CN111373017A

CN111373017A - Liquid crystal composition and liquid crystal display element

Info

Publication number: CN111373017A
Application number: CN201880075272.4A
Authority: CN
Inventors: 橘内崇; 幡野直美
Original assignee: DIC Corp
Current assignee: Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
Priority date: 2017-12-15
Filing date: 2018-11-29
Publication date: 2020-07-03
Anticipated expiration: 2038-11-29
Also published as: TWI763954B; JP6575735B1; WO2019116904A1; CN111373017B; JPWO2019116904A1; TW201930566A; KR20200098501A

Abstract

The object of the present invention is to provide a liquid crystal composition having negative dielectric anisotropy Deltaepsilon and T_NIHigh, Δ n large, γ 1 small; and a VA-type, FFS-type, or IPS-type liquid crystal display element which has no or very few display defects, has a high response speed and a high VHR, and a PSA element using the polymerizable compound. The liquid crystal composition of the present invention solves the above problems by a liquid crystal composition containing a compound of the general formula (i).

Description

Liquid crystal composition and liquid crystal display element

Technical Field

The present invention relates to a liquid crystal composition and a liquid crystal display element using the same.

Background

Liquid crystal display devices have been used in clocks and watches, electronic calculators, and various household electrical appliances, measuring instruments, panels for automobiles, word processors, electronic notebooks, printers, computers, televisions, and the like. Typical 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, OCB (optically compensated birefringence) mode, ECB (voltage controlled birefringence) mode, VA (vertically aligned) mode, CSH (color super vertical) mode, and FLC (ferroelectric liquid crystal). Further, as a driving method, a static driving, a multiplex driving, a simple matrix method, and an Active Matrix (AM) method using a TFT (thin film transistor), a TFD (thin film diode), or the like may be mentioned. Among these display modes, the IPS mode, ECB mode, VA mode, CSH mode, and the like have a characteristic that a liquid crystal composition exhibiting a negative value Δ ∈ (dielectric anisotropy) is used. Among these, the VA display system using AM driving is used for display elements requiring high-speed response and a wide viewing angle, for example, televisions and monitors.

As a liquid crystal composition having a negative value of Δ ∈, liquid crystal compositions using the following liquid crystal compounds (a) to (E) having a 2, 3-difluorophenylene skeleton (see patent document 1) and the like are disclosed.

[ solution 1]

However, any liquid crystal composition cannot achieve both response speed and reliability required for a large-sized liquid crystal display element in particular.

Patent document 2 discloses that the response speed of a vertically aligned liquid crystal cell is increased by using a liquid crystal material having a large index (FoM) expressed by the following numerical expression, but it cannot be said that the response speed is sufficiently satisfied.

[ number 1]

FoM＝K₃₃·Δn²/γ1

In view of the above, in a liquid crystal composition requiring high-speed response and high reliability such as a liquid crystal television, the nematic phase-isotropic liquid phase transition temperature (T) is appropriately adjusted_NI) And refractive index anisotropy (. DELTA.n), and rotational viscosity (. gamma.) are required₁) Small, elastic constant (K)₃₃) Large, gamma₁/K₃₃Small and the voltage holding ratio VHR is high.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2016 and No. 216747

Patent document 2: japanese patent laid-open publication No. 2006-301643

Disclosure of Invention

Problems to be solved by the invention

The present invention addresses the problem of providing a liquid crystal composition having a negative dielectric anisotropy (Δ ∈), and a suitably adjusted T_NIAnd Δ n and γ 1 are small, and a VA-type, FFS-type, or IPS-type liquid crystal display element which uses the liquid crystal composition, has a high response speed, has a high VHR, and has no or very few display defects is provided.

Means for solving the problems

The present inventors have made extensive studies and as a result, have found that the above problems can be solved by a liquid crystal composition containing a compound having a specific chemical structure, and have completed the present invention.

Further, the above problems can be solved by using a polymerizable compound together with the liquid crystal composition, and the present invention has been completed.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention can provide a liquid crystal composition having negative dielectric anisotropy (. DELTA.. di-elect cons.), T_NIThe liquid crystal composition is high in Δ n and small in γ 1, and the present invention can provide a VA-type, FFS-type or IPS-type liquid crystal display element which has no or very few display defects, has a high response speed and has a high VHR, using the liquid crystal composition.

Detailed Description

The liquid crystal composition of the present invention contains a compound having a negative dielectric anisotropy (Δ ∈) represented by the general formula (i); the present invention is a liquid crystal composition further containing a polymerizable compound, and a liquid crystal display element using the liquid crystal composition.

