WO2017188005A1 - Nematic liquid crystal composition, and liquid crystal display element using same - Google Patents

Abstract

[Problem] The present invention addresses the problem that a negative Δε value having a large absolute value, a small rotational viscosity (γ1), a large elastic modulus (K₃₃), a low (solid phase)-(nematic phase) transition temperature (T_cn), a high (nematic phase)-(isotropic liquid phase) transition temperature (T_ni) and a large voltage holding ratio (VHR) are demanded. The present invention also addresses the problem of providing a rapid-response liquid crystal display element of a VA type, a PSVA type, a PSA type, a FFS type or the like, which is produced using the same, rarely undergoes or never undergoes display failures such as burning-in and display unevenness and has excellent display quality. [Solution] Provided are: a liquid crystal composition which contains a compound represented by formula (I-1) as a first component and a compound represented by formula (I-2) as a second component and has a negative dielectric anisotropy (Δε) value; and a liquid crystal display element produced using the liquid crystal composition.

Description

Nematic liquid crystal composition and liquid crystal display device using the same

The present invention relates to a nematic liquid crystal composition having a negative dielectric anisotropy (Δε) useful as a liquid crystal display material, and a liquid crystal display device using the same.

Liquid crystal display elements are used in various household electric appliances, measuring instruments, automobile panels, mobile phones, computers, televisions, etc., including watches and calculators. Typical liquid crystal display methods include TN (twisted nematic), STN (super twisted nematic), DS (dynamic light scattering), GH (guest / host), and IPS (in-plane switching). Type, FFS (fringe field switching) type, OCB (optical compensation birefringence) type, ECB (voltage controlled birefringence) type, VA (vertical alignment) type, PSVA type, PSA type, CSH (color super homeotropic) type, Or FLC (ferroelectric liquid crystal) etc. can be mentioned. Examples of the driving method include static driving, multiplex driving, simple matrix method, active matrix (AM) method driven by TFT (thin film transistor), TFD (thin film diode), and the like.

Among these display methods, the IPS type, FFS type, ECB type, VA type, CSH type, and the like have a feature that a liquid crystal material having a negative value of Δε is used. Among these, the VA type display method by AM driving is used for a display element that requires a high speed and a wide viewing angle, such as a television. The FFS display method is used for mobile applications such as smartphones because high transmittance can be obtained.

Nematic liquid crystal compositions (hereinafter referred to as liquid crystal compositions) used in VA type, FFS type and other display systems are required to have low voltage driving, high speed response, a wide operating temperature range, and high reliability. That is, Δε is negative and the absolute value is large, 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 high voltage holding ratio (VHR) are required. Further, from the setting of Δn × d, which is the product of refractive index anisotropy (Δn) and cell gap (d), it is necessary to adjust Δn of the liquid crystal material to an appropriate range according to the cell gap.

In response to these requirements, the characteristics of liquid crystal compositions have been improved by variously examining compounds having a negative Δε and a large absolute value. For example, a liquid crystal composition using the following liquid crystal compounds (A) and (B) having a 2,3-difluorophenylene skeleton (see Patent Document 1) as a liquid crystal material having a negative Δε is disclosed.

In this liquid crystal composition, liquid crystal compounds (C) and (D) are used as compounds having Δε of approximately 0. However, this liquid crystal composition is used in a liquid crystal composition that requires a high-speed response such as a liquid crystal television. It cannot be said that the viscosity is sufficiently low.

On the other hand, although a liquid crystal composition using a compound represented by the formula (E) has already been disclosed, a liquid crystal composition having a small Δn combined with the liquid crystal compound (D) (see Patent Document 2) and a response speed. Is a liquid crystal composition (see Patent Document 3) in which a compound having an alkenyl group in the molecule (alkenyl compound) is added as in the liquid crystal compound (F) (see Patent Document 3), and the problem of achieving both high Δn and high reliability was there.

A liquid crystal composition using a compound represented by the formula (G) has already been disclosed (see Patent Document 4), but this liquid crystal composition also contains an alkenyl compound as in the above liquid crystal compound (F). Since it is a liquid crystal composition containing a compound, there is a problem that display defects such as image sticking and display unevenness are likely to occur.

In addition, the influence on the display defect of the liquid crystal composition containing the alkenyl compound has already been disclosed (see Patent Document 5), but generally, the η of the liquid crystal composition increases as the content of the alkenyl compound decreases. Since it is difficult to achieve a high-speed response, there is a problem of achieving both suppression of display defects and high-speed response.

Thus, only by combining a compound in which Δε has a negative value and the liquid crystal compounds (C), (D), and (F), both high Δn and low rotational viscosity (γ ₁ ) are achieved, and there is no display defect. Alternatively, it has been difficult to develop a liquid crystal composition having a suppressed Δε.

The PSA (Polymer Sustained Alignment) type, one of the VA display modes, is a structure in which a polymer structure is formed in the cell to control the pretilt angle of the liquid crystal molecules, and features high-speed response and high contrast. Have. In the production, a polymerizable compound-containing liquid crystal composition composed of a polymerizable compound and a liquid crystal compound is injected between the substrates, and a voltage is applied to polymerize the polymerizable compound in a state where the liquid crystal molecules are aligned, thereby aligning the liquid crystal molecules. This is done by fixing. Therefore, a problem peculiar to the PSA type is the occurrence of display defects due to image sticking or the like caused by the reaction product of the polymerizable compound. The cause of this burn-in is the presence of a causative substance in the liquid crystal composition of the PSA element. Specifically, a polymerization reaction product generated in a polymerization process of a polymerizable compound at the time of manufacturing a PSA element has an adverse effect such as image sticking. Further, the polymerizable compound reacts with the components of the liquid crystal composition, and this reaction product has an adverse effect such as image sticking.

In order to solve problems such as display defects due to image sticking, which may be generated in PSA type elements having such useful display performance (contrast and response speed), optimization of polymerizable compounds and components of liquid crystal compositions Optimization has become an issue. In particular, a liquid crystal composition containing a liquid crystal material having an alkenyl group effective for reducing viscosity is effective in reducing the response speed, but a display defect or the like after polymerization of a polymerizable compound, which is a process for producing a PSA display device There may have been problems.

