CN108779395B

CN108779395B - Nematic liquid crystal composition and liquid crystal display element using same

Info

Publication number: CN108779395B
Application number: CN201780018636.0A
Authority: CN
Inventors: 须藤豪; 后藤麻里奈
Original assignee: DIC Corp
Current assignee: Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
Priority date: 2016-04-27
Filing date: 2017-04-13
Publication date: 2022-01-11
Anticipated expiration: 2037-04-13
Also published as: CN108779395A; WO2017188005A1; KR20180134851A; JP6265312B1; JPWO2017188005A1

Abstract

The problem to be solved by the present invention is to require that Δ ∈ be negative, that the absolute value be large, and that the rotational viscosity (γ) be high₁) Low, elastic constant (K)₃₃) Large, solid phase-nematic phase transition temperature (T)_cn) Low nematic-isotropic liquid phase transition temperature (T)_ni) High and high Voltage Holding Ratio (VHR). Further, it is an object of the present invention to provide a VA-type, PSVA-type, PSA-type, FFS-type, or other liquid crystal display device using the same, which has excellent display quality and high-speed response, and in which display defects such as burn-in and display unevenness are not generated or suppressed. A liquid crystal composition having a negative dielectric anisotropy (Delta epsilon) and containing a compound represented by the formula (I-1) as a first component and a compound represented by the formula (I-2) as a second component, and a liquid crystal display element using the same are provided.

Description

Nematic liquid crystal composition and liquid crystal display element using same

Technical Field

The present invention relates to a nematic liquid crystal composition useful as a liquid crystal display material and exhibiting a negative dielectric anisotropy (Δ ∈), and a liquid crystal display element using the same.

Background

Liquid crystal display devices have been used for clocks, calculators, and various household electrical appliances, measuring devices, panels for automobiles, cellular phones, personal computers, televisions, and the like. Representative examples of the liquid crystal display mode include TN (twisted nematic) mode, STN (super twisted nematic) mode, DS (dynamic light scattering) mode, GH (guest host) mode, IPS (in-plane switching) mode, FFS (fringe field switching) mode, OCB (optically compensated birefringence) mode, ECB (voltage controlled birefringence) mode, VA (vertical alignment) mode, PSVA mode, PSA mode, CSH (color super homeotropic) mode, and FLC (ferroelectric liquid crystal). Further, as a driving method, a static driving method, a multiplex driving method, a simple matrix method, and an Active Matrix (AM) method in which driving is performed by a TFT (thin film transistor), a TFD (thin film diode), or the like can be cited.

Among these display modes, the IPS mode, FFS mode, ECB mode, VA mode, CSH mode, and the like have a characteristic of using a liquid crystal material exhibiting a negative Δ ∈. Among them, the VA display system using AM driving is used for display elements requiring high speed and a wide viewing angle, for example, televisions. The FFS type display system can achieve high transmittance, and is used for mobile applications such as a smart phone.

Nematic liquid crystal compositions (hereinafter referred to as liquid crystal compositions) used in display systems such as VA-mode and FFS-mode display systems are required to have low voltage driving, high-speed response, a wide operating temperature range, and high reliability. That is, it is required that Δ ∈ be negative, have a large absolute value, and have rotational viscosity (γ)₁) Low, elastic constant (K)₃₃) Large, solid phase-nematic phase transition temperature (T)_cn) Low nematic-isotropic liquid phase transition temperature (T)_ni) High and high Voltage Holding Ratio (VHR). In addition, Δ n of the liquid crystal material must be adjusted to an appropriate range in conjunction with the cell gap according to the setting of Δ n × d, which is the product of the refractive index anisotropy (Δ n) and the cell gap (d).

In response to such a demand, various studies have been made on compounds having negative Δ ∈ and large absolute values, thereby improving the characteristics of liquid crystal compositions. For example, as a liquid crystal material having a negative Δ ∈, a liquid crystal composition using liquid crystal compounds (a) and (B) having a 2, 3-difluorophenylene skeleton as described below (see patent document 1) is disclosed.

[ solution 1]

The liquid crystal composition uses the liquid crystal compounds (C) and (D) as the compounds having Δ ∈ of substantially 0, but the liquid crystal composition cannot be said to have sufficiently low viscosity in a liquid crystal composition requiring high-speed response such as a liquid crystal television.

[ solution 2]

On the other hand, a liquid crystal composition using a compound represented by formula (E) is disclosed, but the liquid crystal composition is a liquid crystal composition in which Δ n is small in combination with the liquid crystal compound (D) (see patent document 2) and a liquid crystal composition in which a compound having an alkenyl group in the molecule (alkenyl compound) such as the liquid crystal compound (F) is added in order to improve the response speed (see patent document 3), and there is a problem of satisfying both high Δ n and high reliability.

[ solution 3]

Further, a liquid crystal composition using a compound represented by the formula (G) is disclosed (see patent document 4), but since this liquid crystal composition is also a liquid crystal composition containing a compound including an alkenyl compound such as the above-mentioned liquid crystal compound (F), there is a problem that display defects such as burn-in and display unevenness are likely to occur.

[ solution 4]

Among them, an influence of a liquid crystal composition containing an alkenyl compound on a display defect is disclosed (see patent document 5), and in general, if the content of the alkenyl compound is reduced, η of the liquid crystal composition increases and a high-speed response is difficult to achieve, and therefore, there is a problem that both suppression of a display defect and a high-speed response are achieved.

By combining a compound exhibiting a negative value of Δ ∈ with the liquid crystal compounds (C), (D), and (F) in this way, it is difficult to develop a liquid crystal composition that has both high Δ n and low rotational viscosity (γ)₁) And a liquid crystal composition having a negative Δ ∈ and showing no or suppressed display failure.

The PSA (Polymer stabilized Alignment) type, which is one of the VA type display modes, has the following features: the structure in which a polymer structure is formed in a cell in order to control the pretilt angle of liquid crystal molecules has high-speed response and high contrast. The preparation method comprises the following steps: a liquid crystal composition containing a polymerizable compound and a liquid crystal compound is injected between substrates, and the polymerizable compound is polymerized while liquid crystal molecules are aligned by applying a voltage, thereby fixing the alignment of the liquid crystal molecules. Therefore, as a problem specific to PSA type, display defects due to burn-in or the like caused by the reactant of the polymerizable compound may occur. The cause of this burn-in is the presence of a causative substance in the liquid crystal composition of the PSA element. Specifically, when a PSA element is manufactured, a polymerization reaction product generated in the polymerization process of the polymerizable compound causes adverse effects such as burn-in. Further, the polymerizable compound reacts with the components of the liquid crystal composition, and the reactant causes adverse effects such as image sticking.

Optimization of the polymerizable compound and optimization of the composition of the liquid crystal composition are problems of display defects caused by burn-in and the like that may occur in PSA type devices having useful display performance (contrast and response speed). In particular, a liquid crystal composition containing a liquid crystal material having an alkenyl group, which is effective for reducing the viscosity, is effective for reducing the response speed, but problems such as display defects may occur after polymerization of a polymerizable compound in the production process of a PSA-type display device.