[ solution 2]

In the formula, Xⁱ¹And Xⁱ²Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a trifluoromethoxy group,

Yⁱ¹and Yⁱ²Each independently represents-O-, -CF₂-、-CO-、-CXⁱ³Xⁱ⁴-，Yⁱ¹And Yⁱ²Any one or more of (A) represents-O-, Xⁱ³、Xⁱ⁴Independently of each other representⁱ¹The same meaning is given to the same person,

Lⁱ¹、Lⁱ²、Lⁱ³、Lⁱ⁴and Lⁱ⁵Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms or a general formula (L)ⁱ-1) a group represented by,

[ solution 3]

(in the formula, Rⁱ¹Represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms or an alkenyloxy group having 2 to 15 carbon atoms,

Aⁱ¹represents a group selected from the group consisting of:

(a)1, 4-cyclohexylene radical (1-CH present in the radical)₂-or non-contiguous 2 or more-CH₂-may be substituted by-O-or-S-),

(b)1, 4-phenylene (1-CH-present in the group or 2 or more-CH-not adjacent thereto may be substituted by-N-and 1 hydrogen atom present in the group may be substituted by a fluorine atom),

(c)1, 4-cyclohexenyl group, naphthalene-2, 6-diyl group, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl group, decahydronaphthalene-2, 6-diyl group (the hydrogen atom present in the group may be substituted by a fluorine atom, and in addition, 1-CH ═ or non-adjacent 2 or more-CH ═ present in naphthalene-2, 6-diyl group or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl group may be substituted by-N ═ may be added),

Zⁱ¹represents-CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-、-COO-、-OCO-、-CH₂CH₂-、-CF₂CF₂-, -CH-, -CF-, -C.ident.C-or a single bond,

nⁱ¹represents 1 or 2, in nⁱ¹Represents 2 and has a plurality of Aⁱ¹And Zⁱ¹When they are the same, they may be different);

Wⁱ¹is represented by the general formula (W)ⁱ¹-1)、(Wⁱ¹-2) or (W)ⁱ¹-3) a group represented by (a),

[ solution 4]

(wherein:. represents and Lⁱ²Or Yⁱ²＊ denotes a bond with Lⁱ⁵Bonded carbon atomLinkage point of sub-adjacent carbon atoms, Lⁱ⁶、Lⁱ⁷And Lⁱ⁸Independently of each other representⁱ¹The same meaning),

Wⁱ²represents a single bond or-CLⁱ⁹Lⁱ¹⁰-，

(Lⁱ⁹And Lⁱ¹⁰Independently of each other representⁱ¹The same meaning),

Lⁱ¹、Lⁱ²、Lⁱ³、Lⁱ⁴、Lⁱ⁵、Lⁱ⁶、Lⁱ⁷、Lⁱ⁸、Lⁱ⁹and Lⁱ¹⁰1 of-CH present in₂-or non-contiguous 2 or more-CH₂May be substituted by-C.ident.C-, -O-, -COO-, -OCO-or-CO-, and in addition, the hydrogen atoms present in the alkyl or alkenyl groups may be substituted by fluorine atoms).

The lower limit of the content of the compound of the general formula (i) in the liquid crystal composition of the present invention is preferably 0.1 mass%, preferably 0.2 mass%, preferably 0.3 mass%, preferably 0.5 mass%, preferably 1 mass%, preferably 2 mass%, preferably 3 mass%, preferably 4 mass%, the upper limit is preferably 20 mass%, more preferably 15 mass%, more preferably 13 mass%, and even more preferably 10 mass%, and the range of the content is preferably 0.1 to 25 mass%, more preferably 0.1 to 20 mass%, even more preferably 0.1 to 15 mass%, and even more preferably 1 to 15 mass%. Hereinafter, the mass% is described as%.

Attach importance to T_NIWhen the content is small, it is preferable to improve γ₁/K₃₃When importance is attached to the response speed, the preferable content is large.

In the general formula (i), X is preferredⁱ¹And Xⁱ²At least one of them is a fluorine atom, preferably all are fluorine atoms.

Yⁱ¹And Yⁱ²Preferably one is O-and the other is-CH₂-and compounds both of which are-O-, preferably both of which are-O-.

Preferably Lⁱ¹And Lⁱ²Each independently represents a hydrogen atom or a carbon atom having 1 to 15Alkyl group, alkenyl group having 2 to 15 carbon atoms, for lowering γ₁The alkyl group having 1 to 8 carbon atoms or the alkenyl group having 2 to 8 carbon atoms is preferable, and the alkyl group having 1 to 5 carbon atoms or the alkenyl group having 2 to 5 carbon atoms is particularly preferable. Further, the linear form is preferable. In order to increase | Δ ∈ | it is preferably an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, and particularly preferably an alkoxy group having 1 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms. L is preferably L for improving the miscibility with other liquid crystal componentsⁱ¹And Lⁱ²Different, preferably Lⁱ¹And Lⁱ²Is alkoxy or alkenyloxy, particularly preferably Lⁱ¹Is an alkoxy group. At Lⁱ¹And Lⁱ²The hydrogen atoms present in (a) may be substituted by fluorine atoms, preferably not.

