CN112662405A - Liquid crystal composition, liquid crystal display element, and compound - Google Patents
Liquid crystal composition, liquid crystal display element, and compound Download PDFInfo
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- Liquid Crystal Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention addresses the problem of providing a liquid crystal composition that satisfies various characteristics required for an n-type liquid crystal composition having a negative dielectric anisotropy Δ ∈ and has a rotational viscosity γ, a liquid crystal display element using the liquid crystal composition, and a compound suitable for production of the liquid crystal composition1Sufficiently small, elastic constant K11Small, and can achieve high-speed response and high transmittance when used in liquid crystal devices such as liquid crystal TVs. The present invention provides a composition comprising one or more compounds having a specific chemical structureThe liquid crystal composition of the compound and a liquid crystal display element using the liquid crystal composition are provided to solve the problems.
Description
Technical Field
The present invention relates to a liquid crystal composition, a liquid crystal display element using the same, and a compound. More specifically, the present invention relates to a so-called n-type liquid crystal composition exhibiting a negative dielectric anisotropy (Δ ∈), and a compound suitable for the production of the n-type liquid crystal composition.
Background
Liquid crystal display devices are used in various household electric appliances, industrial measuring instruments, automobile panels, cellular phones, smart phones, notebook Personal Computers (PCs), tablet PCs, televisions, and the like, as typified by clocks and desktop computers. Representative examples of liquid crystal display systems include: twisted Nematic (TN) type, Super Twisted Nematic (STN) type, guest-host (GH) type, in-plane switching (IPS) type, Fringe Field Switching (FFS) type, Optically Compensated Birefringence (OCB) type, Electrically Controlled Birefringence (ECB) type, Vertically Aligned (VA) type, Color Super Homeotropic (CSH) type, Ferroelectric Liquid Crystal (FLC) type, and the like. The driving method may be static driving, multiplex driving, simple matrix driving, or Active Matrix (AM) driving by a Thin Film Transistor (TFT), a Thin Film Diode (TFD), or the like. Among these display modes, it is known that when a liquid crystal composition (n-type liquid crystal composition) exhibiting a negative dielectric anisotropy is used, the IPS mode, FFS mode, ECB mode, VA mode, CSH mode, and the like exhibit favorable characteristics.
The display modes using the n-type liquid crystal composition include a vertical Alignment mode represented by a Polymer Stabilized Alignment (PSA) type or a Polymer Stabilized Vertical Alignment (PSVA) type in which Alignment is controlled by polymerizing a VA-type or a polymerizable compound in a liquid crystal phase, and a horizontal Alignment mode represented by an IPS-type or FFS-type. The vertical alignment method is characterized by a wide viewing angle, high transmittance, high contrast, and a high response speed, and is mainly used for large-sized display devices such as Televisions (TVs) and monitors. On the other hand, the horizontal alignment method is adopted in mobile devices such as smartphones and tablet PCs, and is also being adopted in liquid crystal televisions from the viewpoint of a wide viewing angle, high transmittance, low power consumption, and optimality with respect to touch panels. The PSA-type or PSVA-type liquid crystal display device is a device in which a polymer structure is formed in a cell in order to control the pretilt angle of liquid crystal molecules, and is known to have a high-speed response and a high contrast ratio, particularly, in the characteristics of the vertical alignment method.
In recent years, with the progress of high resolution, high frequency driving, and the like of liquid crystal TVs, there has been an increasing demand for liquid crystal compositions that are suitable for high-performance liquid crystal devices and can satisfy various characteristics. However, there is still room for improvement in the liquid crystal compositions described in patent documents 1 to 4 below.
Further, there is a problem that a liquid crystal composition containing a polymerizable compound, which has been conventionally used to contain a polymerizable compound in a liquid crystal composition, does not have characteristics capable of coping with a high-resolution liquid crystal TV such as 4K or 8K. In particular, a high-resolution liquid crystal display element requires high-definition pixels, and thus the size of each pixel is small. Therefore, since the area of the wiring and the light shielding portion is relatively increased, Ultraviolet (UV) light is largely cut off, and the aperture ratio of the liquid crystal display portion is reduced, thereby lowering the transmittance.
In particular, in the case of a vertical alignment liquid crystal display element (hereinafter, sometimes referred to as "VA liquid crystal display element"), it is difficult to sufficiently improve light transmittance only by adjusting the threshold voltage. By shifting (shift) the V-T curve showing the characteristics of applied voltage-transmittance to the low voltage side by lowering the threshold voltage, the transmittance under the low voltage condition can be improved. However, in the above method, the slope of the V-T curve of the VA liquid crystal display element does not become steep and the maximum transmittance does not become high, so that it is difficult to realize high light transmittance at a low driving voltage.
Therefore, with respect to the liquid crystal composition constituting the liquid crystal layer, adjustment is consideredSplay elastic constant (K)11) And bending elastic constant (K)33) Is K11/K33The method of (2). According to the method, the V-T curve of the VA liquid crystal display element becomes steep, and the light transmittance can be improved even at a low driving voltage.
Further, in liquid crystal TVs of higher models and the like, high-frequency driving is progressing, and therefore development of a liquid crystal composition capable of responding to voltage change at high speed is urgently required. In order to respond to a voltage change at high speed, γ, which is a parameter that governs the response speed, is desirable1/K33Is small, so that it is considered to increase the elastic constant K33。γ1Is a parameter indicating rotational viscosity.
From the above, when a liquid crystal composition is used for these liquid crystal display elements, it is desirable that the elastic constant K is high in order to exhibit high transmittance and high-speed response11Small and elastic constant K33Is large.
[ Prior art documents ]
[ patent document ]
[ patent document 1] International publication No. 2010/084823
[ patent document 2] Japanese patent laid-open No. 2016-216747
[ patent document 3] Japanese patent laid-open publication No. 2017-14486
[ patent document 4] Japanese patent No. 6403038 publication
[ patent document 5] Japanese patent No. 6233550
Disclosure of Invention
[ problems to be solved by the invention ]
However, in the liquid crystal composition, due to the elastic constant K11And elastic constant K33Are highly correlated parameters, and therefore it is difficult to reduce the elastic constant K11While increasing the elastic constant K33. Therefore, to reduce γ1/K33In view of reducing the rotational viscosity γ1Rather than increasing the elastic constant K33。
The invention aims to provide a liquidA liquid crystal composition satisfying various characteristics required for an n-type liquid crystal composition having a negative dielectric anisotropy (Delta epsilon) and having a rotational viscosity gamma, a liquid crystal display element using the same, and a compound suitable for production of the liquid crystal composition1Sufficiently small, elastic constant K11Small, and can achieve high-speed response and high transmittance when used in liquid crystal devices such as liquid crystal TVs.
[ means for solving problems ]
The present inventors have conducted extensive studies and as a result, have found that the above problems can be solved by a liquid crystal composition containing one or more compounds having a specific chemical structure, and have completed the present invention.
That is, the liquid crystal composition of the present invention is characterized by containing one or more compounds represented by the general formula (I),
[ solution 1]
(in the formula, R1Represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, wherein-CH in these groups2-or two or more-CHs not adjacent to each other2-may each be independently substituted by-O-or-S-, and in addition, one or two or more hydrogen atoms present in these groups may each be independently substituted by a fluorine atom or a chlorine atom,
ring A1Is 1, 4-cyclohexylene or 1, 4-cyclohexenylene,
A2each independently represents 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 3, 5-difluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 1, 4-cyclohexenylene, 1, 4-bicyclo [2.2.2 ] phenylene]Octylene, piperidine-1, 4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, wherein one or two or more hydrogen atoms of these groups may independently be halogen, cyano, nitro, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a C2 to 1 carbon atom2, the hydrogen atom in the alkyl, alkoxy or alkenyl group may be substituted by halogen, a2When a plurality of them exist, they may be the same or different,
Z0represents-OCH2-、-CH2O-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-or a single bond,
m1represents a number of 0,1 or 2,
wherein m is1Is 1, ring A1And A2Is 1, 4-cyclohexylene and Z0Except for the case of a single bond).
The liquid crystal display element of the present invention is characterized by using the liquid crystal composition.
The compound of the present invention is characterized by being a compound represented by the general formula (I),
[ solution 2]
(in the formula, R1Represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, wherein-CH in these groups2-or two or more-CHs not adjacent to each other2-may each be independently substituted by-O-or-S-, and in addition, one or two or more hydrogen atoms present in these groups may each be independently substituted by a fluorine atom or a chlorine atom,
ring A1Is 1, 4-cyclohexylene or 1, 4-cyclohexenylene,
A2each independently represents 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 3, 5-difluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 1, 4-cyclohexenylene, 1, 4-bicyclo [2.2.2 ] phenylene]Octylene, piperidine-1, 4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, wherein one or two or more hydrogen atoms of these groups may be independently substituted by halogen, cyano, nitro, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms, or the alkyl group, or the alkenyl groupThe oxy group or the hydrogen atom in the alkenyl group may be substituted by halogen, A2When a plurality of them exist, they may be the same or different,
Z0represents-OCH2-、-CH2O-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-or a single bond,
m1represents a number of 0,1 or 2,
wherein m is1Is 1, ring A1And A2Is 1, 4-cyclohexylene and Z0Except for the case of a single bond).
