case where a liquid crystal composition maintaining Tni of the liquid crystal composition of the present invention high and having good temperature stability is required, it is preferred that the lower limit is high and the upper limit is high. Further, when dielectric anisotropy is required to be increased in order to maintain driving voltage low, it is preferred that the lower limit is low and the upper limit is low.
In the fifth component of the present invention, kinds that can combine the compounds represented by General Formula (6a) or (6b) with each other are not particularly limited, and are used by appropriately combining those depending on desired performances such as solubility at low temperature, a transition temperature, electrical reliability and a birefringence. For example, as one embodiment of the present invention, the kind of the compound of General Formula (6a) or (6b) used as the fifth component is that the fifth component is one kind of the compound represented by General Formula (6a) or (6b). Alternatively, in other embodiment of the present invention, the fifth component is two kinds of the compounds represented by General Formula (6a) or (6b). Further, in other embodiment of the present invention, the fifth component is three kinds of the compounds represented by General Formula (6a) or (6b). In other embodiment of the present invention, the fifth component is four kinds of the compounds represented by General Formula (6a) or (6b). In other embodiment of the present invention, the fifth component is five kinds of the compounds represented by General Formula (6a) or (6b). In other embodiment of the present invention, the fifth component is six kinds of the compounds represented by General Formula (6a) or (6b). In other embodiment of the present invention, the fifth component is seven kinds of the compounds represented by General Formula (6a) or (6b). In other embodiment of the present invention, the fifth component is eight kinds of the compounds represented by General Formula (6a) or (6b). In other embodiment of the present invention, the fifth component is nine kinds of the compounds represented by General Formula (6a) or (6b). In other embodiment of the present invention, the fifth component is a system containing ten or more kinds of the compounds represented by General Formula (6a) or (6b).
The lower limit of the dielectric anisotropy (Δ∈) of the compound represented by General Formula (6a) or General Formula (6b) in the present invention is −1 in one embodiment, and −0.9 in another embodiment. In still another embodiment, the value is −0.8, and further in still another embodiment, it is −0.7. In still another embodiment, the value is −0.5, and further in still another embodiment, it is −0.4. On the other hand, the upper limit of the dielectric anisotropy (Δ∈) of the compound represented by General Formula (6a) or General Formula (6b) in the present invention is +1 in one embodiment, and +0.9 in another embodiment. In still another embodiment, the value is +0.8, further in still another embodiment, it is +0.7, further in still another embodiment, it is +0.6, and further in still another embodiment, it is +0.5.
Specifically, the compound represented by General Formula (6a) in the present invention is preferably any of compounds represented by the following formulae (7.1) to (7.60).
The compound represented by General Formula (6b) in the present invention is preferably at least one selected from the group of the formulae (7.71) to (7.85).
Among the compounds represented by General Formulas (6a) and (6b) in the present invention, the compounds of the formulae (7.71) to (7.85) are more preferred.
The total content of the compounds represented by General Formulas (1), (2), (3) and (4) contained in the liquid crystal composition of the present invention is that, as the lower limit, 60 mass % is preferable, 65 mass % is preferable, 70 mass % is preferable, 72 mass % is preferable, 75 mass % is preferable, 77 mass % is preferable, 80 mass % is preferable, 82 mass % is preferable, 85 mass % is preferable, 87 mass % is preferable, 90 mass % is preferable, 92 mass % is preferable, 95 mass % is preferable, 98 mass % is preferable, and 99 mass % is preferable. As the upper limit, 100 mass % is preferable, 99.5 mass % is preferable, 99 mass % is preferable, 98 mass % is preferable, 98 mass % is preferable, 97 mass % is preferable, and 95 mass % is preferable.
The liquid crystal composition of the present invention may contain other components such as general nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, a chiral agent, an antioxidant, an ultraviolet absorber and a polymerizable monomer depending on the use purpose, other than the compounds represented by the above first to fifth components. Of those other components, an antioxidant and an ultraviolet absorber are not particularly limited, and the conventional compounds can be used.
In the case where stability and reliability by UV irradiation are considered to be important in the liquid crystal composition of the present invention, the content of a compound having a chlorine atom as a substituent is preferably 15 mass % or less, more preferably 10 mass % or less, even more preferably 5 mass % or less, and most preferably the embodiment that the compound is not substantially contained, based on the total mass of the composition.
In the liquid crystal composition of the present invention, it is preferred to increase the content of a compound in which a ring structure in the molecule is all a single 6-membered ring. The content of the compound in which a ring structure in the molecular is all a single 6-membered ring is preferably 80 mass % or more, more preferably 90 mass % or more, even more preferably 95 mass % or more, and most preferably the embodiment that a liquid crystal composition is constituted of only a compound in which a ring structure in the molecular is substantially all a single 6-membered ring, based on the total mass of the composition.