In addition, Lⁱ¹And Lⁱ²The following are preferred:

[ solution 5]

To make gamma₁Decrease Rⁱ¹Preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. Further, the linear form is preferable. In order to increase | Δ ∈ | it is preferable to increase the content of an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, and particularly preferable to increase the content of an alkoxy group having 1 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms. In the presence of a plurality of Rⁱ¹In this case, R is preferably used for improving the miscibility with other liquid crystal componentsⁱ¹Preferably a plurality of R's different from each otherⁱ¹Any of which is alkoxy or alkenyloxy, particularly preferably Lⁱ¹R in (1)ⁱ¹Is alkoxy or alkenyloxy. Rⁱ¹The hydrogen atoms present in (a) may be substituted by fluorine atoms, preferably not.

Preferably Aⁱ¹Represents a group selected from the following groups.

[ solution 6]

Specifically, to make γ₁Decrease, preferably A¹Trans-1, 4-cyclohexylene, unsubstituted 1, 4-phenylene, 2-fluoro-1, 4-phenylene or 3-fluoro-1, 4-phenylene, trans-1, 4-cyclohexylene being particularly preferred. In order to improve miscibility with other liquid crystal components, trans-1, 4-cyclohexylene, 2-fluoro-1, 4-phenylene or 3-fluoro-1, 4-phenylene is preferable. To increase T_niPreference is given to unsubstituted 1, 4-phenylene, unsubstituted 1, 4-cyclohexylene, 1, 4-cyclohexenyl or unsubstituted naphthalene-2, 6-diyl. To exhibit a large negative Δ ∈, 2-fluoro-1, 4-phenylene, 3-fluoro-1, 4-phenylene, or 2, 3-difluoro-1, 4-phenylene is preferable. In order to exhibit a large negative Δ ∈ and to have miscibility with other liquid crystal components, Aⁱ¹The total number of fluorine atoms present in (A) is preferably 1 to 4, and particularly preferably 1 to 3.

To make gamma₁Decrease of Zⁱ¹Preferably a single bond, -CH₂CH₂-、-CH₂O-or-OCH₂-, more preferably a single bond or-CH₂CH₂-. To increase T_niPreferably a single bond, -COO-, -OCO-, -CH ≡ CH-or-C.ident.C-, more preferably a single bond, -CH ═ CH-or-C.ident.C-. In order to improve the miscibility with other liquid crystal components, a single bond, -CH is preferable₂CH₂-、-CH₂O-or-OCH₂-. In order to improve long-term reliability in a liquid crystal display device, a single bond is preferable.

nⁱ¹When 2 is represented, it is preferable that plural Z's are presentⁱ¹Any one or more of (1) represents a single bond. Attach importance to gamma₁When n is greater than nⁱ¹Preferably 1. Attach importance to T_niWhen this is the case, it is preferably 2.

Wⁱ¹Preferably of the formula (W)ⁱ¹-1) or (W)ⁱ¹-3)。

Wⁱ²Preferably a single bond.

Lⁱ³Preferably represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or an alkenyloxy group having 2 to 15 carbon atoms, in order to make γ₁The amount of the carbon atom-containing alkyl group is preferably 1 to 8 carbon atoms or 2 to 8 carbon atoms, and more preferably 1 to 5 carbon atoms or 2 to 5 carbon atoms. Further, the linear form is preferable.

Preferably Lⁱ¹、Lⁱ²And Lⁱ³Is a hydrogen atom, preferably Lⁱ¹Or Lⁱ³Is a hydrogen atom. Preferably Lⁱ¹Is alkyl of 1 to 8 carbon atoms or alkoxy of 1 to 8 carbon atoms, Lⁱ²Is a hydrogen atom, Lⁱ³Is an alkyl group having 1 to 8 carbon atoms, preferably Lⁱ¹Is a hydrogen atom, Lⁱ²Is alkyl of 1 to 8 carbon atoms or alkoxy of 1 to 8 carbon atoms, Lⁱ³Is an alkyl group having 1 to 8 carbon atoms.

Preferably Lⁱ⁴And Lⁱ⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms, and preferably represents a hydrogen atom.