As described above, the liquid crystal composition used in VA mode, FFS mode or the like, and the liquid crystal composition for producing PLiquid crystal compositions used for devices whose alignment is controlled by a reactant of a polymerizable compound, such as SVA type and PSA type, are required to have negative Δ ε, a large absolute value, and low rotational viscosity (γ ∈)₁) Large elastic constant (K)₃₃) Low solid phase-nematic phase transition temperature (T)_cn) High nematic phase-isotropic liquid phase transition temperature (T)_ni) And a high Voltage Holding Ratio (VHR). Further, there is a need for a liquid crystal display element which does not suffer from deterioration due to UV irradiation during production and use of the element, does not affect display even if deterioration occurs, does not suffer from display defects such as burn-in and display unevenness, or is suppressed in display defects, and has excellent display quality and high-speed response.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. H8-104869

Patent document 2: european patent application publication No. 0474062

Patent document 3: japanese unexamined patent publication No. 2006-37054

Patent document 4: japanese Kokai publication 2001-354967

Patent document 5: japanese laid-open patent publication No. 2008-144135

Disclosure of Invention

Problems to be solved by the invention

The present invention addresses the problem of providing a liquid crystal composition having negative Δ ∈ and a large absolute value, and having low rotational viscosity (γ)₁) Large elastic constant (K)₃₃) Low solid phase-nematic phase transition temperature (T)_cn) High nematic phase-isotropic liquid phase transition temperature (T)_ni) And a liquid crystal display element such as VA type, PSVA type, PSA type, FFS type, etc., which has a low dissolution stability at low temperature and a high Voltage Holding Ratio (VHR), and in which the reliability of the liquid crystal composition is less reduced after UV irradiation, and which is free from display defects such as burn-in and display unevenness, or in which display defects are suppressed, has excellent display quality, and has a high-speed response.

Means for solving the problems

The present inventors have studied various compounds and found that the above-mentioned problems can be solved by combining specific compounds, and thus have completed the present invention.

A liquid crystal composition having a negative dielectric anisotropy (Delta epsilon) and a liquid crystal display element using the same are provided, the liquid crystal composition of the present invention contains a compound represented by the formula (I-1) as a first component and a compound represented by the formula (I-2) as a second component.

[ solution 5]

(in the formula, R¹¹Represents 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, R¹²Represents 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. )

[ solution 6]

(wherein P represents a polymerizable group, S represents a single bond or a spacer group, and when there are a plurality of S, they may be the same or different, and X represents-O-, -S-, -OCH₂-、-CH₂O-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-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-, -CH-, -CF-or a single bond, and when a plurality of X's are present, they may be the same or different, and A¹、A²、A³、A⁴And A⁵Each independently represents 1, 4-phenylene, naphthalene-1, 4-diyl or naphthalene-2, 6-diyl, in which the hydrogen atoms may be substituted by 1 or more L, A⁵When plural, they may be the same or different, Z¹、Z²And Z³Each independently represents-O-, -S-, -OCH₂-、-CH₂O-、-COO-、-OCO-、-CO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-CH₂CH₂-、-CH₂CF₂-、-CF₂CH₂-、-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-, -CH ═ CH-, -CF ═ CF-, or-C ≡ C-, or a single bond, and R represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group (ペンタフルオロスルフラニル group), a cyano group, a nitro group, an isocyano group, a thioisocyano group, or a straight-chain or branched alkyl group having 1 to 12 carbon atoms, wherein 1-CH-, -CF ≡ C-, -C ≡ C-, or a single bond₂-or non-adjacent 2 or more-CH₂-each independently may be substituted by-O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH ═ CH-COO-, -CH ═ CH-OCO-, -COO-CH ═ CH-, -OCO-CH ═ CH-, -CF ═ CF-, or-C ≡ C-, L represents an integer from 0 to 8, m1, m2, and m3 represent 0 or 1, n represents 0, 1, or 2, L represents a methyl group, a methoxy group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, m1+ m2+ m3 represents 0 or 1. )

ADVANTAGEOUS EFFECTS OF INVENTION

The liquid crystal composition of the present invention has a negative Δ ∈ and a large absolute value, and has a rotational viscosity (γ)₁) Low, elastic constant (K)₃₃) Large, solid phase-nematic phase transition temperature (T)_cn) Low nematic-isotropic liquid phase transition temperature (T)_ni) High, has a solubility stability at low temperature andthe liquid crystal display device has a high Voltage Holding Ratio (VHR), and VA, PSVA, PSA, FFS and the like liquid crystal display devices manufactured using the same have a high VHR, are free from display defects such as burn-in and display unevenness, are suppressed in display defects, have excellent display quality, and have a high-speed response.

Detailed Description

The liquid crystal composition of the present invention contains a compound represented by the general formula (I-1) as a first component.

[ solution 7]

The compound represented by the general formula (I-1) is contained in an amount of 3 to 70% by mass, and the lower limit thereof is preferably 5% by mass, preferably 10% by mass, preferably 15% by mass, preferably 20% by mass, preferably 25% by mass, preferably 30% by mass, preferably 35% by mass, preferably 40% by mass; the upper limit value is preferably 65% by mass, preferably 60% by mass, preferably 55% by mass, preferably 50% by mass, preferably 45% by mass, preferably 40% by mass, preferably 35% by mass, preferably 30% by mass. In further detail, to obtain a low rotational viscosity (γ)₁) The content is preferably 30 to 65% by mass, and when importance is attached to suppression of precipitation at low temperatures, the content is preferably 5 to 30% by mass.

In the general formula (I-1), R¹¹Represents 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, R¹¹Preferably represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, preferably an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms.

In the general formula (I-1), R¹²Represents 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, R¹²Preferably represents an alkyl group having 1 to 5 carbon atomsAn alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and particularly preferably an alkenyl group having 2 to 3 carbon atoms.

Contains a compound represented by the general formula (I-2) as a second component.

[ solution 8]

The compound represented by the general formula (I-2) is characterized by having 4 or more benzene rings or naphthalene rings as aromatic rings and having one polymerizable group. The compound represented by the general formula (I-2) is contained in an amount of 0.01 to 5% by mass, and the lower limit thereof is preferably 0.1% by mass, preferably 0.2% by mass, preferably 0.3% by mass, preferably 0.5% by mass, preferably 1% by mass, 1.5% by mass, preferably 2% by mass; the upper limit value is preferably 4.5% by mass, preferably 4% by mass, preferably 3.5% by mass, preferably 3% by mass, preferably 2.5% by mass, preferably 2% by mass, preferably 1.5% by mass, preferably 1% by mass, preferably 0.5% by mass. More specifically, the content thereof is preferably 0.3 to 3% by mass in order to obtain a high Voltage Holding Ratio (VHR), and when suppression of precipitation at low temperatures is important, the content thereof is preferably 0.1 to 1% by mass.