[ Effect of the invention ]
The liquid crystal composition of the present invention contains the compound represented by the general formula (I), and thus can satisfy various characteristics required for an n-type liquid crystal composition having a negative dielectric anisotropy (. DELTA.. di-elect cons.), and has a rotational viscosity (. gamma.) (see1Sufficiently small, elastic constant K11Small, and can achieve high-speed response and high transmittance when used in liquid crystal devices such as liquid crystal TVs.
Detailed Description
As described above, the present invention relates to a liquid crystal composition, a liquid crystal display element using the liquid crystal composition, and a compound suitable for production of the liquid crystal composition. First, an embodiment of the liquid crystal composition of the present invention will be described below. In the following description, "total amount" means "total mass", and the unit "%" of the content of each compound means "% by mass".
< liquid crystal composition >
The liquid crystal composition of the present invention contains one or more compounds represented by the following general formula (I).
[ solution 3]
In the general formula (I), R1Represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms. Of these radicals-CH2Or two not adjacent to each otherof-CH2-may be independently substituted with-O-or-S-, respectively, and in addition, one or two or more hydrogen atoms present in these groups may be independently substituted with fluorine atom or chlorine atom, respectively. R1More preferably an alkoxy group having 1 to 4 carbon atoms.
Ring A1Each independently is 1, 4-cyclohexylene or 1, 4-cyclohexenylene. From the viewpoint of stability, ring A is preferable1Is a 1, 4-cyclohexylene group.
A2Each independently represents 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 3, 5-difluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 1, 4-cyclohexenylene, 1, 4-bicyclo [2.2.2 ] phenylene]Octylene, piperidine-1, 4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl. One or more hydrogen atoms in these groups may be independently substituted by halogen, cyano, nitro, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms. The hydrogen atom in the alkyl group, alkoxy group or alkenyl group may be substituted with halogen. A. the2When plural ones exist, they may be the same or different.
From the viewpoint of liquid crystallinity, A2Preference is given to cyclohexylene, 1, 4-phenylene or 1, 4-cyclohexenylene. In this case, one or more hydrogen atoms in these groups may be substituted with a halogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms. The hydrogen atom in the alkyl group, alkoxy group or alkenyl group may be substituted with halogen.
Z0represents-OCH2-、-CH2O-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-or a single bond. From the viewpoint of liquid crystallinity, Z is preferred0is-CH2O-、-CH2CH2-or a single bond, more preferably-CH2O-or a single bond.
m1Represents 0,1 or 2. From the viewpoint of solubility, m is preferred1Is 1.
Wherein, the compound represented by the general formula (I)In does not contain m1Is 1, A1And A2Is 1, 4-cyclohexylene and Z0A compound which is a single bond.
The compounds represented by the general formula (I) include compounds represented by the following general formulae (I-A) to (I-X). In the formula, R1Represents a group represented by the formula (I) and R in the formula (I)1The same meaning is used. From the viewpoint of liquid crystallinity, preferred are compounds represented by the general formulae (I-A) to (I-J) and the general formulae (I-L) and (I-M). Further, from the viewpoint of solubility, compounds represented by the general formula (I-A), the general formula (I-B) and the general formula (I-K) are more preferable.
[ solution 4]
[ solution 5]
[ solution 6]
In the present invention, one or more compounds represented by the general formula (I) are contained in an amount of 1 to 100% by mass. From the viewpoint of solubility, the amount is preferably 1 to 80% by mass, and more preferably 2 to 50% by mass. Particularly preferably 2 to 30% by mass.
In the case where importance is attached to reduction in viscosity of the liquid crystal composition, R of the compound represented by the general formula (I)1The alkyl group, alkoxy group, alkenyl group and alkenyloxy group are preferable, the alkyl group and alkoxy group are more preferable, and the alkoxy group is particularly preferable. Further, it is preferable to increase R represented by the general formula (I)1The lower limit of the content of the compound having an alkyl group, an alkoxy group, an alkenyl group, or an alkenyloxy group is preferably 1% by mass, more preferably 2% by mass, more preferably 3% by mass, and still more preferablyIs selected to be 4 mass%.
When the viscosity of the liquid crystal composition is reduced and the stability of the liquid crystal composition against ultraviolet rays is also important, it is preferable to reduce R in the compound represented by the general formula (I)1The content of the compound having an alkyl group, an alkoxy group, an alkenyl group, or an alkenyloxy group is preferably 15% by mass, more preferably 10% by mass, and still more preferably 5% by mass, as the upper limit.
The liquid crystal composition of the present invention contains the compound represented by the general formula (I), and thus can satisfy various characteristics required for an n-type liquid crystal composition having a negative dielectric anisotropy Δ ε and has a rotational viscosity γ1Sufficiently small, elastic constant K11Small size, and can realize high-speed response and high transmittance when used in liquid crystal devices such as liquid crystal TVs.
The liquid crystal composition of the present invention preferably contains one or more compounds selected from the group consisting of compounds represented by the following general formulae (N-01) to (N-05). These compounds correspond to compounds having negative anisotropy in dielectric, Δ ∈ having a negative sign, and the absolute value thereof shows a value greater than 2. The Δ ∈ of the compound is a value extrapolated from a measured value of dielectric anisotropy of a composition in which the compound was added to a composition that was nearly neutral in dielectric properties at 25 ℃.
The liquid crystal composition of the present invention preferably contains one or more compounds selected from the group consisting of compounds represented by the following general formulae (N-01) to (N-05).
[ solution 7]
In the general formula (N-01) to the general formula (N-05), R21And R22Independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, and one or two or more-CH groups which are not adjacent to each other2-independently of each other, -CH ═ CH-, -C ≡ CC-, -O-, -CO-, -COO-or-OCO-substituted, Z1Each independently represents a single bond, -CH2CH2-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-, -CH ═ CH-, -CF ═ CF-or-C ≡ C-, and m independently represents 1 or 2, respectively. Wherein, the compound represented by the general formula (I) is excluded.
In the general formula (N-01) to the general formula (N-05), R21Preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably an alkyl group having 2 to 5 carbon atoms. Wherein, in Z1R is other than a single bond21Preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 2 to 3 carbon atoms.
In the general formula (N-01) to the general formula (N-05), R22Preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and still more preferably an alkoxy group having 1 to 4 carbon atoms.
In the general formula (N-01) to the general formula (N-05), R21And R22When the alkenyl group is an alkenyl group, it is preferably a group represented by any one of formulae (R1) to (R5), and more preferably formula (R1) or formula (R2). The black dots in the formulae represent carbon atoms in the ring structure. Wherein R is21And R22The content of the compound which is an alkenyl group is preferably as small as possible, and preferably not contained.
[ solution 8]
In the general formula (N-04), Z1Each independently represents a single bond, -CH2CH2-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-, -CH-, -CF-or-C.ident.C-, preferably a single bond, -CH ≡ C-2CH2-、-OCH2-、-CH2O-, more preferably a single bond or-CH2O-is formed. When m is 1, Z1Preferably a single bond. When m is 2, Z1Preferably, it is-CH2CH2-or-CH2O-。
The fluorine atom in the compounds represented by the general formulae (N-01) to (N-05) may be substituted with the same halogen group, i.e., chlorine atom. Among them, the content of the compound substituted with a chlorine atom is preferably as small as possible, and preferably not contained.
The hydrogen atom present in the ring of the compounds represented by the general formulae (N-01) to (N-05) may be replaced by a fluorine atom or a chlorine atom, but a chlorine atom is not preferred.
The compounds represented by the general formulae (N-01) to (N-05) are preferably compounds having negative Δ ∈ and an absolute value of greater than 3. In particular, R22Preferably represents an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, and particularly preferably an alkoxy group having 1 to 4 carbon atoms.
The liquid crystal composition of the present invention preferably contains one or more compounds selected from the group consisting of compounds represented by the general formulae (N-01-1) to (N-01-4) as the compound represented by the general formula (N-01). In the formula, R21Denotes the same meaning as described, R23Each independently represents an alkoxy group having 1 to 4 carbon atoms.
[ solution 9]
The liquid crystal composition of the present invention preferably contains both the compound represented by the general formula (N-01-1) and the compound represented by the general formula (N-01-4).
The liquid crystal composition of the present invention preferably contains both the compound represented by the general formula (N-01-3) and the compound represented by the general formula (N-01-4).
The liquid crystal composition of the present invention preferably contains one or more compounds selected from the group consisting of compounds represented by the general formulae (N-02-1) to (N-02-4) as the compound represented by the general formula (N-02). In the formula, R21Denotes the same meaning as described, R23Each independently represents an alkoxy group having 1 to 4 carbon atoms.
[ solution 10]
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (N-02-1).
The liquid crystal composition of the present invention preferably contains both the compound represented by the general formula (N-02-1) and the compound represented by the general formula (N-02-3).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (N-02-1) and a compound represented by the general formula (N-01-4).