Preferably Lⁱ⁶And Lⁱ⁷Each independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms, and preferably a hydrogen atom.

Preferably Lⁱ⁸Represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or an alkenyloxy group having 2 to 15 carbon atoms, and is preferably a hydrogen atom.

Preferably Lⁱ⁹And Lⁱ¹⁰Represents a hydrogen atom.

In the compound represented by the general formula (i), the hetero atoms are not directly bonded to each other.

Among the compounds represented by the general formula (i), the compounds represented by the following general formulae (i-1) to (i-48) are preferable. Among them, particularly preferred compounds are those represented by the general formulae (i-1), (i-2), (i-3), (i-4), (i-5), (i-6), (i-7), (i-8), (i-9), (i-10), (i-11) and (i-12), those represented by the general formulae (i-1), (i-2), (i-3) and (i-4), those represented by the general formulae (i-1) and (i-3), and those represented by the general formula (i-1).

[ solution 7]

(in the formula, Rⁱ¹And Rⁱ²Represents R in the general formula (i)ⁱ¹Same meaning)

[ solution 8]

[ solution 9]

[ solution 10]

The liquid crystal composition of the present invention preferably contains one or more compounds selected from the group of compounds represented by the general formulae (N-01), (N-02), (N-03), (N-04) and (N-05) in addition to the compound represented by the general formula (i). These compounds correspond to compounds having negative anisotropy in dielectric properties. These compounds Δ ∈ have negative signs and their absolute values show values greater than 2. In addition, Δ ∈ of the compound was the following value: the value extrapolated from the measurement of dielectric anisotropy of a composition in which the compound is added to a composition having a dielectric property of approximately neutral at 25 ℃.

[ solution 11]

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, 1 or 2 or more-CH groups not adjacent to each other₂-may be independently substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-or-OCO-, Z¹Each independently represents a single bond, -CH₂CH₂-、-OCH₂-、-CH₂O-、-COO-、-OCO-、-OCF₂-、-CF₂O-, -CH ═ CH-, -CF ═ CF-or-C ≡ C-, and m independently represents 1 or 2, respectively.

R²¹The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms. Wherein Z is¹When it represents other than a single bond, R²¹Preferably an alkyl group having 1 to 3 carbon atoms.

R²²Preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and still more preferably an alkoxy group having 1 to 4 carbon atoms.

R²¹And R²²May be an alkenyl group, preferably a group represented by any one of the formulae (R1) to (R5) (black points in each formula represent carbon atoms in a ring structure), preferably formula (R1) or formula (R2), R²¹And R²²The content of the compound which is an alkenyl group is preferably as small as possible, and the content of the compound which is not contained is preferably large.

[ solution 12]

Z¹Each independently represents a single bond, -CH₂CH₂-、-OCH₂-、-CH₂O-、-COO-、-OCO-、-OCF₂-、-CF₂O-, -CH-, -CF-or-C.ident.C-, preferably a single bond, -CH ≡ C-₂CH₂-、-OCH₂-、-CH₂O-, more preferably a single bond or-CH₂O-。

When m is 1, Z is preferably¹Is a single bond.

When m is 2, Z is preferably¹is-CH₂CH₂-、-CH₂O-。

The fluorine atom of the compounds represented by the general formulae (N-01), (N-02), (N-03), (N-04) and (N-05) may be substituted with a chlorine atom which is also a halogen atom. Among them, the content of the compound substituted with a chlorine atom is preferably as small as possible, and is preferably not contained.

The hydrogen atoms present in the rings of the compounds represented by the general formulae (N-01), (N-02), (N-03), (N-04) and (N-05) may be further substituted with fluorine atoms or chlorine atoms. However, the content of the compound substituted with a chlorine atom is preferably as small as possible, and preferably not contained.

The compounds represented by the general formulae (N-01), (N-02), (N-03), (N-04) and (N-05) are preferably compounds having negative Δ ε and larger absolute values than 3. In particular, R²²Preferably represents an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms.

The compound represented by the general formula (N-01) preferably contains one or more compounds selected from the group consisting of compounds represented by the general formula (N-01-1), the general formula (N-01-2), the general formula (N-01-3) and the general formula (N-01-4).

[ solution 13]

(in the formula, R²¹Represents the same meaning as described above, R²³Each independently represents an alkoxy group having 1 to 4 carbon atoms).

The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (i), a compound represented by the general formula (N-01-1) and a compound represented by the general formula (N-01-4).

When a high VHR is required, that is, when high reliability is required, and further when importance is attached to obtaining a liquid crystal display element which does not exhibit a defect, it is preferable that the compound represented by the general formula (N-01-3) is not contained.