As described above, in a liquid crystal composition used for a VA type or FFS type or the like, or a liquid crystal composition used for producing an element that controls alignment by a reaction product of a polymerizable compound such as a PSVA type or a PSA type. , Δε is negative and absolute value is large, 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 high voltage holding ratio (VHR) have been demanded. In addition, UV irradiation at the time of manufacturing and use of the element does not cause deterioration or the like, even if it does not affect display, and there is no display defect such as image sticking or display unevenness, or excellent display quality. There has been a demand for a liquid crystal display device having a high response speed.

JP-A-8-104869 European Patent Application No. 0474402 JP 2006-37054 A JP 2001-354967 A JP 2008-144135 A

The problem to be solved by the present invention is that Δε is negative and has a large absolute value, low rotational viscosity (γ ₁ ), large elastic constant (K ₃₃ ), low solid phase-nematic phase transition temperature (T _cn ), high nematic Provided is a liquid crystal composition having a phase-isotropic liquid phase transition temperature (T _ni ), a low-temperature dissolution stability and a high voltage holding ratio (VHR), and further reducing the reliability of the liquid crystal composition after UV irradiation. And providing a liquid crystal display element such as a VA type, a PSVA type, a PSA type, and an FFS type that has no display defects such as burn-in and display unevenness using the same, and has excellent display quality and a high-speed response. is there.

The present inventor has studied various compounds and found that the above problems can be solved by combining specific compounds, and has completed the present invention.

The liquid crystal composition of the present invention has the formula (I-1) as the first component

(Wherein R ¹¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxyl 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, R ¹² represents an alkyl group having 1 to 10 carbon atoms, an alkoxyl 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 the second component is a compound of formula (I-2)

(In the formula, P represents a polymerizable group, S represents a single bond or a spacer group, and when a plurality of S are present, they may be the same or different, and X represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—. NH—, —NH—CO—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO— _{, -CH 2 CH 2 -OCO -,} - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH -OCO -, - CH = CH - , - CF = CF- or represents a single bond, they if X there is a plurality may be different even in the ^{same, A 1, A 2, A} 3, A ⁴ and A ⁵ each independently represents 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl, and the hydrogen atom in these groups is one or more L When a plurality of A ⁵ are present, they may be the same or different, and Z ¹ , Z ² , and Z ³ are each independently —O—, — S-, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH _{-, - NH-CO -,} - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 - _{-CF 2 S -, - SCF 2} -, - CH 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 -, - CH = CH-COO -, - CH = CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CH═CH—, —CF═CF— or —C≡ R represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or 1 carbon atom. To 12 linear or branched alkyl groups But one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, - OCO -, - CO- S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═ Optionally substituted by CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C—, wherein l represents an integer from 0 to 8, m1, m2 And m3 represents 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, and m1 + m2 + m3 represents 0 or 1 . The liquid crystal composition having a negative dielectric anisotropy (Δε) is provided, and a liquid crystal display device using the same is provided.

The liquid crystal composition of the present invention has a negative Δε and a large absolute value, a low rotational viscosity (γ ₁ ), a large elastic constant (K ₃₃ ), a low solid phase—nematic phase transition temperature (T _cn ), a high nematic phase— Isotropic liquid phase transition temperature (T _ni ), low-temperature dissolution stability, and high voltage holding ratio (VHR), and VA type, PSVA type, PSA type, FFS type and other liquid crystal display elements manufactured by using this Has a high VHR, has no display defects such as burn-in and display unevenness, or has a high-speed response with excellent display quality.

The liquid crystal composition of the present invention has a general formula (I-1) as a first component

The compound represented by these is contained. The compound represented by the general formula (I-1) is contained in an amount of 3 to 70% by mass, and the lower limit is preferably 5% by mass, preferably 10% by mass, preferably 15% by mass, and preferably 20% by mass. 25% by mass, preferably 30% by mass, preferably 35% by mass, and preferably 40% by mass. The upper limit is preferably 65% by mass, preferably 60% by mass, preferably 55% by mass, and 50% by mass. Is preferable, 45% by mass is preferable, 40% by mass is preferable, 35% by mass is preferable, and 30% by mass is preferable. More specifically, to obtain a low rotational viscosity (γ ₁ ), the content is preferably 30 to 65% by mass. However, when emphasizing the suppression of precipitation at low temperatures, the content is 5 to 30% by mass. preferable.

In general formula (I-1), R ¹¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. R ¹¹ represents an alkyl group having 1 to 5 carbon atoms, an alkoxyl 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 represents an alkyl group having 1 to 5 carbon atoms and an alkenyl group having 2 to 5 carbon atoms, and represents an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms. preferable.
In general formula (I-1), R ¹² represents an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. R ¹² represents an alkyl group having 1 to 5 carbon atoms, an alkoxyl 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, it is 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.

As the second component, general formula (I-2)

The compound represented by these is contained. The compound represented by the general formula (I-2) is characterized by having four or more phenyl rings or naphthalene rings, which are aromatic rings, and 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 is preferably 0.1% by mass, preferably 0.2% by mass, and 0.3% by mass. 0.5% by mass is preferable, 1% by mass is preferable, 1.5% by mass is preferable, and 2% by mass is preferable. The upper limit is 4.5% by mass, preferably 4% by mass, and 3% by mass. 0.5 mass% is preferable, 3 mass% is preferable, 2.5 mass% is preferable, 2 mass% is preferable, 1.5 mass% is preferable, 1 mass% is preferable, and 0.5 mass% is preferable. More specifically, the content is preferably 0.3 to 3% by mass in order to obtain a high voltage holding ratio (VHR). However, when emphasizing the suppression of precipitation at a low temperature, the content is from 0.1. 1% by mass is preferred.