In the liquid crystal composition of the present invention, to suppress deterioration of the liquid crystal composition by oxidation, it is preferred to decrease the content of a compound having a cyclohexenylene group as a ring structure. The content of the compound having a cyclohexenylene group is preferably 10 mass % or less, more preferably 5 mass % or less, and even more preferably the embodiment that the compound is not substantially contained, based on the total mass of the composition.
In the liquid crystal composition of the present invention, in the case of considering the improvement of a viscosity and the improvement of Tni to be important, it is preferred to decrease the content of a compound having a 2-methylbenzene-1,4-diyl group in which a hydrogen atom may be substituted with a halogen, in the molecule. The content of the compound having a 2-methylbenzene-1,4-diyl group in the molecule is preferably 10 mass % or less, more preferably 5 mass % or less, and even more preferably the embodiment that the compound is not substantially contained, based on the total mass of the composition.
Due to expansion of the use of a liquid crystal display element in recent years, great change is appeared in its use method and production method, and to respond to those, optimization has been required in characteristics other than the basic physical properties conventionally known. Specifically, a liquid crystal display element using a liquid crystal composition is that VA type, IPS type and the like are widely used, and regarding its size, a display element having an extra-large screen of 50 inches or more has become to be used. Due to enlargement of a substrate size, an injection method of a liquid crystal composition into a substrate is that a drop injection (ODF: One drop fill) method becomes a mainstream in place of the conventional vacuum injection method (see JP-A 6-235925), and the problem that drop marks when a liquid crystal composition has dropped on a substrate cause the deterioration of display quality has become to be revealed. Further, for the purpose of high speed responsiveness of formation of a pretilt angle of a liquid crystal material in a liquid crystal display element, a PS liquid crystal display element (polymer stabilized) and a PSA liquid crystal display element (polymer sustained alignment) are developed (see JP-A 2002-357830), and the problem of drop marks is becoming large problem. Specifically, the PS or PSA display element is characterized by adding a monomer to a liquid crystal composition and hardening the monomer in the composition. In a liquid crystal composition for active matrix, a usable compound is specified from the necessity of sustaining high voltage holding ratio, and use of a compound having an ester bond therein is restricted. A monomer used in a PSA liquid crystal display element is mainly an acrylate type, and it is general to contain an ester bond in a compound. Such a compound is not generally used as a liquid crystal compound for active matrix (see JP-A 2002-357830). Such a foreign matter induces the generation of drop marks, and deterioration of a yield of a liquid crystal display element by poor display becomes a problem. Further, even in adding additives such as an antioxidant, a light absorber and the like to a liquid crystal composition, deterioration of a yield becomes a problem. Drop marks used herein are defined as the phenomenon that marks of a liquid crystal composition dropped in the case of black display rise up white.
For the suppression of such drop marks, a method of suppressing drop marks generated in relationship to an alignment controlling film by forming a polymer layer in a liquid crystal phase layer by polymerization of a polymerizable compound mixed in a liquid crystal composition is disclosed (JP-A 2006-58755). However, this method has a problem of burn-in of display due to a polymerizable compound added to a liquid crystal, and the effect of suppression of drop marks is not sufficient. Therefore, development of a liquid crystal display element that is difficult to generate burn-in and drop marks is required while maintaining basic characteristic as a liquid crystal display element. The liquid crystal composition of the present invention has the effect of suppressing or reducing the generation of drop marks.
The liquid crystal composition of the present invention preferably further contains a polymerizable monomer. Further, the polymerizable monomer in the present invention is preferably a bifunctional monomer represented by General Formula (8) from the above standpoint:
In General Formula (8), X81 and X82 each independently represent a hydrogen atom or a methyl group, Sp1 and Sp2 each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or —O—(CH2)s— (in the formula, s is an integer of 1 to 7, and an oxygen atom bonds to an aromatic ring),
Z2 represents —OCH2—, —CH2O—, —COO—, —OCO—, —CF2O—, —OCF2—, —CH2CH2—, —CF2CF2—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH2CH2—, —OCO—CH2CH2—, —CH2CH2—COO—, —CH2CH2—OCO—, —COO—CH2—, —OCO—CH2—, —CH2—COO—, —CH2—OCO—, —CY1═CY2— (in the formula, Y1 and Y2 each independently represent a fluorine atom or a hydrogen atom), —C≡C— or a single bond,
B represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond, and
a 1,4-phenylene group in the formula is all that an optional hydrogen atom may be substituted with a fluorine atom.