The compound represented by the general formula (N-02) preferably contains one or more compounds selected from the group consisting of compounds represented by the general formula (N-02-1), the general formula (N-02-2) and the general formula (N-02-3).

[ solution 14]

The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (i) and a compound represented by the general formula (N-02-1).

The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (i) and a compound represented by the general formula (N-02-3).

The liquid crystal composition of the present invention particularly preferably contains a compound represented by the general formula (i), a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4) and a compound represented by the general formula (N-02-1) at the same time.

The liquid crystal composition of the present invention particularly preferably contains a compound represented by the general formula (i), a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4) and a compound represented by the general formula (N-02-3) at the same time.

The compound represented by the general formula (N-03) preferably contains one or more compounds represented by the general formula (N-03-1).

[ solution 15]

(in the formula, R²¹Represents the same meaning as described above, R²³Represents an alkoxy group having 1 to 4 carbon atoms).

The liquid crystal composition of the present invention preferably combines the compound represented by the general formula (i) and the compound represented by the general formula (N-03-1).

The liquid crystal composition of the present invention particularly preferably contains a compound represented by the general formula (i), a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4) and a compound represented by the general formula (N-03-1) at the same time.

The compound represented by the general formula (N-04) preferably contains one or more compounds represented by the general formula (N-04-1).

[ solution 16]

The liquid crystal composition of the present invention particularly preferably contains a compound represented by the general formula (i), a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4) and a compound represented by the general formula (N-04-1) at the same time.

The compound represented by the general formula (N-05) is preferably a compound selected from the group of compounds represented by the formulae (N-05-1) to (N-05-3).

[ solution 17]

The lower limit of the preferable content of the compound represented by the general formula (N-01) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% relative to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, 10%.

The lower limit of the preferable content of the compound represented by the general formula (N-02) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% relative to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, 10%.

The lower limit of the preferable content of the compound represented by the general formula (N-03) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% relative to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, 10%.

The lower limit of the preferable content of the compound represented by the general formula (N-04) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% relative to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, 10%.

The lower limit of the preferable content of the compound represented by the formula (N-05) is 0%, 2%, 5%, 8%, 10%, 13%, 15%, 17%, 20% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%.

The liquid crystal composition of the present invention particularly preferably contains 0.1 to 15% of the compound represented by the general formula (i), 1 to 20% of the compound represented by the general formula (N-01-1), 1 to 30% of the compound represented by the general formula (N-01-4), and 1 to 20% of the compound represented by the general formula (N-04-1).

The liquid crystal composition of the present invention may further contain one or more compounds represented by the general formula (N-06).

[ solution 18]

(in the formula, R²¹And R²²Means the same as defined above)

When various physical properties are to be adjusted, the compound represented by the general formula (N-06) is effective for obtaining a large refractive index anisotropy (. DELTA.n) and a high T_niAs the large. DELTA. epsilon.a compound represented by the general formula (N-06) can be used.

The lower limit of the preferable content of the compound represented by the formula (N-06) is 0%, 2%, 5%, 8%, 10%, 13%, 15%, 17%, 20% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 5%.

The liquid crystal composition of the present invention contains one or more compounds selected from the group of compounds represented by general formulae (NU-01) to (NU-06).

[ solution 19]

(in the formula, R^NU11、R^NU12、R^NU21、R^NU22、R^NU31、R^NU32、R^NU41、R^NU42、R^NU51、R^NU52、R^NU61、R^NU62Each 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, 1 or 2 or more-CH groups which are not adjacent to each other₂-each independently may be substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-, or-OCO-. )

More specifically, R^NU11、R^NU12、R^NU21、R^NU22、R^NU31、R^NU32、R^NU41、R^NU42、R^NU51、R^NU52、R^NU61、R^NU62An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is more preferable. In the case where importance is attached to the response speed, at least 1R is preferable^NU11、R^NU21、R^NU31、R^NU41、R^NU51And R^NU61Is an alkenyl group having 2 to 3 carbon atoms. The compound having such an alkenyl group is preferably 10% or more, preferably 20% or more, preferably 25% or more, preferably 30% or more, preferably 40% or more, preferably 45% or more, preferably 50% or more, relative to the total amount of the liquid crystal composition of the present invention. When high VHR is regarded as important, the amount of the compound having an alkenyl group is preferably 40% or less, preferably 35% or less, and preferably 30% or less.

In order to achieve both high speed and high reliability, it is preferable to use only the general formula (NU-01) as the compound having an alkenyl group, and in this case, R is particularly preferable^NU11Is alkyl of 2 to 4 carbon atoms, R^NU12Is an alkenyl group having 2 to 3 carbon atoms.