The liquid crystal composition of the present invention preferably contains one or more compounds represented by the general formula (N-03-1) as the compound represented by the general formula (N-03). In the formula, R21Denotes the same meaning as described, R23Represents an alkoxy group having 1 to 4 carbon atoms.
[ solution 11]
The liquid crystal composition of the present invention preferably contains both the compound represented by the general formula (N-03-1) and the compound represented by the general formula (N-02-1).
The liquid crystal composition of the present invention preferably contains both the compound represented by the general formula (N-03-1) and the compound represented by the general formula (N-01-4).
The liquid crystal composition of the present invention preferably contains both the compound represented by the general formula (N-03-1), the compound represented by the general formula (N-01-3) and the compound represented by the general formula (N-01-4).
The liquid crystal composition of the present invention preferably contains one or more compounds represented by the general formula (N-04-1) as the compound represented by the general formula (N-04). In the formula, R21Denotes the same meaning as described, R23Represents an alkoxy group having 1 to 4 carbon atoms.
[ solution 12]
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (N-04-1).
The liquid crystal composition of the present invention particularly preferably contains both a compound represented by the general formula (N-04-1) and a compound represented by the general formula (N-01-4).
The liquid crystal composition of the present invention particularly preferably contains both the compound represented by the general formula (N-04-1), the compound represented by the general formula (N-01-3) and the compound represented by the general formula (N-01-4).
The liquid crystal composition of the present invention particularly preferably contains a compound represented by the general formula (N-04-1), a compound represented by the general formula (N-01-4) and a compound represented by the general formula (N-02-1) in combination.
The liquid crystal composition of the present invention particularly preferably contains a compound represented by the general formula (N-04-1), a compound represented by the general formula (N-01-4) and a compound represented by the general formula (N-03-1) at the same time.
The liquid crystal composition of the present invention particularly preferably contains a compound represented by the general formula (N-04-1), a compound represented by the general formula (N-02-1) and a compound represented by the general formula (N-03-1) at the same time.
The liquid crystal composition of the present invention particularly preferably contains a compound represented by the general formula (N-04-1), a compound represented by the general formula (N-01-4), a compound represented by the general formula (N-02-1) and a compound represented by the general formula (N-03-1) in combination.
The liquid crystal composition of the present invention may contain a compound selected from the group consisting of compounds represented by the formulae (N-05-1) to (N-05-3) as the compound represented by the general formula (N-05).
[ solution 13]
The liquid crystal composition of the present invention preferably contains both the compound represented by the general formula (N-05-1) and the compound represented by the general formula (N-03-1), the compound represented by the general formula (N-01-2), and the compound represented by the general formula (N-02-1).
The lower limit of the preferable content of the compound represented by the general formula (N-01) is 0 mass%, 1 mass%, 5 mass%, 10 mass%, 20 mass%, 30 mass%, 40 mass%, 50 mass%, 55 mass%, 60 mass%, 65 mass%, 70 mass%, 75 mass%, and 80 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, 45% by mass, 35% by mass, 25% by mass, 20% by mass, 15% by mass, and 10% by mass.
The lower limit of the preferable content of the compound represented by the general formula (N-02) is 0 mass%, 1 mass%, 5 mass%, 10 mass%, 20 mass%, 30 mass%, 40 mass%, 50 mass%, 55 mass%, 60 mass%, 65 mass%, 70 mass%, 75 mass%, and 80 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, 45% by mass, 35% by mass, 25% by mass, 20% by mass, 15% by mass, and 10% by mass.
The lower limit of the preferable content of the compound represented by the general formula (N-03) is 0 mass%, 1 mass%, 5 mass%, 10 mass%, 20 mass%, 30 mass%, 40 mass%, 50 mass%, 55 mass%, 60 mass%, 65 mass%, 70 mass%, 75 mass%, and 80 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, 45% by mass, 35% by mass, 25% by mass, 20% by mass, 15% by mass, and 10% by mass.
The lower limit of the preferable content of the compound represented by the general formula (N-04) is 0 mass%, 1 mass%, 5 mass%, 10 mass%, 20 mass%, 30 mass%, 40 mass%, 50 mass%, 55 mass%, 60 mass%, 65 mass%, 70 mass%, 75 mass%, and 80 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, 45% by mass, 35% by mass, 25% by mass, 20% by mass, 15% by mass, and 10% by mass.
The lower limit of the preferable content of the compound represented by the formula (N-05) is 0 mass%, 2 mass%, 5 mass%, 8 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, and 20 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 30 mass%, 28 mass%, 25 mass%, 23 mass%, 20 mass%, 18 mass%, 15 mass%, 13 mass%.
The liquid crystal composition of the present invention may further contain one or more compounds represented by the general formula (N-06). In the formula, R21And R22The same meaning as described above is indicated.
[ solution 14]
The compound represented by the general formula (N-06) is effective in adjusting various physical properties and can be used for obtaining a large refractive index anisotropy Δ N and a high nematic phase-isotropic liquid phase transition temperature TNIAnd a large dielectric anisotropy Δ ∈.
The lower limit of the preferable content of the compound represented by the formula (N-06) is 0 mass%, 2 mass%, 5 mass%, 8 mass%, 10 mass%, 13 mass%, 15 mass%, 17 mass%, and 20 mass% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, 13% by mass, 10% by mass, and 5% by mass.
The liquid crystal composition of the present invention preferably contains one or more compounds selected from the group consisting of compounds represented by general formulae (NU-01) to (NU-08), and more preferably contains one or more compounds selected from the group consisting of compounds represented by general formulae (NU-01) to (NU-08).
[ solution 15]
In the formula, RNU11、RNU12、RNU21、RNU22、RNU31、RNU32、RNU41、RNU42、RNU51、RNU52、RNU61、RNU62、RNU71、RNU72、RNU81And RNU82Independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, and one or two or more-CH groups which are not adjacent to each other2-may be independently substituted with-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-, or-OCO-.
When further detailed, RNU11、RNU12、RNU21、RNU22、RNU31、RNU32、RNU41、RNU42、RNU51、RNU52、RNU61、RNU62、RNU71、RNU72、RNU81And RNU82Preferably C1-5 alkyl or C1-5 alkoxy, more preferably C1-5 alkyl. In the case where importance is attached to the response speed, at least one RNU11、RNU21、RNU41And RNU51The alkenyl group preferably has 2 to 3 carbon atoms, and the alkenyl group represented by the formula (R2) is preferred.
The amount of the compound having an alkenyl group is preferably 30% by mass or less, preferably 25% by mass or less, preferably 20% by mass or less, preferably 15% by mass or less, preferably 10% by mass or less, and preferably 5% by mass or less, based on the total amount of the liquid crystal composition of the present invention. When a high Voltage Holding Ratio (VHR) is regarded as important, the compound having an alkenyl group is preferably 10% by mass or less, preferably 5% by mass or less, preferably 1% by mass or less, and preferably none.
In the formula, RNU11、RNU12、RNU21、RNU22、RNU31、RNU32、RNU41、RNU42、RNU51、RNU52、RNU61、RNU62、RNU71、RNU72、RNU81And RNU82Independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, and one or two or more-CH groups which are not adjacent to each other2-may be independently substituted with-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-, or-OCO-.
When further detailed, RNU11、RNU21、RNU31、RNU41、RNU51、RNU61、RNU71、RNU81Particularly preferably an alkyl group having 1 to 5 carbon atoms, RNU12、RNU22、RNU32、RNU42、RNU52、RNU62、RNU72And RNU82Particularly preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-02).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-03).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-03) and a compound represented by the general formula (NU-04).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-03) and a compound represented by the general formula (NU-05).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-06).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-07).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-08).
The liquid crystal composition of the present invention preferably further contains a compound represented by the general formula (NU-01), a compound represented by the general formula (NU-02), and a compound represented by the general formula (NU-04).
The liquid crystal composition of the present invention preferably further contains a compound represented by the general formula (NU-01), a compound represented by the general formula (NU-03), and a compound represented by the general formula (NU-05).
The liquid crystal composition of the present invention preferably further contains a compound represented by the general formula (NU-01), a compound represented by the general formula (NU-02), a compound represented by the general formula (NU-03), and a compound represented by the general formula (NU-05).
The content of the compound represented by the general formula (NU-01) is preferably 1 to 60% by mass, more preferably 10 to 50% by mass, and still more preferably 20 to 40% by mass.
The content of the compound represented by the general formula (NU-02) is preferably 1 to 40% by mass, more preferably 5 to 25% by mass, and still more preferably 5 to 20% by mass.
The content of the compound represented by the general formula (NU-03) is preferably 1 to 20% by mass, more preferably 0 to 15% by mass, and still more preferably 0 to 10% by mass.
The content of the compound represented by the general formula (NU-04) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 3 to 10% by mass.
The content of the compound represented by the general formula (NU-05) is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 3 to 20% by mass.
The content of the compound represented by the general formula (NU-06) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 3 to 10% by mass.
The content of the compound represented by the general formula (NU-07) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 3 to 10% by mass.