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

P is preferably the formula (P-1), the formula (P-2) or the formula (P-3), and particularly preferably the formula (P-1) or the formula (P-2).
S represents a single bond or a spacer group. As the spacer group, for example, an alkylene group having 1 to 20 carbon atoms can be represented, and one or two or more non-adjacent —CH _{2 in the} group can be represented. -May be each independently substituted with -O-, -COO-, -OCO- or -OCO-O-, and when there are a plurality of S, they may be the same or different. . More preferably, S is a spacer group.
A ¹ , A ² , A ³ and A ⁴ each independently represents 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl, and the hydrogen atom in these groups is It may be substituted with one or more L, and when there are multiple A ^5, they may be the same or different, but at least one is substituted with one or more L Is preferred.
A ¹ , A ² , A ³ , A ⁴ and A ⁵ are specifically represented by the following formulas (A-1) to (A-10):

The group chosen from can be mentioned.
L represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group or a methoxy group, and is preferably a fluorine atom, a chlorine atom, a methyl group or a methoxy group. The hydrogen atom of the methyl group or methoxy group may be optionally substituted with a fluorine atom.
l represents 0, 1 or 2, and is preferably 1.
n represents 0, 1 or 2, with 0 being preferred.
Z ¹ , Z ² , and Z ³ are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—, —CO —S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CH ₂ CH ₂ —, —CH ₂ CF ₂ —, —CF ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═CH—COO—, — CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ — OCO—, —CH═CH—, —CF═CF— or —C≡C— or a single bond, and when there are a plurality of them, they may be the same or different, but each independently Single bond, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, — CH ₂ CH ₂ —OCO—, —CH═CH— or —C≡C— is preferred, and at least one of Z ¹ , Z ² and Z ³ is preferably a single bond, A bond is preferred.
X represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—. O—, —CO—NH—, —NH—CO—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CH ═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CH═CH—, —CF═CF— or a single bond, and when a plurality of Xs are present, they may be the same or different. It is preferably —, —COO—, —OCO— or a single bond.
R represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or one —CH ₂ —, or one carbon atom. To twelve straight or branched alkyl groups, but two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH═CH—COO—, —CH═CH—OCO—, —COO. May be substituted by —CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C—, but may be a hydrogen atom, fluorine atom, chlorine atom, cyano group or one or non-adjacent two or more -CH 2 _- pixel It is preferably a linear or branched alkyl group having 1 to 12 carbon atoms which may be independently substituted by —O—, —COO—, —OCO—, —O—CO—O—, Hydrogen atom, fluorine atom, straight chain alkyl group having 1 to 12 carbon atoms, branched alkyl group having 2 to 12 carbon atoms, straight chain alkoxy group having 1 to 12 carbon atoms, branched alkoxy group having 2 to 12 carbon atoms More preferably, it is a group. 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 general formula (I-2) is more preferably a compound represented by general formula (I-3).

In the formula, P and R represent the same meaning as in formula (I-2), and S ¹ and S ² each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, Two or more non-adjacent —CH ₂ — may be replaced by —O—, —COO—, —OCO—, —OCOO—, wherein X ¹ and X ² are each independently —O—, — S-, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH —, —NH—CO—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CH═CH—COO—, — CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO- _{H 2 CH 2 -, - CH} 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO —, —CH═CH—, —CF═CF—, —C≡C— or a single bond, Z ⁴ is a single bond, —O—, —S—, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —SCH ₂ —, — CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CH ₂ CH ₂ —, —CH ₂ CF ₂ —, —CF ₂ CH ₂ —, —CF _{2 CF 2 -, - CH =} CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - _{, - - OO-CH 2 CH} 2 OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH ₂ —COO—, —CH ₂ —OCO—, —CH═CH—, —CF═CF— or —C≡C—, wherein A ⁶ and A ⁷ are each independently a 1,4-phenylene group Represents a naphthalene-2,6-diyl group, and the hydrogen atom in the group may be substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogenated alkoxy group, a halogen atom, a cyano group or a nitro group. , N1 represents 3, but the three A ⁶ and Z ⁴ may be the same or different.

Specifically, the compounds represented by the general formula (I-2) are preferably compounds represented by the following formulas (I-2-1) to (I-2-95).

As the general formula (I-2) as the second component, the general formula (II-rm)

(Wherein P ²¹ represents the same meaning as in formula (P-1), (P-2) or (P-3) in formula (I-2), and S ²¹ represents a single bond or a spacer group. Represents an alkylene group having 1 to 10 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the group are each independently —O—, —COO—, —OCO— or — OCO-O- may be substituted, and ring A ²¹ , ring A ²² , ring A ²³ , and ring A ²⁴ are each independently 1,4-phenylene group, 2-fluoro-1,4-phenylene group, Represents a 3-fluoro-1,4-phenylene group, a 3,5-difluoro-1,4-phenylene group or a 2,3-difluoro-1,4-phenylene group, and R ²¹ represents an alkyl having 1 to 10 carbon atoms. A group having 1 to 10 carbon atoms, an alkoxyl group having 2 to 10 carbon atoms Represents Kenyir group or an alkenyloxy group having 2 to 10 carbon atoms, these one or non-adjacent in group two or more -CH 2 _- are each independently -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—, —CH═CH—, —CF═CF— or —C≡C— may be substituted. ) Is more preferable.

In general formula (II-rm), at least one of ring A ²¹ , ring A ²² , ring A ²³ , and ring A ²⁴ is a 2-fluoro-1,4-phenylene group, 3-fluoro-1,4- The phenylene group, the 3,5-difluoro-1,4-phenylene group, and the 2,3-difluoro-1,4-phenylene group are preferable from the viewpoint of dissolution stability at low temperatures.
In general formula (II-rm), R ²¹ is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. The alkoxyl group is preferable.
More specifically, the compound represented by the general formula (II-rm) is preferably a compound represented by the formula (I-2-100) to the formula (I-2-119).

As a third component, a compound having a negative dielectric anisotropy (Δε) and an absolute value larger than 3 is contained. Specific examples include compounds represented by general formula (II-1) and general formula (II-2).