In the general formula (I-2), P represents a polymerizable group, specifically a group selected from the group consisting of the formulas (P-1) to (P-18).

[ solution 9]

P is preferably a compound of the formula (P-1), the formula (P-2) or the formula (P-3), particularly preferably the formula (P-1) or the formula (P-2).

S represents a single bond or a spacer, and the spacer may be, for example, an alkylene group having 1 to 20 carbon atoms, 1 or 2 or more-CH groups which are not adjacent to each other₂Each independently may be substituted by-O-, -COO-and-OCO-or-OCO-O-substituted, and when a plurality of S groups are present, they may be the same or different. More preferably, S is a spacer group.

A¹、A²、A³And A⁴Each independently represents 1, 4-phenylene, naphthalene-1, 4-diyl or naphthalene-2, 6-diyl, in which the hydrogen atoms may be substituted by 1 or more L, A⁵When a plurality of A's are present, they may be the same or different, and preferably at least 1A⁵Substituted with 1 or more L.

A¹、A²、A³、A⁴And A⁵Specifically, a group selected from the following formulae (A-1) to (A-10) can be mentioned.

[ solution 10]

L represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group or a methoxy group, and preferably a fluorine atom, a chlorine atom, a methyl group or a methoxy group. Wherein the hydrogen atom of the methyl group or methoxy group may be optionally substituted with a fluorine atom.

l represents 0, 1 or 2, preferably 1.

n represents 0, 1 or 2, preferably 0.

Z¹、Z²And Z³Each independently represents-O-, -S-, -OCH₂-、-CH₂O-、-COO-、-OCO-、-CO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-CH₂CH₂-、-CH₂CF₂-、-CF₂CH₂-、-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-、-CH＝CH-、When a plurality of-CF-or-C.ident.C-or single bonds are present, they may be the same or different, and each is independently preferably a single bond, -OCH₂-、-CH₂O-、-COO-、-OCO-、-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂CH₂-OCO-, -CH ═ CH-or-C ≡ C-, preferably Z¹、Z²And Z³At least 1 of them is a single bond, preferably all are single bonds.

X represents-O-, -S-, -OCH₂-、-CH₂O-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-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-, -CH ═ CH-, -CF ═ CF-, or a single bond, and when a plurality of X are present, they may be the same or different, and are preferably-O-, -COO-, -OCO-, or a single bond.

R represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or a linear or branched alkyl group of 1 to 12 carbon atoms, wherein 1-CH₂-or non-adjacent 2 or more-CH₂Each independently of the others may be substituted by-O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH-COO-, -CH-OCO-, -COO-CH-, -OCO-CH-, -CH-, -CF-or-C.ident.C-, and is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or 1 or not adjacent 2 or more-CH-₂Straight-chain or branched alkyl group of 1 to 12 carbon atoms each independently substitutable with-O-, -COO-, -OCO-, -O-CO-O-, more preferably a hydrogen atom, a fluorine atom, a straight-chain alkyl group of 1 to 12 carbon atoms, a branched alkyl group of 2 to 12 carbon atoms, a straight-chain alkoxy group of 1 to 12 carbon atoms2 to 12 branched alkoxy. l represents an integer of 0 to 8, m1, m2 and m3 represent 0 or 1, n represents 0, 1 or 2, and m1+ m2+ m3 represents 0 or 1.

The compound represented by the general formula (I-2) is more preferably a compound represented by the general formula (I-3).

[ solution 11]

Wherein P and R are the same as those in the general formula (I-2), and S¹And S²Each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, 1 or 2 or more-CH groups which are not adjacent to each other₂May be substituted by-O-, -COO-, -OCO-, -OCOO-, X¹And X²Each independently represents-O-, -S-, -OCH₂-、-CH₂O-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-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-, -CH ═ CH-, -CF ═ CF-, -C ≡ C-, or a single bond, Z ≡ C-⁴Represents a single bond, -O-, -S-, -OCH₂-、-CH₂O-、-COO-、-OCO-、-CO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-CH₂CH₂-、-CH₂CF₂-、-CF₂CH₂-、-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-, -CH ═ CH-, -CF ═ CF-or-C ≡ C-, a⁶And A⁷Each independently represents 1, 4-phenylene, naphthalene-2, 6-diyl, in which a hydrogen atom may be substituted by an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, a halogen atom, a cyano group or a nitro group, n1 represents 3, and 3A's present⁶And Z⁴Each may be the same or different.

As the compounds represented by the general formula (I-2), specifically, compounds represented by the following formulae (I-2-1) to (I-2-95) are preferable.

[ solution 12]

[ solution 13]

[ solution 14]

[ solution 15]

[ solution 16]

[ solution 17]

[ solution 18]

[ solution 19]

[ solution 20]

[ solution 21]

[ solution 22]

[ solution 23]

[ solution 24]

[ solution 25]

[ solution 26]

[ solution 27]

[ solution 28]

[ solution 29]

[ solution 30]

As the second component, that is, the compound represented by the general formula (I-2), a compound represented by the general formula (II-rm) is more preferable.

[ solution 31]

(in the formula, P²¹Represents the same meaning as in the formula (P-1), the formula (P-2) or the formula (P-3) of the general formula (I-2), S²¹Represents a single bond or an alkylene group having 1 to 10 carbon atoms as a spacer, 1 or not adjacent 2 or more-CH groups₂Each independently of the others may be substituted by-O-, -COO-, -OCO-or-OCO-O-, ring A²¹Ring A²²Ring A²³Ring A²⁴Each independently represents 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 3, 5-difluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, R²¹Represents 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, 1 or 2 or more-CH groups which are not adjacent to each other₂Each independently may be substituted by-O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH ═ CH-COO-, -CH ═ CH-OCO-, -COO-CH ═ CH-, -OCO-CH ═ CH-, -CF ═ CF-, or-C ≡ C-substitution. )

In the general formula (II-rm), ring A is preferable from the viewpoint of the solubility stability at low temperatures²¹Ring A²²Ring A²³Ring A²⁴At least 1 of them represents 2-fluoro-1, 4-phenylene, 3, 5-difluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene.

In the general formula (II-rm), R²¹The alkyl group having 1 to 10 carbon atoms and the alkoxy group having 1 to 10 carbon atoms are preferable, and the alkyl group having 1 to 5 carbon atoms and the alkoxy group having 1 to 5 carbon atoms are preferable.

As the compounds represented by the general formula (II-rm), more specifically, compounds represented by the formulae (I-2-100) to (I-2-119) are preferable.

[ solution 32]

[ solution 33]

A compound having negative dielectric anisotropy (Delta epsilon) and an absolute value greater than 3 is contained as a third component. Specifically, compounds represented by the general formula (II-1) and the general formula (II-2) are exemplified.