The content of the compound represented by the general formula (NU-08) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 3 to 10% by mass.
The liquid crystal composition of the present invention preferably contains one or more compounds represented by the general formula (I), one or more compounds selected from the group consisting of compounds represented by the general formulae (N-01) to (N-05), and one or more compounds selected from the group consisting of compounds represented by the general formulae (NU-01) to (NU-08), and the total upper limit of the contents of these compounds is preferably 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 89 mass%, 88 mass%, 87 mass%, 86 mass%, 85 mass%, 84 mass%, and the total lower limit of the contents of these compounds is preferably 78 mass%, 80 mass%, 81 mass%, 83 mass%, 85 mass%, 86 mass%, 87 mass%, 88 mass%, 89 mass%, 90 mass%, 91 mass%, 92 mass%, 93 mass%, 94 mass%, 95 mass%, 96 mass%, 97 mass%, 98 mass%, 99 mass%.
The liquid crystal composition of the present invention may further contain a polymerizable compound. Thus, the liquid crystal composition can be used as a liquid crystal composition for PSA mode, PSVA mode, PS mode, or the like. In this case, the polymerizable compound is preferably contained in an amount of 0.01 to 2% by mass.
In more detail, the liquid crystal composition of the present invention preferably contains one or more polymerizable compounds represented by the general formula (RM-1).
[ solution 16]
In the formula, ZM1And ZM2Each independently represent
[ solution 17]
，XM1～XM5Each independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a hydrogen atom or
[ solution 18]
SM1-RM1
，ZM1And ZM2X in (1)M1～XM5Preferably at least one of them is
[ solution 19]
-SM1-RM1
SM1Represents an alkyl group having 1 to 12 carbon atoms or a single bond, and the methylene group in the alkyl group may be substituted by an oxygen atom, -COO-, -OCO-or-OCOO-in such a manner that oxygen atoms are not directly bonded to each other.
RM1Is represented by any one of the following formulae (R-1) to (R-15), preferably formula (R-1) or formula (R-2).
[ solution 20]
In the formula, LM1And LM2Independently of each other, represents a single bond, -O-, -CH2-、-OCH2-、-CH2O-、-CO-、-C2H4-、-COO-、-OCO-、-CH＝CH-COO-、-COO-CH＝CH-、-OCO-CH＝CH-、-CH＝CH-OCO-、-COOC2H4-、-OCOC2H4-、-C2H4OCO-、-C2H4COO-、-OCOCH2-、-CH2COO-、-CH＝CH-、-CF＝CH-、-CH＝CF-、-CF＝CF-、-CF2-、-CF2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-CF2CF2-or-C ≡ C-, LM2When plural, they may be the same or different, and are preferably a single bond, -OCH2-、-CH2O-、-C2H4-、-COO-、-OCO-、-CH＝CH-COO-、-COO-CH＝CH-、-OCO-CH＝CH-、-CH＝CH-OCO-、-COOC2H4-、-OCOC2H4-、-C2H4OCO-、-C2H4COO-、-CF2O-、-OCF2-or-C ≡ C-, more preferably a single bond, -C2H4-、-COO-、-OCO-、-CH＝CH-COO-、-COO-CH＝CH-、-OCO-CH＝CH-、-CH＝CH-OCO-、-COOC2H4-、-OCOC2H4-or-C2H4COO-。
Presence of MM1Represents a 1, 4-phenylene group, a 1, 4-cyclohexylene group or a naphthalene-2, 6-diyl group, wherein a hydrogen atom contained in these groups may be substituted with a fluorine atom, a chlorine atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group or
[ solution 21]
-SM1-RM1
The hydrogen atom in the alkyl or alkoxy group may be substituted with a halogen. MM1When a plurality of them exist, they may be the same or different. MM1Preferably a 1, 4-phenylene group, or a group obtained by substituting a hydrogen atom contained in the above-mentioned group with a fluorine atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.
mM1Represents 0,1 or 2, preferably 0 or 1.
In more detail, as the compound represented by the general formula (RM-1), which is a polymerizable compound, specifically, a compound represented by the following general formula (RM-1A) can be mentioned.
[ solution 22]
In the formula, RM1And SM1R in general formula (RM-1)M1And SM1Same meaning as XM1～XM8Represents hydrogen, fluorine or
[ solution 23]
-SM1-RM1。
In the compound represented by the general formula (RM-1A), the biphenyl skeleton preferably has an unsubstituted structure or a structure represented by any one of the formulae (IV-11) to (IV-14), more preferably an unsubstituted structure or a structure represented by the formula (IV-11).
[ solution 24]
When a liquid crystal composition containing a polymerizable compound having an unsubstituted biphenyl skeleton represented by the formulae (IV-11) to (IV-14) is used, the alignment regulating force in a liquid crystal display element such as a PSA mode, a PSVA mode, or a PS mode becomes optimum, and a good alignment state can be obtained.
The polymerizable compound represented by the general formula (RM-1A) is preferably a compound represented by the following formulae (M1-1) to (M1-4).
[ solution 25]
Further, as the compound represented by the general formula (RM-1), a compound represented by the general formula (RM-1B) can be also exemplified.
[ solution 26]
In the formula, RM1、SM1、LM1、LM2、MM1And mM1R in general formula (RM-1)M1、SM1、LM1、LM2、MM1And mM1Same meaning as XM1～XM5Represents hydrogen, fluorine or
[ solution 27]
-SM1-RM1
The polymerizable compound represented by the general formula (RM-1B) is preferably a compound represented by the following formulae (M1-5) to (M1-22), more preferably a compound represented by the formulae (M1-5) to (M1-21).
[ solution 28]
[ solution 29]
[ solution 30]
The polymerizable compound represented by the general formula (RM-1) has a sufficiently high polymerization rate, and is less likely to precipitate when impregnated into a liquid crystal composition, and the residual amount thereof can be reduced. Therefore, the polymerizable compound-containing liquid crystal composition containing both the compound represented by the general formula (I) and the polymerizable compound, i.e., the compound represented by the general formula (RM-1), can improve the production efficiency by optimizing and reducing the energy cost for production. In addition, in a liquid crystal display element using the liquid crystal composition containing the polymerizable compound, excellent display quality can be obtained in which display defects such as alignment defects and burn-in are not present or are suppressed, and furthermore, a high Voltage Holding Ratio (VHR) and a desired pretilt angle can be satisfied at the same time.
The liquid crystal composition of the present invention may contain one or more compounds having positive dielectric anisotropy, which are described in paragraphs 0236 to 0509 of patent document 5 (japanese patent No. 6233550). Further, a compound having a terphenyl structure or a tetraphenyl structure and having a dielectric anisotropy Δ ∈ of greater than +2 is preferable. The Δ ∈ of the compound is a value extrapolated from a measured value of dielectric anisotropy of a composition in which the compound was added to a composition that was nearly neutral in dielectric properties at 25 ℃. These compounds are used in combination with desired properties such as solubility at low temperatures, transition temperature, electrical reliability, and refractive index anisotropy, and particularly, the reactivity of the polymerizable compound in the liquid crystal composition containing the polymerizable compound can be accelerated.
The lower limit of the content of the compound having a terphenyl structure or a tetraphenyl structure and having a dielectric anisotropy Δ ∈ of more than +2 is preferably 0.1% by mass, 0.5% by mass, 1% by mass, 1.5% by mass, 2% by mass, 2.5% by mass, 3% by mass, 4% by mass, 5% by mass, and 10% by mass, based on the total amount of the liquid crystal composition of the present invention. The upper limit of the preferable content relative to the total amount of the liquid crystal composition of the present invention is, for example, 20 mass%, 15 mass%, 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, and 3 mass% in one embodiment of the present invention.
The liquid crystal composition of the present invention may contain one or more compounds having a nearly neutral dielectric anisotropy (. DELTA.. di-2 to +2) as described in paragraphs 0624 to 0642 of patent document 5 (Japanese patent No. 6233550).
In the case where the liquid crystal composition of the present invention contains a polymerizable compound, polymerization proceeds even in the absence of a polymerization initiator, but a polymerization initiator may be contained in order to promote polymerization. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and acylphosphine oxides.
The liquid crystal composition of the present invention may contain, in addition to the above-mentioned compounds, a conventional nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, an antioxidant, an ultraviolet absorber, a light stabilizer, an infrared absorber, or the like.
The antioxidant may be a hindered phenol represented by general formula (H-1) to general formula (H-4).
[ solution 31]
In the general formula (H-1) to the general formula (H-3), RH1Independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group having 2 to 10 carbon atoms, and one of these groups is-CH2-or two or more non-adjacent-CH2-may be independently substituted with-O-or-S-, respectively, and in addition, one or two or more hydrogen atoms present in these groups may be independently substituted with fluorine atom or chlorine atom, respectively. More specifically, the alkyl group has 2 to 7 carbon atoms, the alkoxy group has 2 to 7 carbon atoms, the alkenyl group has 2 to 7 carbon atoms, or the alkenyloxy group has 2 to 7 carbon atoms, and the alkyl group has 3 to 7 carbon atoms or the alkenyl group has 2 to 7 carbon atoms.