In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 2 to 10 carbon atoms. of it represents alkenyloxy group, ^{R 1} and ^R present in the ² one -CH ₂ - or nonadjacent two or more -CH ₂ - are, each independently -O- or -S- in It may be substituted, and one or more hydrogen atoms present in R ¹ and R ² may be independently substituted with fluorine atoms or chlorine atoms, but R ¹ is An alkyl group having 1 to 5 carbon atoms, an alkoxyl 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 has 1 to 5 carbon atoms. Alkyl group or carbon source The number is more preferably an alkenyl group having 2 to 5, more preferably an alkyl group or an alkenyl group having 2 to 3 carbon atoms, having one to three carbon atoms, R ² is an alkyl group having 1 to 5 carbon atoms, carbon atoms A 1 to 5 alkoxyl group, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms is preferable, and an alkoxyl group having 1 to 5 carbon atoms is more preferable.
In the formula, ring A and ring B are each independently a trans-1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4. -Phenylene group, 3,5-difluoro-1,4-phenylene group, 2,3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] ] Octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group Represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group.
In the formula, Z ¹¹ and Z ²¹ are each independently —OCH ₂ —, —CH ₂ O—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —. or it represents a single _{bond, -CH 2 O -, - CF} 2 O -, - CH 2 CH 2 -, - CF 2 CF 2 - or a single bond are _{preferred, -CH 2 O -, - CH} 2 CH 2 - Alternatively, a single bond is more preferable, and —CH ₂ O— or a single bond is particularly preferable.

The liquid crystal composition of the present invention contains one or more compounds represented by general formula (II-1) and general formula (II-2), but preferably contains 2 to 10 compounds. The content is preferably 10 to 90% by mass, but the lower limit is preferably 15% by mass, preferably 20% by mass, preferably 25% by mass, preferably 30% by mass, and preferably 35% by mass, 40 mass% is preferable, 45 mass% is preferable, 50 mass% is preferable, and the upper limit is preferably 85 mass%, preferably 80 mass%, preferably 75 mass%, preferably 70 mass%, and 65 mass%. Preferably, 60 mass% is preferable, 55 mass% is preferable, 50 mass% is preferable, 45 mass% is preferable, and 40 mass% is preferable.
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). A1) is preferred, a compound represented by the general formula (II-A3) is preferred, a compound represented by the general formula (II-A4) is preferred, The compound represented by the formula (II-A1) is more preferable, and the compound represented by the general formula (II-A4) is further preferable.

In the formula, R ³ and R ⁴ each independently represent the same meaning as R ¹ and R ² .

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). It is preferably a compound represented by B1), preferably a compound represented by the general formula (II-B3), preferably a compound represented by the general formula (II-B4), A compound represented by the formula (II-B5) is preferable, a compound represented by the general formula (II-B6) is preferable, and a compound represented by the general formula (II-B1) is more preferable. The compound of the general formula (II-B3) is more preferable, the compound of the general formula (II-B5) is more preferable, the compound of the general formula (II-B6) is more preferable, Represented by formula (II-B3) Particularly preferably from that compound, it is particularly preferably a compound represented by the general formula (II-B4).

In the formula, R ³ and R ⁴ each independently represent the same meaning as R ¹ and R ² .

More specifically, the third component is preferably a combination of the general formula (II-A1) and the general formula (II-B1), and the general formula (II-A1), the general formula (II-B1) and the general formula A combination of (II-A3) is more preferable, and a combination of general formula (II-A1), general formula (II-B1) and general formula (II-A4) is more preferable.
More specifically, the third component is preferably a combination of the general formula (II-A3) and the general formula (II-B4), and the general formula (II-A3), the general formula (II-B4) and the general formula A combination of (II-B5) is more preferable, and a combination of general formula (II-A3), general formula (II-B4) and general formula (II-B1) is more preferable.
More specifically, the third component is preferably a combination of the general formula (II-A4) and the general formula (II-B4), and the combination of the general formula (II-A4) and the general formula (II-B1) More preferably, it is more preferably a combination of the general formula (II-A4) and the general formula (II-B1) and the general formula (II-B5), and the general formula (II-A4) and the general formula (II- More preferred is a combination of B1) and general formula (II-B3).

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

In the formula, R ⁵ is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, R ⁶ is an alkyl group having 1 to 5 carbon atoms, and an alkoxyl group having 1 to 5 carbon atoms. Represents an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms.
The fourth component is a compound selected from general formula (III-A), general formula (III-D), general formula (III-F), general formula (III-G), and general formula (III-H). It is more preferable that the compound is selected from the general formula (III-A), the general formula (III-F), the general formula (III-G), and the general formula (III-H). -A), a compound selected from general formula (III-G) and general formula (III-H) is more preferable, and general formula (III-A), general formula (III-F) and general formula (III) A compound selected from -H) is also preferred.
In the compounds represented by general formula (III-D), general formula (III-G) and general formula (III-H), R ⁵ represents an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms. 5 alkenyl group having, R ⁶ is preferably an alkoxy group having 1 to 5 alkyl groups or carbon atoms of 1 to 5 carbon atoms, that R ⁵ is an alkenyl group having 2 to 5 carbon atoms More preferably, it is more preferably an alkenyl group having 2 or 3 carbon atoms. In the compound represented by the general formula (III-F), R ⁵ and R ⁶ are each independently 1 to 5 carbon atoms. And an alkenyl group having 2 to 5 carbon atoms.
The content of the fourth component is preferably 1% by mass to 50% by mass, and this lower limit is preferably 3% by mass, preferably 3% by mass, preferably 5% by mass, preferably 10% by mass, 15% % By mass is preferable, 20% by mass is preferable, and 25% by mass is preferable. The upper limit is preferably 45% by mass, preferably 40% by mass, preferably 35% by mass, preferably 30% by mass, and preferably 25% by mass. 20 mass% is preferable, and 15 mass% is preferable.

As a further component, one or more compounds represented by the general formula (V) may be contained.

In the formula, R ²¹ and R ²² are each independently an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. Although an alkenyloxyl group is represented, an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is preferable.

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

As a further component, one or more compounds represented by general formula (VIII-a), general formula (VIII-c) or general formula (VIII-d) can be contained, and the content thereof Are preferably independently from 0 to 10% by mass.

(In the formula, R ⁵¹ and R ⁵² each 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.)

(Expressed in the ^formula, each of ^{R 51} and ^{R 52} are independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group or an alkoxy group having 1 to 4 carbon atoms carbon atoms 2 to ^{5 X 51} and X ⁵² each independently represents a fluorine atom or a hydrogen atom, and at least one of X ⁵¹ and X ⁵² is a fluorine atom.)

(Expressed in the ^formula, each of ^{R 51} and ^{R 52} are independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group or an alkoxy group having 1 to 4 carbon atoms carbon atoms 2 to ^{5 X 51} and X ⁵² each independently represents a fluorine atom or a hydrogen atom, and at least one of X ⁵¹ and X ⁵² is a fluorine atom.)
As a further component, one or more compounds represented by formulas (V-9.1) to (V-9.3) may be contained.