[ chemical 34]

In the formula, R¹And R²Each independently 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, R¹And R²1 of-CH present in₂-or non-adjacent 2 or more-CH₂Each independently can be-O-or-S-substitution, furthermore, R¹And R²Wherein 1 or 2 or more hydrogen atoms present in (A) each independently may be substituted by a fluorine atom or a chlorine atom, R¹Preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, still more preferably an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, R²An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable.

Wherein ring A and ring B each independently represent trans-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] octylene, piperidin-1, 4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, preferably trans-1, 4-cyclohexylene or 1, 4-phenylene.

In the formula, Z¹¹And Z²¹Each independently represents-OCH₂-、-CH₂O-、-CF₂O-、-OCF₂-、-CH₂CH₂-、-CF₂CF₂-or a single bond, preferably-CH₂O-、-CF₂O-、-CH₂CH₂-、-CF₂CF₂-or a single bond, further preferably-CH₂O-、-CH₂CH₂-or a single bond, particularly preferably-CH₂O-or a single bond.

The liquid crystal composition of the present invention contains 1 or 2 or more compounds represented by the general formula (II-1) and the general formula (II-2), and preferably 2 to 10. The content thereof is preferably 10 to 90% by mass, and the lower limit thereof is preferably 15% by mass, preferably 20% by mass, preferably 25% by mass, preferably 30% by mass, preferably 35% by mass, preferably 40% by mass, preferably 45% by mass, preferably 50% by mass; the upper limit value is preferably 85 mass%, preferably 80 mass%, preferably 75 mass%, preferably 70 mass%, preferably 65 mass%, preferably 60 mass%, preferably 55 mass%, preferably 50 mass%, preferably 45 mass%, preferably 40 mass%.

Specifically, the compound represented by the general formula (II-1) is preferably a compound represented by the general formula (II-A1) to the general formula (II-A4), preferably a compound represented by the general formula (II-A1), preferably a compound represented by the general formula (II-A3), preferably a compound represented by the general formula (II-A4), more preferably a compound represented by the general formula (II-A1), and still more preferably a compound represented by the general formula (II-A4).

[ solution 35]

In the formula, R³And R⁴Each independently represents R¹And R²The same meaning is used.

Specifically, the compound represented by the general formula (II-2) is preferably a compound represented by the general formula (II-B1) to the general formula (II-B6), preferably a compound represented by the general formula (II-B1), preferably a compound represented by the general formula (II-B3), preferably a compound represented by the general formula (II-B4), preferably a compound represented by the general formula (II-B5), preferably a compound represented by the general formula (II-B6), more preferably a compound represented by the general formula (II-B1), more preferably a compound represented by the general formula (II-B3), more preferably a compound represented by the general formula (II-B5), more preferably a compound represented by the general formula (II-B6), particularly preferred are compounds represented by the general formula (II-B3), and particularly preferred are compounds represented by the general formula (II-B4).

[ solution 36]

More specifically, the third component is preferably a combination of the general formula (II-A1) and the general formula (II-B1), more preferably a combination of the general formula (II-A1) and the general formula (II-B1) and the general formula (II-A3), and still more preferably a combination of the general formula (II-A1), the general formula (II-B1) and the general formula (II-A4).

More specifically, the third component is preferably a combination of the general formula (II-A3) and the general formula (II-B4), more preferably a combination of the general formula (II-A3) and the general formula (II-B4) and the general formula (II-B5), and still more preferably a combination of the general formula (II-A3), the general formula (II-B4) and the general formula (II-B1).

More specifically, the third component is preferably a combination of the general formula (II-A4) and the general formula (II-B4), preferably a combination of the general formula (II-A4) and the general formula (II-B1), more preferably a combination of the general formula (II-A4), the general formula (II-B1) and the general formula (II-B5), and still more preferably a combination of the general formula (II-A4), the general formula (II-B1) and the general formula (II-B3).

The liquid crystal composition of the present invention preferably contains 1 or 2 or more compounds selected from the group consisting of the compounds of the general formulae (III-A) to (III-J) as the fourth component. However, the compounds represented by the general formula (III-A) do not include the same compounds as those represented by the formula (I-1).

[ solution 37]

In the formula, R⁵Represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, R⁶Represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms.

The fourth component is preferably a compound selected from the group consisting of the compounds of the general formula (III-A), the general formula (III-D), the general formula (III-F), the general formula (III-G) and the general formula (III-H), more preferably a compound selected from the group consisting of the compounds of the general formula (III-A), the general formula (III-F), the general formula (III-G) and the general formula (III-H), still more preferably a compound selected from the group consisting of the compounds of the general formula (III-A), the general formula (III-G) and the general formula (III-H), and also preferably a compound selected from the group consisting of the compounds of the general formula (III-A), the general formula (III-F) and the general formula (III-H).

In addition, among the compounds represented by the general formula (III-D), the general formula (III-G) and the general formula (III-H), R is preferable⁵Is alkyl of 1 to 5 carbon atoms or alkenyl of 2 to 5 carbon atoms, R⁶Is alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 carbon atoms, R⁵More preferably an alkenyl group having 2 to 5 carbon atoms, still more preferably an alkenyl group having 2 or 3 carbon atoms, and in the compound represented by the general formula (III-F), R is⁵And R⁶Each independently is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.

The content of the fourth component is preferably 1 to 50% by mass, and the lower limit thereof is preferably 3% by mass, preferably 5% by mass, preferably 10% by mass, preferably 15% by mass, preferably 20% by mass, preferably 25% by mass, and the upper limit thereof is preferably 45% by mass, preferably 40% by mass, preferably 35% by mass, preferably 30% by mass, preferably 25% by mass, preferably 20% by mass, preferably 15% by mass.

Further, 1 or 2 or more compounds represented by the general formula (V) may be contained as the further component.

[ solution 38]

In the formula, R²¹And R²²Each independently 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, preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.

The content of the general formula (V) is preferably 0 to 20 mass%.

As further components, 1 or 2 or more compounds represented by the general formula (VIII-a), the general formula (VIII-c) or the general formula (VIII-d) may be contained, and the content thereof is preferably 0 to 10% by mass independently of each other.

[ solution 39]

(in the formula, R⁵¹And R⁵²Each independently 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. )

[ solution 40]

(in the formula, R⁵¹And R⁵²Each independently 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, X⁵¹And X⁵²Each independently represents a fluorine atom or a hydrogen atom, X⁵¹And X⁵²At least one of which is a fluorine atom. )

[ solution 41]

As further components, 1 or 2 or more compounds represented by the general formula (V-9.1) to the general formula (V-9.3) may be contained.

[ solution 42]

The liquid crystal composition of the present invention preferably contains the compounds of formula (I-1), formula (I-2), formula (II-A1) and formula (III-A) at the same time, preferably contains the compounds of formula (I-1), formula (I-2), formula (II-A3) and formula (III-A) at the same time, preferably contains the compounds of formula (I-1), formula (I-2), formula (II-A4) and formula (III-A) at the same time, preferably contains the compounds of formula (I-1), formula (I-2), formula (II-B1) and formula (III-A) at the same time, preferably contains the compounds of formula (I-1), formula (I-2), formula (II-B3) and formula (III-A) at the same time, preferably contains the compounds of formula (I-1) and formula (III-A) at the same time, The compounds of the formula (I-2), the formula (II-B4) and the formula (III-A) preferably contain the compounds of the formula (I-1), the formula (I-2), the formula (II-B5) and the formula (III-A) together.