In the general formula (H-4), MH4Represents an alkylene group having 1 to 15 carbon atoms (one or two or more-CH groups in the alkylene group)2-may be substituted by oxygen atoms not directly adjacent to each other by-O-, -CO-, -COO-, -OCO-), -OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CF2CF2-, -CH ═ CH — COO-, -CH ═ CH-OCO-, -COO-CH ═ CH-, -OCO-CH ═ CH-, -C ≡ C-, a single bond, 1, 4-phenylene (any hydrogen atom in the 1, 4-phenylene may be substituted with a fluorine atom) or 1, 4-cyclohexylene, preferably alkylene group having 1 to 14 carbon atoms, preferably having a large carbon number in view of volatility, and preferably having not too large carbon number in view of viscosity, and therefore more preferably having 2 to 12 carbon atoms, and further preferably having a large carbon number in view of viscosityThe carbon number is selected to be 3 to 10, more preferably 4 to 10, still more preferably 5 to 10, and still more preferably 6 to 10.
In general formulae (H-1) to (H-4), one or two or more non-adjacent-CH ═ s in the 1, 4-phenylene group may be substituted with-N ═ s. Further, the hydrogen atoms in the 1, 4-phenylene group may be independently substituted with a fluorine atom or a chlorine atom, respectively.
One or two or more-CH groups which are not adjacent to each other in the 1, 4-cyclohexylene group in the general formula (H-2) or the general formula (H-4)2-may be substituted by-O-or-S-. Further, the hydrogen atoms in the 1, 4-cyclohexylene group may be independently substituted with a fluorine atom or a chlorine atom, respectively.
More specifically, for example, the following formulae (H-11) to (H-15) may be mentioned.
[ solution 32]
In the case where the liquid crystal composition of the present invention contains an antioxidant, the lower limit of the antioxidant is preferably 10 mass ppm, preferably 20 mass ppm, preferably 50 mass ppm, and the upper limit of the antioxidant is 10000 mass ppm, preferably 1000 mass ppm, preferably 500 mass ppm, preferably 100 mass ppm.
The liquid crystal composition of the present invention satisfies various characteristics required for an n-type liquid crystal composition having a negative dielectric anisotropy [ Delta ] [ epsilon ], and has a rotational viscosity [ gamma ]1Sufficiently small, elastic constant K33Large, elastic constant K11Is small. Rotational viscosity gamma1And elastic constant K33Contributes to high-speed responsiveness and has an elastic constant K11And contributes to permeability. Therefore, the liquid crystal composition of the present invention can realize high-speed response and high transmittance when used in a liquid crystal device such as a liquid crystal TV.
< liquid crystal display element >
The liquid crystal display element using the liquid crystal composition of the present invention is a useful element which achieves both high-speed response and high transmittance, is particularly useful for a liquid crystal display element for active matrix driving, and is applicable to a liquid crystal display element for VA mode, PSVA mode, PSA mode, IPS mode, or ECB mode. Among them, the liquid crystal composition of the present invention is suitable for a VA mode, PSVA mode or PSA mode liquid crystal display element.
The liquid crystal display device of the present invention preferably includes: a first substrate and a second substrate arranged oppositely; a common electrode provided on the first substrate or the second substrate; a pixel electrode having a thin film transistor provided on the first substrate or the second substrate; and a liquid crystal layer containing a liquid crystal composition disposed between the first substrate and the second substrate. An alignment film for controlling the alignment direction of liquid crystal molecules may be provided on the side of the first substrate or/and the second substrate facing each other so as to be in contact with the liquid crystal layer. As the alignment film, a vertical alignment film, a horizontal alignment film, or the like can be appropriately selected in accordance with the driving mode of the liquid crystal display element, and a known alignment film such as a rubbing alignment film (for example, polyimide), a photo alignment film (for example, decomposed polyimide), or the like can be used. Further, a color filter may be provided on the first substrate or the second substrate as appropriate, or a color filter may be provided on the pixel electrode or the common electrode.
The liquid crystal display element of the present invention is not particularly limited in each member and manufacturing method, and can be configured and manufactured using a general member and manufacturing method.
When the liquid crystal composition of the present invention contains a polymerizable compound, a method for polymerizing the polymerizable compound is not particularly limited. Among them, in order to obtain good alignment performance of the liquid crystal, it is desirable to carry out polymerization at an appropriate polymerization rate, and therefore, a method of carrying out polymerization by irradiating active energy rays such as ultraviolet rays or electron beams singly or collectively or sequentially is preferable. When ultraviolet light is used, either a polarized light source or an unpolarized light source may be used. In addition, when the polymerization is performed in a state where the liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must be provided with appropriate transparency to the active energy ray. In addition, the following method may also be used: in the case of light irradiation, only a specific portion is polymerized using a mask, and then the orientation state of the unpolymerized portion is changed by changing the conditions such as an electric field, a magnetic field, or temperature, and further, the polymerization is performed by irradiation with an active energy ray. In particular, when ultraviolet exposure is performed, it is preferable to perform ultraviolet exposure while applying a direct current electric field or an alternating current electric field to the liquid crystal composition. The applied ac electric field is preferably an ac electric field having a frequency of 1Hz to 10kHz, more preferably a frequency of 60Hz to 10kHz, and the voltage is selected depending on the desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled according to the applied voltage. In the PSA or PSVA liquid crystal display device, the pretilt angle is preferably controlled to 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast.
In the PSA-type or PSVA-type liquid crystal display device, if the polymerizable compound remains without being polymerized after the device IS manufactured, Image Sticking (IS) occurs. The amount of the residual polymerizable compound is preferably 20ppm or less, more preferably 15ppm or less, particularly preferably 10ppm or less, and particularly preferably 0 or less as the lower limit of detection.
The temperature at the time of irradiation with active energy rays such as ultraviolet rays or electron beams used for polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention is not particularly limited. For example, when the liquid crystal composition of the present invention is applied to a liquid crystal display element including a substrate having an alignment film, it is preferable that the liquid crystal composition is maintained in a temperature range in which a liquid crystal state of the liquid crystal composition is maintained. That is, the polymerization is preferably carried out at 15 to 50 ℃.
As the lamp for generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or the like can be used, and an ultra-high-pressure UV lamp by oxtail (usio) or a fluorescent ultraviolet lamp by TOSHIBA (TOSHIBA) is preferable. The wavelength of the ultraviolet light to be irradiated is preferably ultraviolet light in a wavelength region other than the absorption wavelength region of the liquid crystal composition, and ultraviolet light on the shorter wavelength side is preferably cut off and used as necessary. The intensity of the ultraviolet ray to be irradiated is preferably 0.1mW/cm2～100W/cm2More preferably 2mW/cm2～50W/cm2. IrradiationThe energy of the ultraviolet ray of (2) is suitably adjusted, and preferably 10mJ/cm2～500J/cm2More preferably 100mJ/cm2～200J/cm2。
< method for producing Compound >
In the preparation of the liquid crystal composition of the present invention, suitable are compounds represented by the above general formula (I), more specifically, suitable are compounds represented by the above general formulae (I-A) to (I-X). The compound represented by the general formula (I) can be produced, for example, as follows. Of course, the gist and the application scope of the present invention are not limited to these manufacturing examples.
(production method 1) Synthesis method of Compounds represented by general formula (I-A), general formula (I-B), general formula (I-O) and general formula (I-P)
Production method 1 is a synthesis method represented by the following formula. The general formula (I-Z) comprises the general formula (I-A), the general formula (I-B), the general formula (I-O) and the general formula (I-P).
[ solution 33]
In the formula, R1、Ai1And mi1Represents R in the general formula (I)1、A2And m1，Xi1Represents chlorine, bromine, iodine, benzenesulfonyloxy, p-toluenesulfonyloxy, methanesulfonyloxy, trifluoromethanesulfonyloxy or hydroxy.
The target compounds represented by the general formula (I-Z), i.e., the target compounds represented by the general formulae (I-A), (I-B), (I-O) and (I-P), can be obtained by reacting the compound represented by the general formula (S-2) and a base such as potassium carbonate with the compound represented by the general formula (S-1).
(production method 2) method for synthesizing Compound represented by general formula (I-E)
Production method 2 is a synthesis method represented by the following formula.
[ chemical 34]
First, after preparing a Grignard reagent (Grignard reagent) using 4-bromo-1-iodobenzene and magnesium, it is reacted with methylcyclohexanone. After the obtained compound was dehydrated with p-toluenesulfonic acid, the sonogashira reaction was carried out using 2-methyl-3-butyn-2-ol, tetrakis (triphenylphosphine) palladium as a reaction catalyst, and triethylamine as a base. Further, after the tert-butyl group is deprotected by heating to obtain an acetylene compound, the compound represented by the formula (S-3) is added to carry out the sonogashira reaction again. The obtained compound was placed in an autoclave vessel including a stirring device, and 5% palladium on carbon (aqueous product) and tetrahydrofuran as a solvent were added to conduct a reduction reaction (room temperature, 8 hours) under a hydrogen atmosphere of 0.3 MPa. The obtained compound was taken out, subjected to isomerization reaction using potassium tert-butoxide, and then purified by recrystallization, whereby the target compound represented by the general formula (I-E) was obtained.