The bifunctional monomer represented by General Formula (8) is preferably a diacrylate derivative in which both X81 and X82 represent a hydrogen atom, a dimethacrylate derivative in which both X81 and X82 represent a methyl group, and a compound in which one of X81 and X82 represents a hydrogen atom and other represents a methyl group. Polymerization rate of those compounds is that the diacrylate derivative is most fast, the dimethacrylate is slow and an asymmetric compound is intermediate, and the preferred embodiment can be used depending on its use purpose. In a PSA display element, the dimethacrylate derivative is particularly preferred.
In General Formula (8), Sp1 and Sp2 each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or —O—(CH2)s—. In a PSA display element, at least one of Sp1 and Sp2 is preferably a single bond, and a compound in which both represent a single bond or an embodiment in which one represents a single bond and other represents an alkylene group having 1 to 8 carbon atoms or —O—(CH2)s— is preferred. In this case, an alkyl group having 1 to 4 is preferred, and s is preferably 1 to 4.
In General Formula (8), Z2 is preferably —OCH2—, —CH2O—, —COO—, —OCO—, —CF2O—, —OCF2—, —CH2CH2—, —CF2CF2— or a single bond, more preferably —COO—, —OCO— or a single bond, and particularly preferably a single bond.
In General Formula (8), B represents a 1,4-phenylene group in which optional hydrogen atom may be substituted with a fluorine atom, a trans-1,4-cyclohexylene group or a single bond, and a 1,4-phenylene group or a single bond is preferred. In the case where B represents a ring structure other than a single bond, Z2 is preferably a linking group other than a single bond, and in the case where B is a single bond, Z2 is preferably a single bond.
In the liquid crystal composition of the present invention, the content of the polymerizable monomer represented by General Formula (8) is preferably 0.05 to 1 mass %, more preferably 0.1 to 0.5 mass %, even more preferably 0.1 to 0.4 mass %, particularly preferably 0.1 to 0.3 mass %, and most preferably 0.15 to 0.3 mass %, based on the whole amount (100 mass %) of the liquid crystal composition.
When the content of the polymerizable monomer is 0.1 to 0.3 mass %, it is preferred in the standpoint of a balance between display characteristics and reliability of a liquid crystal display element.
From those points, in General Formula (8), specifically the ring structure between Sp1 and Sp2 is preferably the structures described below.
In General Formula (8), B represents a single bond, and in the case where the ring structure is formed by two rings, B preferably represents the following formulae (VIIIa-1) to (VIIIa-5):
(in General Formulas (VIIIa-1) to (VIIIa-5), both ends bond to Sp1 or Sp2),
more preferably represents General Formulas (VIIIa-1) to (VIIIa-3), and particularly preferably represents the formula (VIIIa-1).
In the polymerizable monomer containing those frameworks, alignment regulating force after polymerization is optimum to a PSA type liquid crystal display element, and good alignment state is obtained. As a result, display unevenness is suppressed or does not occur at all.
From the above, as the polymerizable monomer in the present invention, the formulae (8.1) to (8.4) are particularly preferred, and above all, the formula (8.2) is most preferred.
In the above formulae (8.1) to (8.4), Sp2 represents an alkylene group having 2 to 5 carbon atoms.
In the case of adding a monomer to the liquid crystal composition of the present invention, polymerization proceeds even in the case where a polymerization initiator is not present, but to accelerate the polymerization, a polymerization initiator may be contained. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and acylphosphine oxides. Further, to improve storage stability, a stabilizer may be added. Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, t-butyl catechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols and nitroso compounds.
It has been confirmed that the liquid crystal composition and/or the liquid crystal composition containing a polymerizable monomer of the present invention are effective to the suppression of drop marks.
The liquid crystal composition containing a polymerizable monomer of the present invention (hereinafter this may be referred to as the polymerizable monomer-containing liquid crystal composition) is useful for liquid crystal display elements and especially useful for active matrix drive liquid crystal display elements, and can be used in PSA-mode, PSVA-mode, VA-mode, IPS-mode, FFS-mode or ECB-mode liquid crystal display elements.
The polymerizable monomer-containing liquid crystal composition of the present invention can be given alignment performance through polymerization of the polymerizable monomer contained therein via UV irradiation, and is used in a liquid crystal display element in which the amount of the transmitted light is controlled by birefringence of the liquid crystal composition. Regarding liquid crystal display elements, the composition is useful for AM-LCD (active matrix liquid crystal display element), TN (nematic liquid crystal display element), STN-LCD (supertwisted nematic liquid crystal element), OCB-LCD and IPS-LCD (in-plane switching liquid crystal display element), especially useful for AM-LCD, and can be used in transmission-type or reflection-type liquid crystal display elements.