In order to achieve both high speed and high reliability, it is preferable to use a compound having an alkenyl group represented by the general formula (NU-01) or the general formula (NU-05), and in this case, R is particularly preferable^NU11Is alkyl of 2 to 4 carbon atoms, R^NU12Is an alkenyl group having 2 to 3 carbon atoms, preferably R^NU51Is alkenyl of 2 to 3 carbon atoms, R^NU52Is an alkyl group having 2 to 3 carbon atoms.

In order to achieve both high speed and high reliability, it is preferable to use a compound having an alkenyl group represented by the general formula (NU-01), the general formula (NU-05) or the general formula (NU-04), and in this case, R is particularly preferable^NU11Is alkyl of 2 to 4 carbon atoms, R^NU12Is an alkenyl group having 2 to 3 carbon atoms, preferably R^NU51And R^NU41Is alkenyl of 2 to 3 carbon atoms, R^NU52And R^NU42Is an alkyl group having 2 to 3 carbon atoms.

The liquid crystal composition of the present invention preferably contains compounds represented by the general formulae (NU-01) and (NU-02).

The liquid crystal composition of the present invention preferably contains compounds represented by the general formulae (NU-01) and (NU-03).

The liquid crystal composition of the present invention preferably contains compounds represented by the general formulae (NU-04) and (NU-05).

The liquid crystal composition of the present invention preferably contains compounds represented by the general formulae (NU-05) and (NU-06).

The liquid crystal composition of the present invention preferably contains compounds represented by the general formulae (NU-01) and (NU-05).

The liquid crystal composition of the present invention preferably contains compounds represented by the general formulae (NU-01) and (NU-06).

The liquid crystal composition of the present invention preferably contains compounds represented by the general formula (NU-01), the general formula (NU-05) and the general formula (NU-06).

The content of the compound represented by the general formula (NU-01) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and still more preferably 25 to 45% by mass.

The content of the compound represented by the general formula (NU-02) is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and still more preferably 5 to 20% by mass.

The content of the compound represented by the general formula (NU-03) is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, and still more preferably 0 to 10% by mass.

The content of the compound represented by the general formula (NU-04) is preferably 3 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 3 to 10% by mass.

The content of the compound represented by the general formula (NU-05) is preferably 0 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 3 to 20% by mass.

The content of the compound represented by the general formula (NU-06) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 3 to 10% by mass.

The liquid crystal composition of the present invention may contain one or two or more polymerizable compounds.

The liquid crystal composition of the present invention may contain one or more polymerizable compounds represented by the general formula (RM) as the polymerizable compound.

[ solution 20]

(in the formula, R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴、R¹⁰⁵、R¹⁰⁶、R¹⁰⁷And R¹⁰⁸Each independently represents P¹³-S¹³Any one of an alkyl group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, an alkoxy group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, a fluorine atom or a hydrogen atom, P¹¹、P¹²And P¹³Each independently represents a polymerizable group represented by the formula (Re-1) to (Re-9),

[ solution 21]

(in the formula, R¹¹、R¹²、R¹³、R¹⁴And R¹⁵Each independently represents an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a hydrogen atom, and m^r5、m^r7、n^r5And n^r7Each independently represents 0, 1 or 2, m^r5、m^r7、n^r5And/or n^r7When 0 is represented, it represents a single bond),

S¹¹、S¹²and S¹³Each independently represents a single bond or an alkylene group having 1 to 15 carbon atoms, 1-CH in the alkylene group₂-or 2 or more-CH not adjacent₂May be substituted by-O-, -OCO-or-COO-, and a plurality of P's are present¹³And S¹³Each of them may be the same or different).

The liquid crystal composition containing the polymerizable compound represented by the general formula (RM) is suitable for producing a PSA-type or PSVA-type liquid crystal display device. It is also suitable for fabricating an NPS type liquid crystal display element. Further, it is preferable to produce a PI-less type liquid crystal display element characterized by having no alignment film.

Since the liquid crystal composition containing the compound represented by the general formula (i) and the polymerizable compound represented by the general formula (RM) has an appropriately high polymerization rate, a desired pretilt angle can be provided within a short ultraviolet irradiation time. Further, the residual amount of the polymerizable compound after polymerization can be reduced. This can improve the production efficiency of manufacturing the PSA-type or PSVA-type liquid crystal display element. Further, it is possible to achieve an effect that a display failure (for example, a failure such as screen burn-in) due to a change in the pre-tilt angle does not occur or the occurrence of the display failure is extremely small. The display defect in the present specification means a display defect due to a change in the pretilt angle with time, a display defect due to the residual amount of an unreacted polymerizable compound, and a display defect due to a decrease in the voltage holding ratio.