(production method 3) method for synthesizing Compound represented by general formula (I-I)
Production method 3 is a synthesis method represented by the following formula.
[ solution 35]
After preparing Grignard reagent by using 4-bromo-1-chloro-3-fluorobenzene and magnesium, reacting with methylcyclohexanone. After the obtained compound was dehydrated with p-toluenesulfonic acid, the compound represented by the formula (S-4) was added, followed by suzuki coupling reaction in a tetrahydrofuran solvent, whereby the target compound represented by the general formula (I-I) was obtained.
(production method 4) method for synthesizing Compound represented by general formula (I-L)
Production method 4 is a synthesis method represented by the following formula.
[ solution 36]
The compound represented by the general formula (I-I) obtained by the production method 3 was placed in an autoclave vessel equipped with a stirrer, and 5% palladium on carbon (aqueous product) and tetrahydrofuran as a solvent were added to conduct a reduction reaction in a hydrogen atmosphere of 0.3MPa (room temperature, 8 hours). The obtained compound was taken out, subjected to isomerization using potassium tert-butoxide, and then purified by recrystallization, whereby the target compound represented by the general formula (I-L) was obtained.
[ examples ]
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the compositions of examples and comparative examples below, "%" means "% by mass".
In the examples, the following abbreviations are used for the description of the compounds.
(side chain)
-n-CnH2n+1Straight chain alkyl group having carbon number n
n-CnH2n+1-linear alkyl group having n carbon atoms
-On-OCnH2n+1Straight chain alkoxy group having carbon number n
nO-CnH2n+1O-straight chain alkoxy group having n carbon atoms
-V-CH＝CH2
V-CH2＝CH-
-V1-CH＝CH-CH3
1V-CH3-CH＝CH-
-F-F
-OCF3-OCF3
(linking group)
-1O--CH2-O-
-O1--O-CH2-
-2--CH2-CH2-
-COO--COO-
-OCO--OCO-
-single bond
(Ring structure)
[ solution 37]
In the examples, the measured properties are as follows. Unless otherwise specified, each physical property value was measured by the method described in the institute of electronic Information Technology industry (Japan Electronics and Information Technology Industries Association, JEITA) ED-2521B published by the 3 rd revision of the society of electronic Information Technology Industries in 2009.
Tni: nematic phase-isotropic liquid phase transition temperature (. degree.C.)
Δ n: refractive index anisotropy at 20 DEG C
Δ ε: dielectric anisotropy at 20 DEG C
γ1: rotational tack (mPa. multidot.s) at 20 DEG C
K11: splay elastic constant (pN) at 20 ℃
K33: bending elastic constant (pN) at 20 DEG C
VHR: under an illumination of 313nm for 60 minutes, 3mW/cm2Voltage holding ratio (%), measured at 1V, 60Hz and 60 ℃ after UV light of (1)
< 1. preparation and evaluation of Compounds
In the following examples, the hydrogen pressure is a pressure at which the atmospheric pressure is 0 MPa. The purity of the compound was analyzed by Gas Chromatography (GC). The analysis conditions are as follows.
(GC analysis conditions)
Pipe column: agilent Technologies, J & W Column (Column) DB-1HT, 15m × 0.25mm × 0.10 μm
Temperature program: 100 deg.C (1 min) - (20 deg.C/min) -250 deg.C- (10 deg.C/min) -380 deg.C- (7 deg.C/min) -400 deg.C (2.64 min)
Injection port temperature: 350 deg.C
Detector temperature: 400 deg.C
[ example 1]
The target compound represented by formula (1) is obtained by a production method represented by the following formula.
[ solution 38]
First, 84g of trans-4-methylcyclohexylcarbinol, 125g of 4-ethoxy-2, 3-difluorophenol, 200g of triphenylphosphine and 700mL of tetrahydrofuran were added to a reaction vessel including a stirring device, a thermometer and a cooling tube under a nitrogen atmosphere, stirred, and cooled to-10 ℃. 144g of azodicarboxyldiisopropyl group was added dropwise thereto, and after stirring at-10 ℃ for 1 hour, the mixture was warmed to room temperature and stirred for 4 hours. Then, the obtained solution was cooled to 0 ℃ and 30mL of water was added, the solvent was distilled off under reduced pressure, 1260mL of hexane, 140mL of toluene, 700mL of methanol, and 50mL of water were added to the obtained residue, the organic layer was separated, washed twice with 1050mL of water/methanol (volume ratio 2/1), and dried with addition of anhydrous sodium sulfate. The obtained solution was concentrated to obtain 154g of a compound as a crude product. Then, by using a mixed solvent of acetone and methanol and repeating recrystallization, 100g of 1-ethoxy-2, 3-difluoro-4- (trans-4-methylcyclohexylmethoxy) benzene as a compound represented by formula (1) was obtained.
Next, the obtained compound represented by formula (1) was evaluated. The results are as follows.
GC purity: 99.8 percent
Phase transition temperature (. degree. C.): cr 34N
1H-Nuclear Magnetic Resonance (NMR) (solvent: deuterated chloroform): δ: 0.88(s,3H),0.90-1.90(m,13H),3.76-3.77(m,2H),3.96-3.99(m,2H),6.58-6.64(m,2H)
[ example 2]
The target compound represented by formula (2) is obtained by a production method represented by the following formula.
[ solution 39]
In a reaction vessel including a stirring device, a thermometer, and a cooling tube under a nitrogen atmosphere, 137g of (trans, trans-4' -methylbicyclohexyl-4-yl) methanol, 125g of 4-ethoxy-2, 3-difluorophenol, 200g of triphenylphosphine, and 700mL of tetrahydrofuran were added and stirred, and cooled to-10 ℃. 144g of azodicarboxyldiisopropyl group was added dropwise thereto, and the mixture was stirred at-10 ℃ for 1 hour, then warmed to room temperature, and stirred for 4 hours. Next, the obtained solution was cooled to 0 ℃, water was added to 30mL, the solvent was distilled off under reduced pressure, 1260mL of hexane, 140mL of toluene, 700mL of methanol, and 350mL of water were added to the obtained residue, the organic layer was separated, washed twice with water/methanol (volume ratio 2/1)1050mL, and dried by adding anhydrous sodium sulfate. The obtained solution was concentrated to obtain 200g of a crude compound. Then, by repeated recrystallization using a mixed solvent of acetone and methanol, 131g of the compound represented by formula (2), i.e., trans-4- (4-ethoxy-2, 3-difluorophenoxymethyl) -4' -methylbicyclohexyl was obtained.
Next, the obtained compound represented by formula (2) was evaluated. The results are as follows.
GC purity: 99.8 percent
Phase transition temperature (. degree. C.): cr 66N 110Iso
1H-NMR (solvent: deuterated chloroform): 0.86(s,3H),1.34(s,3H),0.84-2.08(m,20H),3.74-3.76(m,2H),4.02-4.08(m,2H),6.59-6.61(m,2H)
[ example 3]
The target compound represented by formula (3) is obtained by the production method represented by the following formula.
[ solution 40]
First, in a reaction vessel including a stirrer, a cooler and a thermometer, 4.2g of magnesium and 10mL of tetrahydrofuran were added under a nitrogen atmosphere, and 100mL of a tetrahydrofuran solution containing 30g of 4-bromo-1-chlorobenzene was added dropwise. After completion of the dropwise addition, the reaction mixture was reacted at room temperature for 2 hours, and then 60mL of a tetrahydrofuran solution containing 20g of methylcyclohexanone was added dropwise. After completion of the dropwise addition, the reaction was carried out at room temperature for 3 hours. After completion of the reaction, the reaction mixture was cooled to 5 ℃ or lower, 150mL of 10% hydrochloric acid was added to stop the reaction, 50mL of toluene was added, the organic layer was washed with saturated sodium bicarbonate and saturated brine, and the solvent was distilled off to obtain 36g of the compound represented by formula (S-3).
Then, 36g of the obtained compound represented by the formula (S-3), 180mL of toluene, and 1.5g of p-toluenesulfonic acid monohydrate were placed in a reaction vessel equipped with a stirrer, a Dean-Stark moisture meter, a cooler, and a thermometer, and heated under reflux for 4 hours. After completion of the reaction, the reaction vessel was cooled, 150mL of saturated sodium bicarbonate was added, and the organic layer was concentrated to obtain 28g of the compound represented by the formula (S-4).