With reference to the liquid crystal display elements and the contents of
The substrates 2 and 8 on which the transparent electrode (layer) or TFT has been formed are combined in such a manner that the transparent electrodes (layers) 6 and 14 could face inside. In this case, the distance between the substrates may be controlled using a spacer (not shown). In this case, it is desirable to control the space in such a manner that the thickness of the light control layer to be formed could be 1 to 100 μm, more preferably 1.5 to 10 μm (see
In the case where a polarizer is used, it is desirable to control the product of the refractive index anisotropy Δn and the cell thickness d of the liquid crystal so as to realize a maximum contrast. In the case where the element has two polarizers 1 and 9, it is possible to control the polarization axis of each polarizer so as to better the viewing angle and the contrast (see
For the method for introducing a polymerizable monomer-containing liquid crystal composition into the space for liquid crystal composition to house the liquid crystal composition therein, as formed by sticking the two substrates to face to each other as mentioned above, an ordinary vacuum injection method or ODF method may be employed. However, the vacuum injection method of introducing a polymerizable monomer-containing liquid crystal composition has a problem of forming injection marks though drop marks are not formed, and in the present invention, producing liquid crystal displays using an ODF method is preferred.
As a method for polymerizing a polymerizable monomer in the present invention, a suitable polymerization rate is desired for realizing good alignment performance of liquid crystal, and therefore, a polymerization method according to single, combined or sequential irradiation with active energy rays such as UV rays, electron beams or the like is preferred. In the case where UV rays are used, a polarizing light source may be used, or a non-polarizing light source may be used. In the case where the polymerizable monomer-containing liquid crystal composition is polymerized while sandwiched between two substrates, at least the substrate on the irradiation side must give suitable transparency for active energy rays. In addition, a different method may also be employed, in which, a mask is used in photoirradiation so as to polymerize a specific part alone, and then the conditions of electric field, magnetic field, temperature and the like are changed to change the alignment state in the unpolymerized part, and the composition is further polymerized by additional active energy ray irradiation. In particular, in UV exposure, it is desirable to apply an alternating electric field to the polymerizable monomer-containing liquid crystal composition during UV exposure. The alternating electric field is preferably an alternate current of a frequency of 10 Hz to 10 kHz, more preferably a frequency of 60 Hz to 10 kHz, and the voltage may be selected depending on the desired pretilt angle of the liquid crystal display element. In other words, the pretilt angle of the liquid crystal display element can be controlled by the voltage to be applied. In an MVA-mode liquid crystal display element, the pretilt angle is preferably controlled to be 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast.
The temperature at the time when active energy rays such as UV rays, electron beams or the like are irradiated is preferably within a temperature range in which the liquid crystal composition of the present invention can have a liquid crystal state. Preferably, the polymerization is carried out at a temperature close to room temperature, typically at a temperature of 15 to 35° C. A metal halide lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp and the like can be used as a lamp to generate UV rays. Regarding the wavelength of the UV rays to be irradiated, UV rays having a wavelength region not the absorption wavelength region of the liquid crystal composition are preferably irradiated and, if desired, it is desirable to cut UV rays in irradiation. The intensity of the UV rays to be irradiated is preferably 0.1 mW/cm2 to 100 mW/cm2, more preferably 2 mW/cm2 to 50 mW/cm2. The energy amount of the UV rays to be irradiated may be suitably controlled, but is preferably 10 mJ/cm2 to 500 mJ/cm2, more preferably 100 mJ/cm2 to 200 mJ/cm2. In irradiation with UV rays, the intensity may be changed. The time for UV irradiation may be suitably selected depending on the intensity of the UV rays to be irradiated, but is preferably 10 seconds to 3600 seconds, preferably 10 seconds to 600 seconds.
As described above, in the process of producing a liquid crystal display element, the occurrence of drop marks is greatly influenced by a liquid crystal material to be injected, but the influence is not avoided even by the structure of a liquid crystal display element. Particularly, in a color filter or a thin-film transistor formed in a liquid crystal display element, only a thin alignment film, a transparent electrode or the like is a member separating a liquid crystal composition. Therefore, the occurrence of drop marks is influenced by, for example, a combination of a chemical structure of a pigment used in a color filter or a chemical structure of a color filter resin and a liquid crystal composition having a specific chemical structure.
From the above, the liquid crystal display element using the liquid crystal composition of the present invention is a useful element that achieves both high response and suppression of poor display, is particularly useful in an active matrix driving liquid crystal display element, and can be applied to VA mode, PSVA mode, FFS mode, PSA mode, IPS mode or ECB mode.