The liquid crystal composition of the present invention further preferably contains the compounds of formula (I-1), formula (I-2), formula (II-A1), formula (II-B1) and formula (III-A) at the same time, further preferably contains the compounds of formula (I-1), formula (I-2), formula (II-A3), formula (II-B5) and formula (III-A) at the same time, further preferably contains the compounds of formula (I-1), formula (I-2), formula (II-A1), formula (II-B4) and formula (III-A) at the same time, further preferably contains the compounds of formula (I-1), formula (I-2), formula (II-A1), formula (II-B5) and formula (III-A) at the same time.

The liquid crystal composition of the present invention further preferably contains the compounds of formula (I-1), formula (I-2), formula (II-A4), formula (II-B5) and formula (III-H) together, further preferably contains the compounds of formula (I-1), formula (I-2), formula (II-A1), formula (II-B1) and formula (III-H) together, further preferably contains the compounds of formula (I-1), formula (I-2), formula (II-A1), formula (II-B1), formula (II-B3) and formula (III-H) together.

In the liquid crystal composition of the present invention, the total content of the first component, the second component, the third component and the fourth component is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and particularly preferably 85 to 100% by mass.

In the liquid crystal composition of the present invention, the total content of the first component, the second component, the third component, the fourth component and the compound represented by the general formula (V) is preferably 88 to 100% by mass, more preferably 93 to 100% by mass, and particularly preferably 97 to 100% by mass.

The liquid crystal composition of the present invention has a dielectric anisotropy (. DELTA.. di-elect cons.) at 25 ℃ of-2.0 to-8.0, preferably-2.0 to-6.0, more preferably-2.0 to-5.0, and particularly preferably-2.5 to-4.5.

The liquid crystal composition of the present invention has a refractive index anisotropy (. DELTA.n) at 25 ℃ of 0.08 to 0.14, more preferably 0.09 to 0.13, and particularly preferably 0.09 to 0.12. More specifically, the thickness is preferably 0.10 to 0.13 in the case of a thin cell gap, and preferably 0.08 to 0.10 in the case of a thick cell gap.

The liquid crystal composition of the present invention has a rotational viscosity (gamma) at 25 DEG C₁) Is from 60 to 200 mPas, the upper limit value is preferably 190 mPas, preferably 180 mPas, preferably 170 mPas, preferably 160 mPas, preferably 150 mPas, preferably 140 mPas, preferably 130 mPas, preferably 125 mPas.

Solid phase-nematic phase transition temperature (T) of the liquid crystal composition of the present invention_cn) Is from-60 ℃ to-15 ℃, more preferably from-60 ℃ to-20 ℃, and particularly preferably from-60 ℃ to-25 ℃.

Nematic phase-isotropic liquid phase transition temperature (T) of liquid crystal composition of the present invention_ni) From 60 ℃ to 120 ℃, more preferably from 70 ℃ to 100 ℃, and particularly preferably from 70 ℃ to 85 ℃.

Elastic constant (K) at 25 ℃ of the liquid crystal composition of the present invention₃₃) Is 10pN to 20pN, more preferably 12pN to 18pN, and particularly preferably 13pN to 17 pN.

The liquid crystal composition of the present invention has a Voltage Holding Ratio (VHR) of 70% to 100%, preferably 75% to 100%, preferably 80% to 100%, preferably 85% to 100%. The measurement conditions were 1V, 3Hz, and 60 ℃ and were values obtained by performing VHR measurement after 12(J) UV irradiation with a high-pressure mercury lamp.

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 (HALS), a self-aligning compound, an infrared absorber, or the like.

The liquid crystal composition of the present invention contains the polymerizable compound represented by the general formula (I-2), and may contain other polymerizable compounds.

Specifically, for example, a polymerizable compound such as a biphenyl derivative or a terphenyl derivative is included, and in this case, the content is 0.01 to 2% by mass. More specifically, one or more polymerizable compounds represented by the general formula (M) may be contained.

[ solution 43]

In the general formula (M), X²⁰¹And X²⁰²Each independently represents a hydrogen atom, a methyl group or-CF₃And (4) a base. Preferably X²⁰¹And X²⁰²Diacrylate derivatives each having a hydrogen atom and dimethacrylate derivatives each having a methyl group are also preferable, and compounds in which one is a hydrogen atom and the other is a methyl group are also preferable. Preferred compounds may be used according to the application, and in the PSA display element, the polymerizable compound represented by the general formula (M) preferably has at least 1 methacrylate derivative, and also preferably has 2.

In the general formula (M), Sp²⁰¹And Sp²⁰²Each independently represents a single bond, an alkylene group having 1 to 8 carbon atoms or-O- (CH)₂)_s- (wherein s represents an integer of 2 to 7, and an oxygen atom is bonded to the ring). In the liquid crystal display element of the PSA mode, Sp is preferable²⁰¹And Sp²⁰²At least one of them is a single bond, preferably a compound of both single bonds, or one is a single bond and the other is an alkylene group having 1 to 8 carbon atoms or-O- (CH)₂)_sIn this case, the alkylene group having 1 to 4 carbon atoms is preferable, and s is preferably 1 to 4.

In the general formula (M), ring M²⁰¹Ring M²⁰²And ring M²⁰³Each independently represents trans-1, 4-cyclohexylene (1 or non-adjacent 2 or more-CH groups in the group)₂-may be substituted by-O-or-S-. ) 1, 4-phenylene (1 or non-adjacent 2 or more of the groups-CH ═ may be substituted by-N ═ or. ) 1, 4-cyclohexenylene, 1, 4-bicyclo [2.2.2]Octylene, piperidine-1, 4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, the hydrogen atoms in the groups each independently being possibly substituted by a fluorine atom, -CF₃A group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or any one of the formulae (R-1) to (R-15).

[ solution 44]

In the general formula (M), Z²⁰¹And Z²⁰²Each independently 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, Y)¹And Y²Each independently represents a fluorine atom or a hydrogen atom. ) -C.ident.C-or a single bond, preferably-COO-, -OCO-, -CH-COO-, -CH-OCO-, -COO-CH-, -OCO-CH-, -COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂CH₂-OCO-, -C.ident.C-or a single bond, and further preferably-COO-, -OCO-, -CH-COO-, -CH-OCO-, -COO-CH-, -OCO-CH-, -COO-CH-₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂CH₂-OCO-or a single bond.

In the general formula (M), n²⁰¹Represents 0, 1 or 2, preferably 0 or 1. However, the ring M²⁰²And Z²⁰²When a plurality of the organic compounds are present, they may be different from each other or the same.