The liquid crystal composition of the present invention preferably contains a compound of formula (I-1), formula (I-2), general formula (II-A1) and general formula (III-A) at the same time. -1), formula (I-2), general formula (II-A3) and general formula (III-A) are preferably contained at the same time, and the compounds of formula (I-1), formula (I-2), It is preferable to simultaneously contain the compounds of the general formula (II-A4) and the general formula (III-A), and the compounds of the formula (I-1), the formula (I-2), the general formula (II-B1) and the general formula (II) It is preferable to contain the compound of III-A) at the same time, and simultaneously contain the compounds of formula (I-1), formula (I-2), general formula (II-B3) and general formula (III-A). And compounds of formula (I-1), formula (I-2), general formula (II-B4) and general formula (III-A) Preferably it contains sometimes formula (I-1), formula (I-2), preferably contains the general formula (II-B5) and a compound of general formula (III-A) at the same time.

The liquid crystal composition of the invention simultaneously contains compounds of formula (I-1), formula (I-2), general formula (II-A1), general formula (II-B1) and general formula (III-A) More preferably, the compounds of formula (I-1), formula (I-2), general formula (II-A3), general formula (II-B5) and general formula (III-A) are contained simultaneously. Is more preferable, and it further contains a compound of the formula (I-1), formula (I-2), general formula (II-A1), general formula (II-B4) and general formula (III-A) at the same time. It is more preferable that the compounds of formula (I-1), formula (I-2), general formula (II-A1), general formula (II-B5) and general formula (III-A) are simultaneously contained.

The liquid crystal composition of the invention simultaneously contains compounds of formula (I-1), formula (I-2), general formula (II-A4), general formula (II-B5) and general formula (III-H) More preferably, the compounds of formula (I-1), formula (I-2), general formula (II-A1), general formula (II-B1) and general formula (III-H) are contained simultaneously. Are more preferred, and are represented by the formulas (I-1), (I-2), (II-A1), (II-B1), (II-B3) and (III-H). More preferably, the compounds are contained simultaneously.

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, and preferably 80 to 100% by mass. More preferred is 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 88 to 100% by mass. It is preferably 93 to 100% by mass, more preferably 97 to 100% by mass.

The liquid crystal composition of the present invention has a dielectric anisotropy (Δε) at −25 ° C. of −2.0 to −8.0, preferably −2.0 to −6.0, -5.0 is more preferable, and -2.5 to -4.5 is particularly preferable.

The liquid crystal composition of the present invention has a refractive index anisotropy (Δn) at 25 ° C. of 0.08 to 0.14, more preferably 0.09 to 0.13, and 0.09 to 0.12. Particularly preferred. More specifically, it is preferably 0.10 to 0.13 when dealing with a thin cell gap, and preferably 0.08 to 0.10 when dealing with a thick cell gap.

The liquid crystal composition of the present invention has a rotational viscosity (γ ₁ ) at 25 ° C. of 60 to 200 mPa · s, and the upper limit is preferably 190 mPa · s, preferably 180 mPa · s, preferably 170 mPa · s, preferably 160 mPa · s. 150 mPa · s, preferably 140 mPa · s, preferably 130 mPa · s, and preferably 125 mPa · s.

The liquid crystal composition of the present invention has a solid phase-nematic phase transition temperature (T _cn ) of −60 ° C. to −15 ° C., more preferably −60 ° C. to −20 ° C., and −60 ° C. to −25 ° C. Particularly preferred.
The liquid crystal composition of the present invention has a nematic phase-isotropic liquid phase transition temperature (T _ni ) of 60 ° C. to 120 ° C., more preferably 70 ° C. to 100 ° C., and particularly preferably 70 ° C. to 85 ° C.
The liquid crystal composition of the present invention has an elastic constant (K ₃₃ ) at 25 ° C. of 10 pN to 20 pN, more preferably 12 pN to 18 pN, and particularly preferably 13 pN 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%, and preferably 85% to 100%. However, the measurement conditions are 1 V, 3 Hz, and 60 ° C., and VHR measurement is performed after UV (12 J) irradiation with a high-pressure mercury lamp.

In addition to the above-mentioned compounds, the liquid crystal composition of the present invention contains ordinary nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, antioxidants, ultraviolet absorbers, light stabilizers (HALS), spontaneous alignment compounds, infrared absorbers, and the like. It may be contained.

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

Specifically, for example, polymerizable compounds such as biphenyl derivatives and terphenyl derivatives can be mentioned, and in such a case, 0.01 to 2% by mass is contained. More specifically, the general formula (M)

1 type, or 2 or more types can be contained.

In the general formula (M), X ²⁰¹ and X ²⁰² each independently represent a hydrogen atom, a methyl group, or a —CF ₃ group. X ²⁰¹ and X ²⁰² are each preferably a diacrylate derivative that is a hydrogen atom, and a dimethacrylate derivative that is both a methyl group, and a compound in which one is a hydrogen atom and the other is a methyl group. A preferred compound can be used depending on the application, but in the PSA display element, the polymerizable compound represented by the general formula (M) preferably has at least one methacrylate derivative, and preferably has two.

In the general formula (M), Sp ²⁰¹ and Sp ²⁰² are each independently a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH ₂ ) _s — (wherein s is 2 to 7 And an oxygen atom is bonded to the ring. In the PSA mode liquid crystal display element, at least one of Sp ²⁰¹ and Sp ²⁰² is preferably a single bond, either a single bond compound or one of which is a single bond and the other is an alkylene having 1 to 8 carbon atoms. Group or —O— (CH ₂ ) _s —, in which case an alkylene group having 1 to 4 carbon atoms is preferred, and s is preferably 1 to 4.

In general formula (M), ring M ²⁰¹ , ring M ²⁰² and ring M ²⁰³ are each independently a trans-1,4-cyclohexylene group (one or non-adjacent two or more —CH in the group). ₂ — may be substituted by —O— or —S—), 1,4-phenylene group (one or two or more non-adjacent —CH═ in the group is substituted by —N═. 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, deca Represents a hydronaphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and each hydrogen atom in the group independently represents a fluorine atom, a —CF ₃ group, An alkyl group having 1 to 10 carbon atoms, 1 carbon atom To 10 alkoxyl groups or formulas (R-1) to (R-15).