The liquid crystal composition of the present invention includes the compounds of General Formulas (1) and (2) as essential components, and as more preferred embodiment, can contain at least one kind selected from the group consisting of the compounds represented by General Formulas (3), (4), (6a), (6b) and (8). In this case, the contents are preferably the following contents.
The proportion of the compounds having two or more fluorine atoms in one molecule, specifically the compounds represented by General Formulas (1), (2), (3) and (4), occupied in each compound constituting the liquid crystal composition of the present invention is preferably 40 to 90 mass %, more preferably 45 to 85 mass %, and even more preferably 50 to 80 mass %, in the liquid crystal composition. Specifically described in more detail, in the case of considering response speed to be important, the proportion is preferably 50 to 60 mass %, and in the case of considering driving voltage to be important, the proportion is preferably 60 to 80 mass %.
A second aspect of the present invention is a liquid crystal display element using the liquid crystal composition of the present invention.
The second preferred embodiment of the liquid crystal display element of the present invention is a liquid crystal display element having a second substrate 8 provided with a common electrode 6, a first substrate 2 containing a pixel electrode including a transparent conductive material and a thin-film resistor layer 3 that forms a thin-film transistor controlling the pixel electrode provided on each pixel, and a liquid crystal composition (or a liquid crystal layer 5) interposed between the first substrate 2 and the second substrate 8, wherein alignment during non-application of voltage of a liquid crystal molecule in the liquid crystal composition is nearly vertical to the substrates 2 and 6, and characterized by using the liquid crystal composition of the present invention as the liquid crystal composition. In other words, the liquid crystal display element containing the liquid crystal composition of the present invention is arranged so as to separate the first substrate 2 and the second substrate 8, and the liquid crystal composition (or the liquid crystal layer 5) is filled between the first substrate 2 and the second substrate 8.
As shown in
Specifically, the liquid crystal display element 10 of the present invention is so designed that the second polarizer 1, the second substrate 2, the thin-film transistor-containing electrode layer (or also referred to as thin-film transistor layer) 3, the alignment film 4, the liquid crystal composition-containing layer 5, the alignment film 4, the common electrode 6, the color filter 7, the first substrate 8 and the first polarizer 9 are laminated in that order.
As other preferred embodiment of the liquid crystal display element 10 of the present invention, it may be a so-called color filter on array (COA), and the color filter 7 may be provided between the thin-film transistor layer 3 and the liquid crystal layer 5, or the color filter 7 may be provided between the thin-film transistor layer 3 and the second substrate 2.
As shown in
A common line 29 is provided in parallel to the gate electrode 26. The common line 29 is connected with the common electrode 22 so as to supply common signal to the common electrode 22.
In the present invention, the thin-film transistor can be preferably used in an inverted staggered type liquid crystal display element as shown in the drawing. The gate wiring 25, the data wiring 24 and the like are preferably a metal film, and the case of using an aluminum wiring is particularly preferred. Further, the gate wiring 25 and the data wiring 24 are overlapped through a gate insulting film.
In the configuration of
Preferred one embodiment of the configuration of a thin-film transistor in the liquid crystal display element of the present invention has, for example, a gate electrode 11 formed on the surface of the substrate 2, a gate insulating layer 13 provided so as to cover the gate electrode 11 and further cover a surface of the substrate 2, a semiconductor layer 17 formed on a surface of the gate insulating layer 13 so as to face the gate electrode 11, a protective layer 18 provided so as to cover a part of a surface of the semiconductor layer 17, a drain electrode 15 provided so as to cover one side edge of the protective layer 18 and the semiconductor layer 17 and further to be brought into contact with the gate insulating layer 13 formed on a surface of the substrate 2, source electrodes 19a and 19b provided so as to cover other side edge of the protective layer 18 and the semiconductor layer 17 and further to be brought into contact with the gate insulating layer 13 formed on a surface of the substrate 2, a transparent electrode 14 provided so as to cover the source electrodes 19a and 19b and further to cover nearly the entire surface of the gate insulating layer 13 following the gate insulating layer 13, and a protective layer 101 (not shown in
As shown in
Amorphous silicon, polycrystalline silicon or the like can be used in the semiconductor layer 17 in the present invention, but use of a transparent semiconductor film such as ZnO, IGZO (In—Ga—Zn—O), ITO or the like can suppress harmful effect of light carrier due to light absorption, and this is preferred from the standpoint of increasing an aperture ratio of an element.
The ohmic contact layer 15 may be provided between the semiconductor layer 13 and the drain electrode 16 or the source electrode 17 for the purpose of reducing a width and a height of Schottky barrier. A material having added thereto impurities such as phosphorus in high concentration, such as n-type amorphous silicon or n-type polycrystalline polysilicon, can be used in the ohmic contact layer.