The polymerizable compound may contain at least 1 species represented by the general formula (M), preferably 1 to 5 species, and more preferably 1 to 3 species.

The content of the general formula (M) is preferably 0.01 to 2.00% by mass, more preferably 0.05 to 1.00% by mass, and particularly preferably 0.10 to 0.50% by mass.

More specifically, n in the formula (M)²⁰¹In the case of 0, Sp²⁰¹And Sp²⁰²Preferably a ring structure therebetweenAre the formulae (XXa-1) to (XXa-5), more preferably the formulae (XXa-1) to (XXa-3), and particularly preferably the formulae (XXa-1) or (XXa-2). Wherein both ends of formula are connected to Sp²⁰¹Or Sp²⁰²。

[ solution 45]

[ solution 46]

[ solution 47]

[ solution 48]

[ solution 49]

The polymerizable compound represented by the general formula (M) containing these skeletons has an effect that the orientation constraint force after polymerization is most suitable for the PSA mode liquid crystal display element and a good orientation state can be obtained, and thus display unevenness is suppressed or not generated at all.

As described above, as the polymerizable compound, compounds represented by the formulae (XX-1) to (XX-10) are preferable, and the formulae (XX-1) to (XX-4) are more preferable.

[ solution 50]

In formulae (XX-1) to (XX-10), Sp^xxRepresents an alkylene group having 1 to 8 carbon atoms or-O- (CH)₂)_s- (wherein s represents an integer of 2 to 7, and an oxygen atom is bonded to the ring).

In the formulae (XX-1) to (XX-10), the hydrogen atom in the 1, 4-phenylene group may be further substituted by-F, -Cl, -CF₃、-CH₃Any one of the formulae (R-1) to (R-15).

N in the general formula (M)²⁰¹In the case of 1, polymerizable compounds such as those of the formulae (M31) to (M48) are preferable.

[ solution 51]

The hydrogen atoms in the 1, 4-phenylene and naphthyl groups of the formulae (M31) to (M48) may further be replaced by-F, -Cl, -CF₃、-CH₃Any one of the formulae (R-1) to (R-15).

The polymerizable compound represented by the general formula (M) containing these skeletons has an orientation constraint force after polymerization that is most suitable for a PSA mode liquid crystal display device, and has an effect of suppressing display unevenness or completely preventing display unevenness because a good orientation state can be obtained.

As the polymerizable compound represented by the general formula (M), polymerizable compounds such as the formulae (Ia-1) to (Ia-31) are also preferable.

[ solution 52]

[ Hua 53]

[ solution 54]

[ solution 55]

More specifically, as the polymerizable compound, for example, a 3-functional polymerizable compound such as the formula (M301) to the formula (M316) is also preferable.

[ solution 56]

The hydrogen atoms in the 1, 4-phenylene and naphthyl groups in the formulae (M301) to (M316) may further be replaced by-F, -Cl, -CF₃、-CH₃And (4) substitution.

Further, as the antioxidant to be added to the liquid crystal composition of the present invention, hindered phenols represented by general formulae (H-1) to (H-4) are preferable.

[ solution 57]

In the general formulae (H-1) to (H-4), R^H1Represents 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, 1-CH present in the group₂-or non-adjacent 2 or more-CH₂Each independently may be substituted by-O-or-S-, and furthermore, 1 or more than 2 hydrogen atoms present in the group may each independently be substituted by fluorine atoms or chlorine atoms. More specifically, an alkyl group having 2 to 7 carbon atoms, an alkoxy group having 2 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms is preferable, and an alkyl group having 3 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms is more preferable.

In the general formula (H-4), M^H4Represents an alkylene group having 1 to 15 carbon atoms (1 or 1 of the alkylene group)More than 2-CH₂-may be substituted by-O-, -CO-, -COO-, -OCO-in such a way that the oxygen atoms are not directly adjacent. ) -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 trans 1, 4-cyclohexylene, and the number of carbon atoms is preferably a large value in view of volatility, and the rotational viscosity (γ ≡ C-₁) The number of carbon atoms is preferably not excessively large, and therefore, the number of carbon atoms is more preferably 2 to 12, still more preferably 3 to 10, still 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), 1 or more non-adjacent 2 or more of 1, 4-phenylene groups may be substituted with — N ═ group. Further, each hydrogen atom in the 1, 4-phenylene group may be independently substituted with a fluorine atom or a chlorine atom.

1 or non-adjacent 2 or more-CH groups in the 1, 4-cyclohexylene groups in the general formulae (H-1) to (H-4)₂-may be substituted by-O-or-S-. Further, each hydrogen atom in the 1, 4-cyclohexylene group may be independently substituted with a fluorine atom or a chlorine atom.

Further specifically, the formulae (H-11) to (H-15) may be exemplified.

The liquid crystal composition of the present invention may contain the antioxidant in an amount of 1 mass ppm or more, preferably 10 mass ppm or more, preferably 20 mass ppm or more, preferably 50 mass ppm or more. The upper limit of the content 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 is useful for a liquid crystal display element, particularly a liquid crystal display element for active matrix driving, and is useful for a liquid crystal display element for PSA mode, PSVA mode, VA mode, IPS mode, or ECB mode.

The liquid crystal composition of the present invention is used for a liquid crystal display element in which the amount of transmitted light is controlled by the birefringence of the liquid crystal composition, and the liquid crystal composition is imparted with liquid crystal alignment ability by polymerizing the polymerizable compound contained therein by irradiation with ultraviolet rays. The liquid crystal display element is useful for AM-LCD (active matrix liquid crystal display element), TN (nematic liquid crystal display element), STN-LCD (super twisted nematic liquid crystal display element), OCB-LCD, and IPS-LCD (in-plane switching liquid crystal display element), and is particularly useful for AM-LCD, and can be used for transmissive or reflective liquid crystal display elements. Further, the present invention can be applied to a liquid crystal display element having no alignment film.

As the two substrates of the liquid crystal cell used in the liquid crystal display element, a transparent material having flexibility such as glass or plastic may be used, and one of the substrates may be an opaque material such as silicon. The transparent substrate having a transparent electrode layer can be obtained by, for example, sputtering Indium Tin Oxide (ITO) on a transparent substrate such as a glass plate.

The color filter can be produced by, for example, a pigment dispersion method, a printing method, an electrodeposition method, a dyeing method, or the like. A method for manufacturing a color filter by a pigment dispersion method will be described as an example, in which a curable coloring composition for a color filter is applied to the transparent substrate, subjected to patterning treatment, and then cured by heating or light irradiation. This process is performed for 3 colors of red, green, and blue, respectively, thereby forming a pixel portion for a color filter. Further, a pixel electrode provided with an active element such as a TFT, a thin film diode, or a metal insulator metal resistivity element may be provided on the substrate.