In the above general formula (RM), R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴、R¹⁰⁵、R¹⁰⁶、R¹⁰⁷And R¹⁰⁸Each independently represents P¹³-S¹³Any one of an alkyl group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, an alkoxy group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, a fluorine atom and a hydrogen atom is preferably an alkyl group and an alkoxy group, and the number of carbon atoms is preferably 1 to 16, more preferably 1 to 10, further preferably 1 to 8, further preferably 1 to 6, and further preferably 1 to 3. The alkyl group and the alkoxy group may be linear or branched, and are particularly preferably linear.

In the above general formula (RM), R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴、R¹⁰⁵、R¹⁰⁶、R¹⁰⁷And R¹⁰⁸Preferably represents P¹³-S¹³Any one of an alkoxy group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, a fluorine atom and a hydrogen atom, and further preferably represents P¹³-S¹³Any one of an alkoxy group having 1 to 3 carbon atoms, a fluorine atom, or a hydrogen atom. The alkoxy group has preferably 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

In addition, P¹¹、P¹²And P¹³The polymerizable groups may be the same (formulae (Re-1) to (Re-9)) or different polymerizable groups.

In the above general formula (RM), P¹¹、P¹²And P¹³Each independently preferably represents formula (Re-1), formula (Re-2), formula (Re-3), formula (Re-4), formula (Re-5) or formula (Re-7), more preferably formula (Re-1), formula (Re-7)(Re-2), formula (Re-3) or formula (Re-4), more preferably formula (Re-1), and still more preferably an acrylic group or a methacrylic group.

P¹¹And P¹²At least one of them is preferably represented by the formula (Re-1), more preferably an acrylic group or a methacrylic group, still more preferably a methacrylic group, and particularly preferably P¹¹And P¹²Is methacrylic acid group.

In the above general formula (RM), S¹¹、S¹²And S¹³Each independently is preferably a single bond or an alkylene group having 1 to 5 carbon atoms, and particularly preferably a single bond. S¹¹、S¹²And S¹³In the case of a single bond, the residual amount of the polymerizable compound after ultraviolet irradiation is sufficiently small, and display defects due to changes in the pretilt angle are less likely to occur, and display defects in PSA-type or PSVA-type liquid crystal display elements are not generated or are very rarely generated. At S¹¹、S¹²And S¹³When the number of carbon atoms is 1 to 3, the liquid crystal display device is suitable for NPS type liquid crystal display devices.

The lower limit of the content of the polymerizable compound represented by the general formula (RM) in the liquid crystal composition of the present invention is preferably 0.01 mass%, preferably 0.02 mass%, preferably 0.03 mass%, preferably 0.04 mass%, preferably 0.05 mass%, preferably 0.06 mass%, preferably 0.07 mass%, preferably 0.08 mass%, preferably 0.09 mass%, preferably 0.1 mass%, preferably 0.12 mass%, preferably 0.15 mass%, preferably 0.17 mass%, preferably 0.2 mass%, preferably 0.22 mass%, preferably 0.25 mass%, preferably 0.27 mass%, preferably 0.3 mass%, preferably 0.32 mass%, preferably 0.35 mass%, preferably 0.37 mass%, preferably 0.4 mass%, preferably 0.42 mass%, preferably 0.45 mass%, preferably 0.5 mass%, preferably 0.55 mass%. The upper limit of the content of the polymerizable compound represented by the general formula (RM) in the liquid crystal composition of the present invention is preferably 5 mass%, preferably 4.5 mass%, preferably 4 mass%, preferably 3.5 mass%, preferably 3 mass%, preferably 2.5 mass%, preferably 2 mass%, preferably 1.5 mass%, preferably 1 mass%, preferably 0.95 mass%, preferably 0.9 mass%, preferably 0.85 mass%, preferably 0.8 mass%, preferably 0.75 mass%, preferably 0.7 mass%, preferably 0.65 mass%, preferably 0.6 mass%, preferably 0.55 mass%, preferably 0.5 mass%, preferably 0.45 mass%, preferably 0.4 mass%.

More specifically, the content is preferably 0.2 to 0.6% by mass in order to obtain a sufficient pretilt angle or a small residual amount of the polymerizable compound or a high Voltage Holding Ratio (VHR), and when suppression of precipitation at low temperatures is considered important, the content is preferably 0.01 to 0.4% by mass. Particularly, when a fast response speed is obtained, it is preferable to increase the content to 2% by mass.

When a plurality of polymerizable compounds represented by the general formula (RM) are contained, the content of each is preferably 0.01 to 0.4% by mass. Therefore, in order to solve all of these technical problems, it is particularly preferable to adjust the polymerizable compound represented by the general formula (RM) to a range of 0.1 to 0.6 mass%.