The gate wiring 26, the data wiring 25 and the common wiring 29 are preferably a metal film. Al, Cu, Au, Ag, Cr, Ta, Ti, Mo, W, Ni or its alloy is more preferred, and use of a wiring of Al or its alloy is particularly preferred. The insulating protective layer 18 is a layer having insulating function, and is formed by silicon nitride, silicon dioxide, silicon oxynitride film or the like.
In the embodiments shown in
Particularly, in the case of using the above inverted staggered type as a thin-film transistor in the liquid crystal display element of the present invention, the drain electrode 15 is formed so as to cover the gate electrode 11. As a result, the area of the drain electrode 15 tends to be increased. Generally, it is the ordinary embodiment that a drain electrode is formed by a metal material such as copper, aluminum, chromium, titanium, molybdenum or tantalum, and is subjected to a passivation treatment. However, for example, as shown in
However, it is considered in the liquid crystal display element containing the liquid crystal composition of the present invention that the problem of the occurrence of drop marks can be reduced from, for example, the standpoint of delicate balance between a member of a liquid crystal display element and surface free energy or adsorption energy of the liquid crystal composition of the present invention.
The second preferred embodiment of the liquid crystal display element of the present invention is a liquid crystal display element in which a first substrate having on the surface thereof a first alignment layer and a thin-film transistor-containing electrode layer and a second substrate having on the surface thereof a second alignment layer are arranged so as to separate such that the alignment layers face with each other, and a liquid crystal layer containing a liquid crystal composition is filled between the first substrate and the second substrate, wherein the thin-film transistor containing electrode layer preferably includes plural gate wirings and data wirings provided in a network shape, a thin-film transistor provided at each intersection between the gate wirings and the data wirings, a pixel electrode connected to the thin-film transistor, and a common electrode provided on the first substrate separating from the pixel electrode. Further, the first alignment layer and the second alignment layer provided adjacent to the liquid crystal layer are preferably an alignment film inducing homogeneous alignment to the liquid crystal composition.
Specifically, the liquid crystal display element is preferably designed such that a second polarizer, a second substrate, a thin-film transistor-containing electrode layer (or also referred to as a thin-film transistor layer), an alignment film, a liquid crystal composition-containing liquid crystal layer, an alignment film, a color filter, a first substrate and a first polarizer are laminated in this order.
Electric field (E) generated between the common electrode and the pixel electrode can have a plane surface direction component by providing the common electrode and pixel electrode separated with each other on the same substrate (or electrode layer). As a result, for example, when an alignment film inducing homogeneous alignment to a liquid crystal composition is used in the alignment layer, liquid crystal molecules arranged in a plane direction that is an alignment direction of an alignment film before applying voltage between a common electrode and a pixel electrode shield light, and when voltage is applied, the liquid crystal molecules rotate horizontally by the electric field (E) applying to a plane surface direction, and are arranged along the electric field direction, thereby an element shielding light can be provided.
The form of the liquid crystal display element of the present invention may be a so-called color filter on array (COA). A color filter may be provided between a thin-film transistor-containing electrode layer and a liquid crystal layer, or a color filler may be provided between the thin-film transistor-containing electrode layer and a second substrate.
More preferred embodiment (IPS) of the second embodiment of the present invention is a liquid crystal display element in which a first substrate having on the surface thereof an alignment layer and a thin-film transistor-containing electrode layer and a second substrate having on the surface thereof an alignment layer are arranged so as to separate such that the alignment layers face with each other, and a liquid crystal composition-containing liquid crystal layer is filled between the first substrate and the second substrate, wherein the thin-film transistor-containing electrode layer includes plural gate wirings and data wirings provided in a network shape, a thin-film transistor provided at each intersection between the gate wirings and the data wirings, a pixel electrode connected to the thin-film transistor, and a common electrode provided on the first substrate separated from the pixel electrode, and the shortest separation distance d between the adjacent common electrode and pixel electrode is preferably longer than the shortest separation distance D between the mutual alignment layers.