Next, 15g of the obtained compound represented by the formula (S-4), 16g of 4-ethoxy-2, 3-difluoro-phenylboronic acid, 61g of potassium carbonate, 250mL of tetrahydrofuran, and 25mL of water were charged into a reaction vessel equipped with a stirrer, a cooler, and a thermometer under a nitrogen atmosphere, and stirred. Then, 1.6g of tetrakis-triphenylphosphine palladium was added as a catalyst at room temperature, followed by refluxing with heat and stirring for 4 hours. After cooling, 200mL of water and 250mL of toluene were added to separate the organic layer, and the organic layer was washed with 250mL of water and 250mL of saturated saline. Then, anhydrous sodium sulfate was added thereto, followed by drying, removal of the organic solvent by distillation under reduced pressure, and purification of the obtained residue by silica gel column chromatography gave 16g of 4-phenyl (4-ethoxy-2, 3-difluorophenyl) -1-methylcyclohexyl-3-ene, which is the compound represented by chemical formula (3).
Next, the obtained compound represented by the chemical formula (3) was evaluated. The results are as follows.
GC purity: 99.9 percent
Phase transition temperature (. degree. C.): cr 124N 139Iso
1H-NMR (solvent: deuterated chloroform): δ: 0.95(d,3H),1.34(t,3H),1.45(m,2H),1.63(s,1H),1.93-2.19(m,4H),4.12(q,2H),5.90-5.97(m,1H),7.08-7.12(m,1H),7.49-7.57(m,5H)
13C-NMR (solvent: deuterated chloroform): δ: 14.7,20.9,28.3,30.2,30.4,35.2,64.6,110.0,118.5,122.3,123.6,126.8,127.7,135.5,135.7,141.1,148.8
[ example 4]
The target compound represented by chemical formula (4) is obtained by a production method represented by the following formula.
[ solution 41]
First, 10g of the compound represented by the formula (3) synthesized in example 3, 1g of 5% palladium on carbon, 150mL of tetrahydrofuran, and 20mL of ethanol were charged into an autoclave vessel equipped with a stirrer, and reduction was carried out using 0.3MPa of hydrogen (room temperature, 8 hours). After the obtained reaction solution was filtered with a filtering agent, the organic solvent was distilled off under reduced pressure. Then, the obtained reaction product, 100mL of N, N-dimethylformamide and 2g of potassium tert-butoxide were charged into a reaction vessel equipped with a stirrer, a cooler and a thermometer under a nitrogen atmosphere, and the mixture was stirred at 90 ℃ for 4 hours. After cooling, 200mL of water and 100mL of toluene were added to separate the organic layer, and 250mL of water and 250mL of saturated saline were further used to wash the organic layer. Then, anhydrous sodium sulfate was added thereto and the mixture was dried, the organic solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography and recrystallization from ethyl acetate to obtain 16g of 4-ethoxy-2, 3-difluoro-4' - (trans-4-methylcyclohexyl) biphenyl, a compound represented by chemical formula (4).
Next, the obtained compound represented by the chemical formula (4) was evaluated. The results are as follows.
GC purity: 99.6 percent
Phase transition temperature (. degree. C.): cr 94N 98Iso
1H-NMR (solvent: deuterated chloroform): δ: 0.87(d,3H),1.32(t,3H),1.38-1.47(m, 3H)H),1.59-1.63(m,4H),1.83-1.87(m,2H),2.70-2.73(m,1H),4.12(q,2H),5.90-5.97(m,1H),7.08-7.12(m,1H),7.34-7.38(m,2H),7.49-7.57(m,3H)
13C-NMR (solvent: deuterated chloroform): δ: 14.7,20.9,28.3,30.2,30.4,31.6,33.2,64.6,110.0,118.5,122.3,123.6,126.8,127.7,135.5,135.7,141.3,148.6
< 2. preparation and evaluation of liquid Crystal composition
First, the liquid crystal compositions (LC-1) to (LC-9) of examples 4 to 13 and the liquid crystal compositions (C-1) to (C-4) of comparative examples 1 to 4 were prepared, and their physical property values were measured. The component ratios of these liquid crystal compositions are shown in tables 1 to 3, and the physical property values thereof are shown in tables 4 to 6.
Next, VA liquid crystal display elements were obtained by injecting each of these liquid crystal compositions into a cell with Indium Tin Oxide (ITO) coated with a polyimide alignment film causing vertical (homeotropic) alignment with a cell gap of 3.0 μm by a vacuum injection method.
The VA liquid crystal display devices using the liquid crystal compositions obtained in examples 4 to 13 were subjected to an electro-optical characteristic evaluation test using an optical evaluation apparatus (OCA-100). The driving voltage and transmittance were measured from the V-T curve at this time. Further, the elastic constant and the low-temperature storage property were measured.
Response speed: the response speed was measured at a Von of 5V, a Voff of 0.5V and a measurement temperature of 20 ℃ using DMS703 available from Autronic-Melchers as a measurement instrument. The ^ mark in tables 4 to 6 means a sufficiently fast response, the good-quality mark means a fast response, and the × mark means a slow response.
Driving voltage: a60 Hz rectangular wave was applied to a VA mode liquid crystal display device, and a response time-VT curve was measured. The voltage at which the transmittance reached 90% was measured according to the VT curve and used as the driving voltage. The good mark means an appropriate driving voltage.
Transmittance: the transmittance was measured when a voltage of 0V to 10V was applied to the cell. The good marks in tables 4 to 6 indicate sufficiently high transmittance, and the x mark indicates low transmittance.
Elastic constant: the splay elastic constant and the bend elastic constant of each liquid crystal composition were measured at 20 ℃ using an elastic constant measuring system ("EC-1 type", manufactured by toyoyang technologies).
Low-temperature storage property: after the polymerizable compound-containing liquid crystal compositions of examples 14 to 49 were cooled at-20 ℃ for 240 hours, the presence or absence of the deposition of the polymerizable compound was observed as an index of low-temperature storage stability. The good marks in tables 4 to 6 mean no precipitation and no display defects such as bright spots, the Δ mark means the smectic property, and the × mark means precipitation.
[ Table 1]
[ Table 2]
[ Table 3]
[ Table 4]
[ Table 5]
[ Table 6]
As shown in tables 4 to 6, examples were confirmedThe liquid crystal compositions of examples 5 to 7 had rotational viscosity γ higher than that of the liquid crystal composition of comparative example 11And elastic constant K11Small, rotational viscosity gamma1Relative to elastic constant K33Ratio of (a) to (b), i.e. gamma1/K33Small value of (A), a parameter that governs the steepness of the electro-optic effect, namely K11/K33Sufficiently small, and excellent in response speed and transmittance.
In addition, the same results as those obtained when the liquid crystal compositions of examples 5 to 7 and the liquid crystal composition of comparative example 1 were compared were obtained when the liquid crystal compositions of examples 8 to 10 and the liquid crystal composition of comparative example 2 were compared, when the liquid crystal compositions of examples 11 to 12 and the liquid crystal composition of comparative example 3 were compared, and when the liquid crystal composition of example 13 and the liquid crystal composition of comparative example 4 were compared.
From the above, it was confirmed that the embodiments solve the problems of the present invention.
Further, the polymerizable compound-containing liquid crystal compositions of examples 14 to 49 were prepared by mixing these liquid crystal compositions with one or two of the polymerizable compounds represented by the above-mentioned formulae (M1-2), (M1-3), (M1-5) to (M1-9), (M1-12) to (M1-14) and (M1-16). The formulation ratios of the liquid crystal composition and the polymerizable compound are shown in tables 7 to 13.
[ Table 7]
[ Table 8]
[ Table 9]
[ Table 10]
[ Table 11]
[ Table 12]
[ Table 13]
Further, the liquid crystal compositions containing the polymerizable compounds of examples 14 to 49 were injected into ITO-equipped cells each having a cell gap of 3.0 μm and coated with a polyimide alignment film causing vertical alignment by a vacuum injection method, to obtain Vertical Alignment (VA) liquid crystal display elements. The obtained VA liquid crystal display element was used with 100mW/cm while applying a rectangular wave of 10V and 100Hz-2A high-pressure mercury lamp with an intensity of (365nm) was used for the exposure of 10J. Then, by performing 100J exposure in a voltage-off state, a Polymer Stabilized Vertical Alignment (PSVA) liquid crystal display element was obtained.
The VA liquid crystal display devices and PSVA liquid crystal display devices using the liquid crystal compositions containing the polymerizable compounds of examples 14 to 49 were measured for response speed, drive voltage, low-temperature storage stability, and transmittance in the same manner as the VA liquid crystal display devices using the liquid crystal compositions of examples 4 to 13, and the same results as those were obtained.
Next, the amount of the polymerizable compound remaining in the liquid crystal display devices obtained in examples 14 to 49 was confirmed, and as a result, the remaining amount was sufficiently small. This confirmed that the PSVA liquid crystal display device was less likely to cause display defects due to a change in the pretilt angle.
Further, an antioxidant-containing liquid crystal composition (example 50) in which an antioxidant represented by the following formula (H-2-R3) was added in an amount of 50ppm to the liquid crystal composition of example 4, an antioxidant-containing liquid crystal composition (example 51) in which an antioxidant represented by the formula (H-3-R3) was added in an amount of 30ppm to the liquid crystal composition of example 4, and an antioxidant-containing liquid crystal composition (example 52) in which an antioxidant represented by the formula (H-4-M8) was added in an amount of 50ppm to the liquid crystal composition of example 4 were prepared.