In the general formula (M), Z ²⁰¹ and Z ²⁰² each independently represent —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, — CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO —, —CH ₂ —OCO—, —CY ¹ ═CY ² — (wherein Y ¹ and Y ² each independently represents a fluorine atom or a hydrogen atom), —C≡C— or a single bond Represents —COO—, —OCO—, —CH═CH—COO—, — H = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO-, —CH ₂ CH ₂ —OCO—, —C≡C— or a single bond is preferable, —COO—, —OCO—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH _{-, - OCO-CH = CH} -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO- or a single bond is more preferable.

In the general formula (M), n ²⁰¹ represents 0, 1 or 2, with 0 or 1 being preferred. However, when there are a plurality of rings M ²⁰² and Z ²⁰² , they may be different or the same.

It may contain at least one polymerizable compound represented by formula (M), preferably 1 to 5 types, more preferably 1 to 3 types.
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 0.10 to 0.50% by mass. It is particularly preferred.

More specifically, in the general formula (M), when n ²⁰¹ is 0, the ring structure between Sp ²⁰¹ and Sp ²⁰² is preferably a formula (XXa-1) to a formula (XXa-5), The formula (XXa-1) to the formula (XXa-3) are more preferable, and the formula (XXa-1) or the formula (XXa-2) is particularly preferable. However, both ends of the equation shall be connected to Sp ²⁰¹ or Sp ²⁰² .

The polymerizable compound represented by the general formula (M) containing these skeletons is suitable for a PSA mode liquid crystal display element because of its alignment regulating force after polymerization, and a good alignment state can be obtained, thereby suppressing display unevenness. There is an effect that does not occur at all.

From the above, as the polymerizable compound, a compound represented by the formula (XX-1) to the general formula (XX-10) is preferable, and a formula (XX-1) to a formula (XX-4) is more preferable.

In formula (XX-1) to general formula (XX-10), Sp ^xx represents 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 formula (XX-1) to general formula (XX-10), the hydrogen atom in the 1,4-phenylene group is further —F, —Cl, —CF ₃ , —CH ₃ , formula (R-1) To any one of formulas (R-15).

In the general formula (M), when n ²⁰¹ is 1, for example, a polymerizable compound such as the formula (M31) to the formula (M48) is preferable.

The hydrogen atoms in the 1,4-phenylene group and naphthalene group in the formula (M31) to the formula (M48) are further represented by —F, —Cl, —CF ₃ , —CH ₃ , and the formula (R-1) to the formula It may be substituted by any of (R-15).

The polymerizable compound represented by the general formula (M) containing these skeletons is suitable for a PSA mode liquid crystal display element because of its alignment regulating force after polymerization, and a good alignment state can be obtained, thereby suppressing display unevenness. There is an effect that does not occur at all.

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

More specifically, as the polymerizable compound, for example, trifunctional polymerizable compounds such as formula (M301) to formula (M316) are also preferable.

The hydrogen atoms in the 1,4-phenylene group and naphthalene group in the formulas (M301) to (M316) may be further substituted with —F, —Cl, —CF ₃ , or —CH ₃ .
Further, as the antioxidant to be added to the liquid crystal composition of the present invention, hindered phenols represented by general formula (H-1) to general formula (H-4) are preferable.

In general formulas (H-1) to (H-4), R ^H1 represents an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or It represents an alkenyloxy group having 2 to 10 carbon atoms, one -CH ₂ present in the radical - or non-adjacent two or more -CH ₂ - are each independently -O- or -S- In addition, one or two or more hydrogen atoms present in the group may be independently substituted with a fluorine atom or a chlorine atom. More specifically, it is an alkyl group having 2 to 7 carbon atoms, an alkoxyl 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. 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 ^{(H4), M H4} is -CH ₂ 1, two or more of the alkylene group (the alkylene group having from 1 to 15 carbon atoms - as the oxygen atoms are not directly adjacent, - O—, —CO—, —COO—, —OCO— may be substituted.), —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, — OCF ₂ —, —CF ₂ CF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, — C≡C—, a single bond, a 1,4-phenylene group (any hydrogen atom in the 1,4-phenylene group may be substituted with a fluorine atom) or a trans-1,4-cyclohexylene group. Preferably an alkylene group having 1 to 14 carbon atoms, The Although consideration of the number of carbon atoms is larger numerical Preferably, rotational viscosity (gamma ₁₎ consider the number of carbon atoms from that it is preferred not too large, more preferably 2 to 12 carbon atoms, carbon atoms 3 10 is more preferred, 4 to 10 carbon atoms are more preferred, 5 to 10 carbon atoms are more preferred, and 6 to 10 carbon atoms are still more preferred.
In general formula (H-1) to general formula (H-4), one or more non-adjacent —CH═ in the 1,4-phenylene group may be substituted by —N═. In addition, each hydrogen atom in the 1,4-phenylene group may be independently substituted with a fluorine atom or a chlorine atom.
In general formula (H-1) to general formula (H-4), one or more non-adjacent —CH ₂ — in the 1,4-cyclohexylene group is replaced by —O— or —S—. May be. In addition, each hydrogen atom in the 1,4-cyclohexylene group may be independently substituted with a fluorine atom or a chlorine atom.
More specifically, for example, the formulas (H-11) to (H-15) can be given.

The liquid crystal composition of the present invention may contain 1 ppm by mass or more of an antioxidant, preferably 10 ppm by mass or more, preferably 20 ppm by mass or more, and more preferably 50 ppm by mass or more. Although the upper limit of content of antioxidant is 10000 mass ppm, 1000 mass ppm is preferable, 500 mass ppm is preferable, and 100 mass ppm is preferable.

The liquid crystal composition of the present invention is useful for a liquid crystal display device, particularly useful for a liquid crystal display device for driving an active matrix, and used for a liquid crystal display device for PSA mode, PSVA mode, VA mode, IPS mode or ECB mode. Can do.