More preferred embodiment of the liquid crystal display element is described below using
As shown in
In the present specification, the liquid crystal display element having the condition that the shortest separation distance d between the adjacent common electrode and pixel electrode is longer than the shortest separation distance G of the mutual alignment layers is called an IPS system liquid crystal display element, and the element having the condition that the shortest separation distance d between the adjacent common electrode and pixel electrode is shorter than the shortest separation distance G of the mutual alignment layers is called FFS. Therefore, only that the shortest separation distance d between the adjacent common electrode and pixel electrode is longer than the shortest separation distance G of the mutual alignment layers is the condition of an IPS system. Therefore, there is not limitation in the positional relationship in a thickness direction between the surface of the common electrode and the surface of the pixel electrode. For this reason, in the IPS system liquid crystal display element of the present invention, the pixel electrode may be provided at a liquid crystal layer side than the common electrode as shown in
The embodiment relating to the position in a thickness direction between the pixel electrode and the common electrode is described below as other embodiment of the IPS system or FFS system liquid crystal display element of the present invention.
The configuration as more preferred embodiment of the second embodiment (IPS system or FFS system liquid crystal display element) of the present invention is that the pixel electrode and the common electrode are formed on the same substrate, similar to the exploded view of
The structure of the electrode layer 3 shown in
In the case of the IPS system (the condition that the shortest separation distance d between the adjacent common electrode and pixel electrode is longer that the shortest separation distance G of mutual alignment layers (or distance between substrates), if the shortest separation distance d between the adjacent common electrode and pixel electrode is longer than the shortest separation distance G of the mutual alignment layers, the electric field (E) formed between the common electrode and the pixel electrode is that the component in a surface direction (electric field in a horizontal direction) increases, thereby orienting liquid crystal molecules in a horizontal direction. As a result, the IPS or FFS system liquid crystal display element is that as shown in the drawing, when electric field is formed between the pixel electrode 121 and the common electrode 122, liquid crystal oriented in a horizontal direction rotates in a horizontal direction, thereby a transmission amount of incident light from a backlight can be controlled. The IPS and FFS mode liquid crystal display elements have the merits of wide viewing angle and high contrast. However, because the common electrode 122 is formed by the same metal material as the data wiring or the gate wiring, there are problems that aperture ratio and transmittance are low, and color changes by a viewing angle.
In the IPS and FFS system liquid crystal display elements, the first alignment layer and second alignment layer provided adjacent to the liquid crystal layer are preferably an alignment film that induces homogeneous alignment to the liquid crystal composition. For example, when an alignment film that induces homogeneous alignment to the liquid crystal composition is used as the alignment layer, liquid crystal molecules arranged in a surface direction that is an alignment direction of the alignment film before applying voltage between the common electrode and the pixel electrode shield light. On the other hand, when voltage is applied, electric field (E) is applied in a plane direction. As a result, liquid crystal molecules rotate horizontally, and can be arranged along the electric field direction.
The term “on the substrate” in the present specification includes the state of not only direct contact with a substrate, but indirect contact, that is, the state of being supported on a substrate.
Other preferred embodiment (FFS) in the liquid crystal display composition of the present invention is a liquid crystal display element in which a first substrate having on the surface thereof a first alignment layer and a thin-film transistor-containing electrode layer, and a second substrate having on the surface thereof a second alignment layer are arranged by separating such that the alignment layers face with each other, and the space between the first substrate and the second substrate is filled with a liquid crystal composition-containing liquid crystal layer, wherein the thin-film transistor-containing electrode layer includes plural gate wirings and data wirings provided in a network shape, a thin-film transistor provided at each intersection between the gate wirings and the data wirings, a pixel electrode connected to the thin-film transistor, and a common electrode provided on the first substrate separating from the pixel electrode, and the shortest separation distance d between the adjacent common electrode and pixel electrode is preferably shorter than the shortest separation distance G between the mutual alignment layers.
The FFS system liquid crystal display element utilizes fringe electric field, and when the shortest separation distance d between the adjacent common electrode and pixel electrode is shorter than the shortest separation distance D between mutual alignment layers, fringe electric field is formed between the common electrode and the pixel electrode, and alignment in a horizontal direction and a vertical direction of liquid crystal molecules can be efficiently utilized. Specifically, in the case of the FFS system liquid crystal display element, electric field in a horizontal direction formed in a vertical direction to a line forming a comb shape of the pixel electrode 21, and radial electric field can be utilized.
Further, in the case of the FFS system liquid crystal display element, when voltage is applied to liquid crystal molecules arranged such that a long axis direction is parallel to an alignment direction of the alignment layer, equipotential line of radial electric field is formed between the pixel electrode 121 and the common electrode 122 up to the upper part of the pixel electrode 121 and the common electrode 122, and liquid crystal molecules in the liquid crystal layer 5 rotate in the liquid crystal layer 5 along the electric field formed. Particularly, the liquid crystal composition of the present invention uses liquid crystal molecules having negative dielectric anisotropy. Therefore, a long axis direction of the liquid crystal molecules rotates so as to go straight to the electric field direction formed. The liquid crystal molecules located near the pixel electrode 21 are easy to receive the influence of fringe electric field, but liquid crystal molecules having negative dielectric anisotropy are that polarization direction is on a short axis of molecules. Therefore, the long axis direction does not rotate in a direction going straight to the alignment layer 4, and the long axis direction of all liquid crystal molecules in the liquid crystal layer 5 can maintain a parallel direction to the alignment film 4. Therefore, excellent transmittance characteristic can be obtained as compared with the FFS system liquid crystal display element using liquid crystal molecules having positive dielectric anisotropy.