[ solution 42]
Using the obtained antioxidant-containing liquid crystal compositions of examples 50 to 52, a VA liquid crystal display element was produced in the same manner as described above, and then VHR was evaluated.
From the VHR results, it was confirmed that the VA liquid crystal display devices using the antioxidant-containing liquid crystal compositions of examples 50 to 52 were more reliable and excellent in thermal stability than the VA liquid crystal display device using the antioxidant-free liquid crystal composition of example 14.
As described above, it was confirmed that the liquid crystal composition of the present invention is an excellent liquid crystal composition which can achieve all of high-speed response, low driving voltage, good low-temperature storage stability, and high transmittance when used in a VA liquid crystal display element and a PSVA display element.
Claims (13)
1. A liquid crystal composition comprising one or more compounds represented by the general formula (I),
in the formula, R1Represents an alkyl group having 1 to 8 carbon atoms or a carbon atomAlkenyl group of the sub-number 2 to 8, -CH in these groups2-or two or more-CHs not adjacent to each other2-may each be independently substituted by-O-or-S-, and in addition, one or two or more hydrogen atoms present in these groups may each be independently substituted by a fluorine atom or a chlorine atom,
ring A1Is 1, 4-cyclohexylene or 1, 4-cyclohexenylene,
A2each independently represents 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 3, 5-difluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 1, 4-cyclohexenylene, 1, 4-bicyclo [2.2.2 ] phenylene]Octyl, piperidine-1, 4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, wherein one or two or more hydrogen atoms of these groups may be independently substituted by halogen, cyano, nitro, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms, wherein a hydrogen atom of the alkyl group, the alkoxy group or the alkenyl group may be substituted by halogen, A2When a plurality of them exist, they may be the same or different,
Z0represents-OCH2-、-CH2O-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-or a single bond,
m1represents a number of 0,1 or 2,
wherein m is1Is 1, ring A1And A2Is 1, 4-cyclohexylene and Z0Except for the case of a single bond.
2. A liquid-crystal composition according to claim 1, wherein ring A in the formula (I)1Is a 1, 4-cyclohexylene group.
3. The liquid crystal composition according to claim 1 or 2, wherein m in the general formula (I)1Is 1.
4. A liquid crystal composition according to any one of claims 1 to 3, wherein A in the general formula (I)2Is 1, 4-cyclohexylene, 1, 4-phenylene or 1, 4-phenyleneOne or more hydrogen atoms in the cyclohexenyl group can be substituted by halogen, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, or alkenyl group having 2 to 12 carbon atoms, and the hydrogen atoms in the alkyl group, the alkoxy group, or the alkenyl group can be substituted by halogen.
5. The liquid crystal composition according to any one of claims 1 to 4, further comprising one or more compounds selected from the group consisting of compounds represented by general formulae (N-01) to (N-05) except the compound represented by general formula (I),
in the formula, R21And R22Independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, and one or two or more-CH groups which are not adjacent to each other2-may be independently substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-or-OCO-,
Z1each independently represents a single bond, -CH2CH2-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-, -CH-, -CF-or-C.ident.C-,
m independently represents 1 or 2.
6. The liquid crystal composition according to any one of claims 1 to 5, further comprising one or more compounds selected from the group consisting of compounds represented by general formulae (NU-01) to (NU-08),
in the formula, RNU11、RNU12、RNU21、RNU22、RNU31、RNU32、RNU41、RNU42、RNU51、RNU52、RNU61、RNU62、RNU71、RNU72、RNU81And RNU82Independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, and one or two or more-CH groups which are not adjacent to each other2-may be independently substituted with-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-, or-OCO-.
7. The liquid crystal composition according to claim 6, wherein the total content of the one or more compounds represented by the general formula (I), the one or more compounds selected from the group consisting of the compounds represented by the general formulae (N-01) to (N-05), and the one or more compounds selected from the group consisting of the compounds represented by the general formulae (NU-01) to (NU-08) is 80 to 100% by mass.
8. The liquid crystal composition according to any one of claims 1 to 7, further comprising one or more polymerizable compounds represented by the general formula (RM-1),
in the formula, ZM1And ZM2Each independently represent
XM1～XM5Each independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a hydrogen atom or
-SM1-RM1，
XM1～XM5At least one table ofDisplay device
-SM1-RM1，
SM1Represents an alkylene group having 1 to 12 carbon atoms or a single bond, wherein-CH in the alkylene group2May be substituted by oxygen atoms, -COO-, -OCO-or-OCOO-, in such a way that the oxygen atoms are not directly bonded to one another,
RM1represents any one of the following formulae (R-1) to (R-15),
LM1and LM2Each independently represents a single bond, -O-, -CH2-、-OCH2-、-CH2O-、-CO-、-C2H4-、-COO-、-OCO-、-CH＝CH-COO-、-COO-CH＝CH-、-OCO-CH＝CH-、-CH＝CH-OCO-、-COOC2H4-、-OCOC2H4-、-C2H4OCO-、-C2H4COO-、-OCOCH2-、-CH2COO-、-CH＝CH-、-CF＝CH-、-CH＝CF-、-CF＝CF-、-CF2-、-CF2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-CF2CF2-or-C ≡ C-, LM2When a plurality of them exist, they may be the same or different,
MM1represents a 1, 4-phenylene group, a 1, 4-cyclohexylene group or a naphthalene-2, 6-diyl group, wherein a hydrogen atom contained in these groups may be substituted with a fluorine atom, a chlorine atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group or
-SM1-RM1，
The hydrogen atom in the alkyl or alkoxy group may be substituted by halogen,
mM1represents a number of 0,1 or 2,
XM1～XM5、SM1、RM1、LM2and MM1When a plurality of them exist, they may be the same or different.
9. The liquid crystal composition according to claim 8, comprising one or more compounds represented by the general formula (I), one or more compounds selected from the group consisting of compounds represented by the general formulae (N-01) to (N-05), one or more compounds selected from the group consisting of compounds represented by the general formulae (NU-01) to (NU-08), and a polymerizable compound represented by the general formula (RM-1), and further comprising an antioxidant, an ultraviolet absorber, a light stabilizer and an infrared absorber, which are optionally contained.
10. A liquid crystal display element using the liquid crystal composition according to any one of claims 1 to 9.
11. A liquid crystal display element for active matrix driving, using the liquid crystal composition according to any one of claims 1 to 9.
12. A polymer-stabilized alignment type, vertical alignment type or polymer-stabilized vertical alignment type liquid crystal display element using the liquid crystal composition as claimed in any one of claims 1 to 9.
13. A compound represented by the general formula (I),
in the formula, R1Represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, wherein-CH in these groups2-or two or more-CHs not adjacent to each other2-may each be independently substituted by-O-or-S-, and in addition, one or two or more hydrogen atoms present in these groups may each be independently substituted by a fluorine atom or a chlorine atom,
ring A1Is 1, 4-cyclohexylene or 1, 4-cyclohexenylene,
A2each independently represents 1, 4-ylideneCyclohexyl, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 3, 5-difluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 1, 4-cyclohexenylene, 1, 4-bicyclo [2.2.2 ] phenylene]Octyl, piperidine-1, 4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, wherein one or two or more hydrogen atoms of these groups may be independently substituted by halogen, cyano, nitro, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms, wherein a hydrogen atom of the alkyl group, the alkoxy group or the alkenyl group may be substituted by halogen, A2When a plurality of them exist, they may be the same or different,
Z0represents-OCH2-、-CH2O-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-or a single bond,
m1represents a number of 0,1 or 2,
wherein m is1Is 1, ring A1And A2Is 1, 4-cyclohexylene and Z0Except for the case of a single bond.
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| CN103348283A (en) * | 2011-12-19 | 2013-10-09 | Dic株式会社 | Liquid crystal display device |
| JP5510617B1 (en) * | 2013-03-26 | 2014-06-04 | Ｄｉｃ株式会社 | Liquid crystal composition and liquid crystal display device using the same |
| CN104428396A (en) * | 2013-01-21 | 2015-03-18 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display device using same |
| CN104837957A (en) * | 2012-12-12 | 2015-08-12 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display element using same |
| CN105518105A (en) * | 2013-09-06 | 2016-04-20 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display element using same |
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| US11008515B2 (en) | 2017-11-24 | 2021-05-18 | Merck Patent Gmbh | Liquid-crystalline medium |
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| CN103348283A (en) * | 2011-12-19 | 2013-10-09 | Dic株式会社 | Liquid crystal display device |
| CN104837957A (en) * | 2012-12-12 | 2015-08-12 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display element using same |
| CN104428396A (en) * | 2013-01-21 | 2015-03-18 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display device using same |
| JP5510617B1 (en) * | 2013-03-26 | 2014-06-04 | Ｄｉｃ株式会社 | Liquid crystal composition and liquid crystal display device using the same |
| US20160075946A1 (en) * | 2013-03-26 | 2016-03-17 | Dic Corporation | Liquid crystal composition and liquid crystal display device using the same |
| CN105518105A (en) * | 2013-09-06 | 2016-04-20 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display element using same |
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