The liquid crystal composition of the present invention is a liquid crystal display element in which a polymerizable compound contained therein is polymerized by ultraviolet irradiation to impart liquid crystal alignment ability, and the amount of transmitted light is controlled using the birefringence of the liquid crystal composition Used for. As liquid crystal display elements, 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) However, it is particularly useful for AM-LCDs and can be used for transmissive or reflective liquid crystal display elements. Further, it can be applied to a liquid crystal display element having no alignment film.

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

The color filter can be prepared by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. A method for producing a color filter by a pigment dispersion method will be described as an example. A curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be created. In addition, a pixel electrode provided with an active element such as a TFT, a thin film diode, or a metal insulator metal specific resistance element may be provided on the substrate.

The substrate is opposed so that the transparent electrode layer is on the inside. In that case, you may adjust the space | interval of a board | substrate through a spacer. In this case, it is preferable to adjust so that the thickness of the obtained light control layer is 1 to 100 μm. More preferably, the thickness is 1.5 to 10 μm. When a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so that the contrast is maximized. In addition, when there are two polarizing plates, the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good. Furthermore, a retardation film for widening the viewing angle can also be used. Examples of the spacer include glass particles, plastic particles, alumina particles, and a photoresist material. Thereafter, a sealant such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal inlet provided, the substrates are bonded together, and heated to thermally cure the sealant.

As a method of sandwiching the polymerizable compound-containing liquid crystal composition between the two substrates, a normal vacuum injection method or an ODF method can be used.

As a method for polymerizing a polymerizable compound, an appropriate polymerization rate is desirable in order to obtain good alignment performance of liquid crystals. Therefore, active energy rays such as ultraviolet rays or electron beams are irradiated singly or in combination or sequentially. The method of polymerizing by is preferred. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. In addition, when the polymerization is performed in a state where the polymerizable compound-containing liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must be given appropriate transparency to the active energy rays. I must. Moreover, after polymerizing only a specific part using a mask during light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as an electric field, a magnetic field, or temperature, and further irradiation with active energy rays is performed. Then, it is possible to use a means for polymerization. In particular, when ultraviolet exposure is performed, it is preferable to perform ultraviolet exposure while applying an alternating electric field to the liquid crystal composition of the invention. The alternating electric field to be applied is preferably an alternating current having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 60 Hz to 10 kHz, and the voltage is selected depending on a desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element is controlled by the applied voltage. In the MVA mode liquid crystal display element, it is necessary to control the pretilt angle from about 80 degrees to about 88 degrees from the viewpoint of alignment stability and contrast. However, by using the liquid crystal composition of the present invention, it is desirable to control the pretilt angle. The pretilt angle can be controlled.

The temperature during irradiation is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition of the present invention is maintained. Polymerization is preferably performed at a temperature close to room temperature, that is, typically at a temperature of 15 to 35 ° C. As a 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. Moreover, as a wavelength of the ultraviolet-rays to irradiate, it is preferable to irradiate the ultraviolet-ray of the wavelength range which is not the absorption wavelength range of a liquid crystal composition, and it is preferable to cut and use an ultraviolet-ray as needed. Intensity of ultraviolet irradiation is ^preferably from 0.1mW / cm 2 ~ 100W / cm 2, 2mW / cm 2 ~ 50W / cm 2 is more preferable. The amount of energy of ultraviolet rays to be irradiated can be adjusted as appropriate, but is preferably 10 mJ / cm ² to 500 J / cm ^{2, and} more preferably 100 mJ / cm ² to 200 J / cm ² . When irradiating with ultraviolet rays, the intensity may be changed. The time for irradiating with ultraviolet rays is appropriately selected depending on the intensity of the irradiated ultraviolet rays, but is preferably from 10 seconds to 3600 seconds, and more preferably from 10 seconds to 600 seconds.

EXAMPLES The present invention will be described in further detail with reference to examples below, but the present invention is not limited to these examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.
The following abbreviations are used for the description of compounds in the examples.
(Side chain)
-n -C _n H _{2n + 1} linear alkyl group with n carbon atoms n- C _n H _{2n + 1} -linear alkyl group with n carbon atoms -On -OC _n H _{2n + 1} carbon number n Linear alkoxyl group nO- C _n H _{2n + 1} O- linear alkoxyl group of n carbon atoms -V -CH = CH ₂
V- CH ₂ = CH-
-V1 -CH = CH-CH ₃
1V- CH ₃ -CH = CH-
-2V -CH ₂ -CH ₂ -CH = CH ₃
V2- CH ₃ = CH-CH ₂ -CH _2-
-2V1 -CH ₂ -CH ₂ -CH = CH-CH ₃
1V2- CH ₃ -CH = CH-CH ₂ -CH _2-
(Linking group)
-CF2O- -CF ₂ -O-
-OCF2- -O-CF ₂ -
-1O- -CH ₂ -O-
-O1- -O-CH _2-
-COO- -COO-
(Ring structure)

In the examples, the measured characteristics are as follows.

T _ni : Nematic phase-isotropic liquid phase transition temperature (° C.)
T _cn : Solid phase-nematic phase transition temperature (° C)
Δn: Refractive index anisotropy at 25 ° C. Δε: Dielectric anisotropy at 25 ° C. γ ₁ : Rotational viscosity at 25 ° C. (mPa · s)
K ₃₃ : Elastic constant at 25 ° C. K ₃₃ (pN)
VHR: Voltage holding ratio (%) after UV irradiation with 12 (J) with a high-pressure mercury lamp
(Comparative Examples 1 to 5 and Examples 1 to 13)
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 (implemented) Liquid crystal compositions of Example 2), LC-3 (Example 3) and LC-4 (Example 4) were prepared, and their physical properties were measured. The composition of the liquid crystal composition and the results of its physical properties are shown in Table 1.