The minimum separation distance d between the pixel electrode and the common electrode can be adjusted as a (average) film thickness of the gate insulating film 12. In other words, in the embodiment of
As shown in
The present invention is described in detail with reference to Examples given hereinunder, but the scope of the present invention should not be limited to these Examples. “%” in the compositions of the following Examples and Comparative Examples means “% by mass”. In Examples, the properties measured and the evaluations are as follows.
The following abbreviations are used in describing the compounds used in Examples.
(Side Chain)
−n —CnH2n+1, a linear alkyl group having n's carbon atoms.
n− CnH2n+1—, a linear alkyl group having n's carbon atoms.
−On —OCnH2n+1, a linear alkoxyl group having n's carbon atoms.
nO− CnH2n+1O—, a linear alkoxyl group having n's carbon atoms.
−V —CH═CH2
V− CH2═CH—
−V1 —CH═CH—CH3
1V− CH3—CH═CH—
−2V —CH2—CH2—CH═CH3
V2− CH3═CH—CH2—CH2—
−2V1 —CH2—CH2—CH═CH—CH3
1V2− CH3—CH═CH2—CH2—CH2
—COO— —COO—
—OCO— —OCO—
(Ring Structure)
Liquid crystal compositions having formulations shown in the following Table 1 were prepared, and the physical properties thereof were measured. The results are shown in the following Tables.
The VA liquid crystal display element shown in
Tni: Nematic phase-isotropic liquid phase transition temperature (° C.)
Δn: Refractive index anisotropy at 25° C.
Δ∈: Dielectric anisotropy at 25° C.
η: Viscosity at 20° C. (mPa·s)
γ1: Rotational viscosity at 25° C. (mPa·s)
Initial voltage holding ratio (initial VHR): Voltage holding ratio (%) at 343 K under the condition of a frequency of 6 Hz and an applied voltage of 5V.
VHR after heat resistance test: A TEG (test element group) for evaluation of electro-optical properties filled with a liquid crystal composition sample was held in a constant-temperature tank at 130° C. for 1 hours, and then VHR thereof was measured under the same condition as that of the above-mentioned VHR measurement method.
Light resistance test used an ultra-high pressure mercury lamp (manufactured by ATLAS, SUNTEST CPS+, 50 lamp output: 500 W, illumination in 300 to 400 nm: 50 W/m2). A sample of 2 cc was placed in a glass bottle having an inner diameter of 25 mm, light resistance test was performed (20 minutes) and the change with time of resistivity was examined.
Burn-in evaluation of a liquid crystal display element was performed as follows. After displaying a predetermined fixed pattern in a display area for an optional test time of 1000 hours, test time until an afterimage of the fixed pattern when uniform display was conducted on the entire surface reaches unacceptable afterimage level was measured.
1) The test time used herein means a display time of a fixed pattern, longer time indicates that the occurrence of afterimage is suppressed and performance is high.
2) Unacceptable afterimage level is a level that afterimage that fails in pass/fail judgment of shipping is observed. The level was visually determined by the following four-grade evaluation. Performance is high as test time is longer.
Sample A: 1,000 hours
Sample B: 500 hours
Sample C: 200 hours
Sample D: 100 hours
The performance is A>B>C>D.
Test results of light resistance of the liquid crystal compositions prepared in Examples 1 to 19 showed that specific resistance value was decreased at most 1/50 by UV irradiation for 20 minutes. On the other hand, it was confirmed that specific resistance value was decreased 1/100 or less in the liquid crystal compositions of Comparative Examples 1 and 2.
Each constitution in each embodiment described above, the combination thereof and the like are one example, and addition, omission, substitution and other modifications of constitution can be made without departing the spirit and scope of the present invention. Further, the present invention is not limited by each embodiment, and is limited by only the scope of claims.
The liquid crystal composition of the present invention can be widely applied to fields of a liquid crystal display element and a liquid crystal display.
Number | Date | Country | Kind |
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2014-150713 | Jul 2014 | JP | national |
Filing Document | Filing Date | Country | Kind |
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PCT/JP2015/076440 | 9/17/2015 | WO | 00 |