The substrates are opposed to each other with the transparent electrode layer being an inner side. In this case, the interval between the substrates may be adjusted with spacers interposed therebetween. In this case, the thickness of the light control layer is preferably adjusted to 1 to 100 μm. More preferably 1.5 to 10 μm, and when a polarizing plate is used, the product of the refractive index anisotropy Δ n of the liquid crystal and the cell thickness d is preferably adjusted so that the contrast becomes maximum. In the case of two polarizing plates, the polarizing axes of the polarizing plates may be adjusted so that the viewing angle and the contrast are good. Further, a retardation film for enlarging the viewing angle can be used. Examples of the spacer include glass particles, plastic particles, alumina particles, and photoresist. Thereafter, a sealant such as an epoxy-based thermosetting composition is screen-printed on the substrates so as to provide a liquid crystal injection port, the substrates are bonded to each other, and the sealant is thermally cured by heating.

The method of sandwiching the liquid crystal composition containing the polymerizable compound between the two substrates may use a common vacuum infusion method, ODF method, or the like.

In order to obtain good alignment properties of liquid crystals, a suitable polymerization rate is desired as a method for polymerizing the polymerizable compound, and therefore, a method for polymerizing the polymerizable compound by irradiating active energy rays such as ultraviolet rays or electron rays singly or in combination or in sequence is preferred. 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 containing the polymerizable compound is sandwiched between two substrates, at least the substrate on the irradiation surface side must have appropriate transparency to the active energy ray. Further, the following method may also be used: when light is irradiated, only a specific portion is polymerized using a mask, and then, the orientation state of an unpolymerized portion is changed by changing conditions such as an electric field, a magnetic field, or temperature, and further, the portion is polymerized by irradiation with an active energy ray. In particular, when ultraviolet exposure is performed, it is preferable to perform ultraviolet exposure while applying an alternating-current electric field to the liquid crystal composition of the present invention. The alternating electric field applied is preferably an alternating current with a frequency of 10Hz to 10kHz, more preferably a frequency of 60Hz to 10kHz, the voltage being selected in dependence on the desired pretilt angle of the liquid crystal display element. I.e. the pretilt angle of the liquid crystal display element is controlled by the applied voltage. In MVA mode liquid crystal display elements, the pretilt angle must be controlled to about 80 degrees to about 88 degrees from the viewpoints of alignment stability and contrast, and by using the liquid crystal composition of the present invention, the pretilt angle can be controlled to a desired value.

The temperature during irradiation is preferably such that the liquid crystal of the liquid crystal composition of the present invention is maintainedTemperature range of the state. The polymerization is preferably carried out at a temperature close to room temperature, i.e., typically 15 to 35 ℃. 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. Further, as the wavelength of the ultraviolet rays to be irradiated, ultraviolet rays having a wavelength region not in the absorption wavelength region of the liquid crystal composition are preferably irradiated, and the ultraviolet rays are preferably filtered 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. The amount of energy of the ultraviolet rays to be irradiated can be appropriately adjusted, and is preferably 10mJ/cm²To 500J/cm²More preferably 100mJ/cm²To 200J/cm². The intensity can also be varied when ultraviolet light is irradiated. The time for irradiating ultraviolet rays is appropriately selected depending on the intensity of the ultraviolet rays to be irradiated, and is preferably 10 seconds to 3600 seconds, and more preferably 10 seconds to 600 seconds.

Examples

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the compositions of examples and comparative examples below, "%" means "% by mass".

The compounds in the examples are described below.

(side chain)

-n -C_nH_2n+1Straight chain alkyl group having carbon number n

n- C_nH_2n+1-linear alkyl group having n carbon atoms

-On -OC_nH_2n+1Straight chain alkoxy group having carbon number n

nO- C_nH_2n+1O-straight chain alkoxy group having n 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＝CH-CH₂-CH₂-

(linking group)

-CF2O- -CF₂-O-

-OCF2- -O-CF₂-

-1O- -CH₂-O-

-O1- -O-CH₂-

-COO- -COO-

(Ring structure)

[ solution 58]

The properties measured in the examples are as follows.

T_ni: nematic phase-isotropic liquid phase transition temperature (. degree.C.)

T_cn: solid phase-nematic phase transition temperature (. degree.C.)

Δ n: refractive index anisotropy at 25 DEG C

Δ ε: anisotropy of dielectric constant at 25 DEG C

γ₁: rotational tack at 25 ℃ (mPa. multidot.s)

K₃₃: elastic constant K at 25 DEG C₃₃(pN)

VHR: voltage holding ratio after 12(J) UV irradiation with a high-pressure mercury lamp (%)

Comparative examples 1 to 4 and examples 1 to 4

Liquid crystal compositions of LC-A (comparative example 1), LC-B (comparative example 2), LC-C (comparative example 3), LC-D (comparative example 4), LC-1 (example 1), LC-2 (example 2), LC-3 (example 3) and LC-4 (example 4) were prepared, and their physical property values were measured. The composition of the liquid crystal composition and the results of the physical property values are shown in table 1.

[ Table 1]

It was confirmed that in the liquid crystal composition LC-1 of the present invention, Δ ε is negative, the absolute value is large, γ 1 is low, and K is₃₃Large, T_cnLow, T_niHigh and VHR high. In LC-1, the nematic phase was maintained as a result of a 100-hour low-temperature storage test at-25 ℃. The response speed of the liquid crystal display element using the same was measured, and as a result, the liquid crystal display element exhibited a sufficiently high-speed response. Further, it was confirmed that there was no display defect such as burn-in or display unevenness. Here, the cell thickness was 3.3um, the alignment film was JALS2096, and the response speed was measured under conditions of Von 6V, Voff of 1V and a measurement temperature of 30 ℃, and DMS703 from AUTRONIC-MELCHERS corporation was used.

In addition, a liquid crystal display element of the PSVA mode was produced using a liquid crystal composition obtained by adding 0.35 mass% of the compound of formula (XX-2) as a polymerizable compound to 99.65 mass% of each of the liquid crystal compositions of LC-1 to LC-4, and no display failure was observed in any of the elements, and it was confirmed that the response was sufficiently high-speed.

(examples 5 to 8)

Furthermore, a liquid crystal display element of the PSVA mode was produced using a liquid crystal composition obtained by adding 0.3 mass% of the formula (XX-4) as a polymerizable compound to 99.7 mass% of each of the liquid crystal compositions LC-1 to LC-4, and no display failure was observed in any of the elements, and it was confirmed that the response was sufficiently high-speed.

(examples 9 to 12)

A PSVA mode liquid crystal display element was produced using a liquid crystal composition obtained by adding 0.35 mass% of the compound of formula (XX-2) as a polymerizable compound to 99.65 mass% of liquid crystal composition LC-A, and as a result, a burn-in phenomenon was observed.