The liquid crystal composition LC-1 of the present invention was confirmed to have a negative Δε and a large absolute value, low γ1, large K ₃₃ , low T _cn , high T _ni and high VHR. As a result of a low-temperature storage test at −25 ° C. for 100 hours in LC-1, it was confirmed that the nematic phase was maintained. When the response speed of the liquid crystal display element using this was measured, it was sufficiently high-speed response. It was also confirmed that there were no display defects such as burn-in and display unevenness. The cell thickness was 3.3 μm, the alignment film was JALS2096, the response speed measurement conditions were Von 6 V, Voff 1 V, measurement temperature 30 ° C., and DUT 703 manufactured by AUTRONIC-MELCHERS.
Further, a liquid crystal composition in which 0.35% by mass of the compound of the formula (XX-2) is added as a polymerizable compound to 99.65% by mass of each of the LC-1 to LC-4 above. Thus, a PSVA mode liquid crystal display element was manufactured, and it was confirmed that there was no display defect in any of the elements and the response was sufficiently fast. (Examples 5 to 8)
Further, by using a liquid crystal composition in which 0.3% by mass of the formula (XX-4) is added as a polymerizable compound to 99.7% by mass of each liquid crystal composition of LC-1 to LC-4, PSVA A mode liquid crystal display device was manufactured, and it was confirmed that there was no display defect in any of the devices and the response was sufficiently fast. (Examples 9 to 12)
A liquid crystal display element of PSVA mode is obtained using a liquid crystal composition in which 0.35% by mass of the compound of formula (XX-2) is added as a polymerizable compound to 99.65% by mass of the liquid crystal composition LC-A. When fabricated, a burn-in phenomenon was observed. (Comparative Example 5)
Further, a liquid crystal composition LC-5 (Example 13) in which the 3-Cy-Cy-V compound of Example 1 was substituted with a V-Cy-Cy-V compound was prepared, and the physical properties thereof were measured. Γ ₁ superior to that of Example 1 was obtained.

From the above, the liquid crystal composition of the present invention has a negative Δε and a large absolute value, a low rotational viscosity (γ ₁ ), a large elastic constant (K ₃₃ ), a low solid phase-nematic phase transition temperature (T _cn ). , High nematic phase-isotropic liquid phase transition temperature (T _ni ), low-temperature dissolution stability and high voltage holding ratio (VHR), and VA type, PSVA type, PSA type, FFS produced using this It has been confirmed that the liquid crystal display element such as a mold has a high VHR, has a high-speed response with excellent display quality, and has no or suppressed display defects such as image sticking and display unevenness.

Claims (11)

As the first component, the general formula (I-1)

(Wherein R ¹¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxyl 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, R ¹² represents an alkyl group having 1 to 10 carbon atoms, an alkoxyl 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. As a second component, the general formula (I-2)

(In the formula, P represents a polymerizable group, S represents a single bond or a spacer group, and when a plurality of S are present, they may be the same or different, and X represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—. NH—, —NH—CO—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO— _{, -CH 2 CH 2 -OCO -,} - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH -OCO -, - CH = CH - , - CF = CF- or represents a single bond, they if X there is a plurality may be different even in the ^{same, A 1, A 2, A} 3, A ⁴ and A ⁵ each independently represents 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl, and the hydrogen atom in these groups is one or more L When a plurality of A ⁵ are present, they may be the same or different, and Z ¹ , Z ² , and Z ³ are each independently —O—, — S-, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH _{-, - NH-CO -,} - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 - _{-CF 2 S -, - SCF 2} -, - CH 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 -, - CH = CH-COO -, - CH = CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO—, —CH═CH—, —CF═CF— or —C≡ R represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group or one —CH ₂ - or a straight chain of 1 to 12 carbon atoms Although represents a branched alkyl group, two or more -CH ₂ nonadjacent - each independently -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—, —CH═CH—, —CF═CF— or —C≡C—, wherein l represents an integer of 0 to 8, m1, m2 and m3 Represents 0 or 1, n represents 0, 1 or 2, L represents a fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group or methoxy group, and m1 + m2 + m3 represents 0 or 1. A liquid crystal composition having a negative dielectric anisotropy (Δε) containing a compound represented by The dielectric anisotropy (Δε) at 20 ° C. is in the range of −2.0 to −8.0, and the refractive index anisotropy (Δn) at 20 ° C. is in the range of 0.08 to 0.14. The liquid crystal according to claim 1, wherein the rotational viscosity (γ1) at 20 ° C is in the range of 60 to 200 mPa · s, and the nematic phase-isotropic liquid phase transition temperature (T _ni ) is in the range of 60 ° C to 120 ° C. Composition. As the third component, general formula (II-1) and general formula (II-2)

Wherein R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 2 carbon atoms. represents 10 alkenyloxy group, ^{R 1} and ^R present in the ² one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O- and / or -S And one or more hydrogen atoms present in R ¹ and R ² may be independently substituted with a fluorine atom or a chlorine atom. Are independently trans-1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5- Difluoro-1,4-phenylene group, 2 , 3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6 -Represents a diyl group, a decahydronaphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, wherein Z ¹¹ and Z ²¹ each independently represent —OCH ₂ -, —CH ₂ O—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ — or a single bond)) The liquid crystal composition according to claim 1 or 2, comprising one or more kinds. As the fourth component, from general formula (III-A) to general formula (III-J)

(Wherein R ⁵ is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, R ⁶ is an alkyl group having 1 to 5 carbon atoms, and an alkoxyl having 1 to 5 carbon atoms. Group, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms, provided that the compound represented by the general formula (III-A) is represented by the general formula (I-1). 4. The liquid crystal composition according to claim 1, wherein the liquid crystal composition contains one or more compounds selected from the group of compounds represented by: 5. The liquid crystal composition according to claim 3, comprising a compound represented by the general formula (II-1) and a compound represented by the general formula (II-2) at the same time. The general formula (II-1) is changed from the general formula (II-A1) to the general formula (II-A4).

And the general formula (II-2) is changed from the general formula (II-B1) to the general formula (II-B6).

The liquid crystal composition according to claim 3, wherein: 4. The liquid crystal composition according to claim 3, comprising one or more compounds selected from the group of compounds wherein R ^{1 in} general formula (II-1) and general formula (II-2) is a propenyl group. Formula (IV)

(Wherein R ⁷ and R ⁸ are each independently formulas (R-1) to (R-15)

X ¹ to X ⁸ each independently represents a trifluoromethyl group, a trifluoromethoxy group, a fluorine atom or a hydrogen atom. 8) The liquid crystal composition according to any one of claims 1 to 7. The liquid crystal display element using the liquid-crystal composition of any one of Claim 1 to 8. A liquid crystal display element for active matrix driving using the liquid crystal composition according to claim 1. A VA-type, FFS-type, PSA-type, and PSVA-type liquid crystal display element using the liquid crystal composition according to any one of claims 1 to 8.