Comparative example 5

Further, a liquid crystal composition LC-5 (example 13) was prepared by replacing the compound of 3-Cy-Cy-V of example 1 with the compound of V-Cy-Cy-V, and the physical property values thereof were measured, whereby γ which was more excellent than that of example 1 was obtained₁。

As described above, it was confirmed that, in the liquid crystal composition of the present invention, Δ ε isNegative and large absolute value, rotational viscosity (gamma)₁) Low, elastic constant (K)₃₃) Large, solid phase-nematic phase transition temperature (T)_cn) Low nematic-isotropic liquid phase transition temperature (T)_ni) The liquid crystal display device has high solubility stability at low temperature and high Voltage Holding Ratio (VHR), and VA, PSVA, PSA, FFS and other liquid crystal display devices manufactured using the liquid crystal display device have high VHR, no burn-in, no display defects such as display unevenness or suppressed display defects, excellent display quality and high-speed response.

Claims

1. A liquid crystal composition having a negative dielectric anisotropy [ Delta ] [ epsilon ] contains a compound represented by the general formula (I-1) as a first component and a compound represented by the general formula (I-2) as a second component,

[ solution 1]

In the formula (I-1), R¹¹Represents 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, R¹²Represents 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,

[ solution 2]

In the formula (I-2), P represents any one of the formulae (P-1) to (P-3),

s represents a single bond or a spacer, and when a plurality of S exist, they may be the same or different, and X represents-O-, -S-、-OCH₂-、-CH₂O-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-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-, -CH-, -CF-or a single bond, and when a plurality of X's are present, they may be the same or different, and A¹、A²、A³、A⁴And A⁵Each independently represents 1, 4-phenylene, naphthalene-1, 4-diyl or naphthalene-2, 6-diyl, in which the hydrogen atoms may be substituted by 1 or more L, A⁵When plural, they may be the same or different, Z¹、Z²And Z³Each independently represents-O-, -S-, -OCH₂-、-CH₂O-、-COO-、-OCO-、-CO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-CH₂CH₂-、-CH₂CF₂-、-CF₂CH₂-、-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-, -CH ═ CH-, -CF ═ CF-, or-C ≡ C-, or a single bond, and R represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or a straight-chain or branched-chain alkyl group having 1 to 12 carbon atoms, wherein 1-CH-, -CH ≡ CH-, -CF ≡ C-group₂-or non-adjacent 2 or more-CH₂Each independently of the others may be substituted by-O-, -S-, l represents an integer from 0 to 8, m1, m2 and m3 represent 0 or 1,n represents 0, 1 or 2, L represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group or a methoxy group, and m1+ m2+ m3 represents 0 or 1.

2. The liquid crystal composition according to claim 1, having a dielectric anisotropy Δ ∈ at 20 ℃ in the range of-2.0 to-8.0, a refractive index anisotropy Δ n at 20 ℃ in the range of 0.08 to 0.14, a rotational viscosity γ 1 at 20 ℃ in the range of 60 to 200 mPas, and a nematic phase-isotropic liquid phase transition temperature T_niIn the range of 60 ℃ to 120 ℃.

3. The liquid crystal composition according to claim 1 or 2, comprising 1 or 2 or more compounds selected from the group consisting of compounds represented by the general formula (II-1) and the general formula (II-2) as a third component,

[ solution 3]

In the formula, R¹And R²Each independently 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, R¹And R²1 of-CH present in₂-or non-adjacent 2 or more-CH₂Each independently of the others may be substituted by-O-and/or-S-, in addition, R¹And R²Wherein 1 or 2 or more hydrogen atoms present in (A) may be independently substituted with a fluorine atom or a chlorine atom, and ring A and ring B each independently represent a trans-1, 4-cyclohexylene group, a1, 4-phenylene group, a 2-fluoro-1, 4-phenylene group, a3, 5-difluoro-1, 4-phenylene group, a 2, 3-difluoro-1, 4-phenylene group, a1, 4-cyclohexenylene group, a1, 4-bicyclo [2.2.2]Octylene, piperidine-1, 4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, Z¹¹And Z²¹Each independently represents-OCH₂-、-CH₂O-、-CF₂O-、-OCF₂-、-CH₂CH₂-、-CF₂CF₂-or a single bond.

4. The liquid crystal composition according to claim 1 or 2, comprising 1 or 2 or more compounds selected from the group consisting of compounds represented by the general formulae (III-A) to (III-J) as a fourth component,

[ solution 4]

In the formula, R⁵Represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, R⁶Represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms, but the same compounds as those represented by the general formula (I-1) are not included in the compounds represented by the general formula (III-A).

5. The liquid crystal composition according to claim 3, which contains both the compound represented by the general formula (II-1) and the compound represented by the general formula (II-2).

6. The liquid crystal composition of claim 3, wherein the general formula (II-1) is a general formula (II-A1) to a general formula (II-A4),

[ solution 5]

The general formula (II-2) is a general formula (II-B1) to a general formula (II-B6),

[ solution 6]

7. The liquid crystal composition according to claim 3, comprising 1 or 2 or more kinds of R selected from the group consisting of general formula (II-1) and general formula (II-2)¹Is propyleneCompounds of the group of compounds of the formulae (I).

8. The liquid crystal composition according to claim 1 or 2, comprising one or more polymerizable compounds represented by the general formula (M),

in the general formula (M),

X²⁰¹and X²⁰²Each independently represents a hydrogen atom, a methyl group or-CF₃The base group is a group of a compound,

Sp²⁰¹and Sp²⁰²Each independently represents a single bond, an alkylene group having 1 to 8 carbon atoms or-O- (CH)₂)_s-, formula-O- (CH)₂)_sIn which s represents an integer from 2 to 7 and the oxygen atom is bonded to the ring,

ring M²⁰¹Ring M²⁰²And ring M²⁰³Each independently represents trans-1, 4-cyclohexylene, 1, 4-phenylene, 1, 4-cyclohexenylene, 1, 4-bicyclo [2.2.2]Octylene, piperidine-1, 4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, the hydrogen atoms in the groups each independently being possibly substituted by a fluorine atom, -CF₃A group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or any one of the substituents of the formulae (R-1) to (R-15), 1 or not adjacent 2 or more-CH groups in the trans-1, 4-cyclohexylene group₂-is optionally substituted by-O-or-S-, 1 of the 1, 4-phenylene radicals or more than 2 non-adjacent-CH-groups are optionally substituted by-N-,

Z²⁰¹and Z²⁰²Each independently 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-, -C.ident.C-or a single bond, of the formula-CY¹＝CY²In (Y)¹And Y²Each independently represents a fluorine atom or a hydrogen atom,

n²⁰¹represents a number of 0, 1 or 2,

ring M²⁰²And Z²⁰²When a plurality of the organic compounds are present, they may be different from each other or the same.

9. A liquid crystal display element using the liquid crystal composition according to any one of claims 1 to 8.

10. A liquid crystal display element for active matrix driving, which uses the liquid crystal composition according to any one of claims 1 to 8.

11. A VA-type, FFS-type, PSA-type, PSVA-type liquid crystal display element using the liquid crystal composition according to any one of claims 1 to 8.