Specifically, the polymerizable compounds represented by the general formula (RM) according to the present invention are preferably compounds represented by the general formulae (RM-1) to (RM-10), and PSA type liquid crystal display elements using the same have a small amount of the residual polymerizable compounds, a sufficient pretilt angle, and no or very few defects such as alignment defects and display defects due to changes in the pretilt angle.

[ solution 22]

[ solution 23]

In the formula, R^M1And R^M2Each independently represents an alkyl group having 1 to 5 carbon atoms, a fluorine atom, or a hydrogen atom, and more preferably represents an alkyl group having 1 carbon atom or a hydrogen atom.

The liquid crystal composition of the present invention may contain one or more compounds having a terphenyl structure or a quaterphenyl structure and having a dielectric anisotropy Δ ∈ of more than +2, that is, compounds having a positive dielectric anisotropy. The Δ ∈ of the compound is a value obtained by extrapolating from a measured value of dielectric anisotropy of a composition in which the compound was added to a composition having a substantially neutral dielectric property at 25 ℃. The compound is used in combination with desired properties such as solubility at low temperatures, transition temperature, electrical reliability, refractive index anisotropy, and the like, and particularly, the reactivity of the polymerizable compound in the liquid crystal composition containing the polymerizable compound can be accelerated.

The lower limit of the preferable content of the compound having a terphenyl structure or a quaterphenyl structure and having a dielectric anisotropy Δ ∈ of more than +2 is 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, and 10%, with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, and 3% of the total amount of the liquid crystal composition of the present invention, for example.

The liquid crystal composition of the present invention may contain, in addition to the above-mentioned compounds, a conventional nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, antioxidant, ultraviolet absorber, photostabilizer, infrared absorber, or the like.

Examples of the antioxidant include hindered phenols (hindered phenols) represented by general formulae (H-1) to (H-4).

[ solution 24]

In the general formulae (H-1) to (H-3), R^H1Each 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, and 1-CH present in the group₂-or 2 or more-CH not adjacent₂Each independently of the others may be substituted by-O-or-S-and, in addition, present in the radicals1 or 2 or more hydrogen atoms of (a) may be independently substituted with a fluorine atom or a chlorine atom, respectively. 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 2 or more-CH groups in the alkylene group)₂-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-COO-, -CH-OCO-, -COO-CH-, -OCO-CH-, -CH-, -C.ident.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 number of carbon atoms is preferably a large number in view of volatility, is preferably not excessively large in view of viscosity, 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 nonadjacent 2 or more of 1, 4-phenylene groups may be substituted with — N ═ c. 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 group in the general formula (H-2) and the general formula (H-4)₂-may be substituted by-O-or-S-. Further, the hydrogen atoms in the 1, 4-cyclohexylene group may each independently be substituted with a fluorine atom or a chlorine atom.

More specifically, for example, the following may be mentioned formulas (H-11) to (H-15).

[ solution 25]

When the antioxidant is contained in the liquid crystal composition of the present invention, the content is preferably 10 mass ppm or more, preferably 20 mass ppm or more, and preferably 50 mass ppm or more. The upper limit when the antioxidant is contained is 10000 ppm by mass, preferably 1000 ppm by mass, preferably 500 ppm by mass, preferably 100 ppm by mass.

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 ℃, particularly preferably from 70 ℃ to 85 ℃. In the present invention, T represents 60 ℃ or higher_NiHigh.

In the case of liquid crystal television applications, T_NiPreferably 70 to 80 ℃ in the case of mobile use, T_NiPreferably 80 to 90 ℃ and T is used for outdoor Display such as PID (Public Information Display)_NiPreferably from 90 to 110 ℃.

The liquid crystal composition of the present invention has a refractive index anisotropy (. DELTA.n) at 20 ℃ of 0.08 to 0.14, more preferably 0.09 to 0.13, and particularly preferably 0.09 to 0.12. In further detail, it is preferably 0.10 to 0.13 when corresponding to a thin cell gap, and 0.08 to 0.10 when corresponding to a thick cell gap. In the present invention, 0.09 or more is expressed as Δ n being large.

Rotational viscosity at 20 ℃ of the liquid Crystal composition of the present invention (. gamma.)₁) Is from 50 to 160 mPas, preferably from 55 to 160 mPas, preferably from 60 to 160 mPas, preferably from 80 to 150 mPas, preferably from 90 to 140 mPas, preferably from 90 to 130 mPas, preferably from 100 to 130 mPas.

The liquid crystal composition of the present invention has a dielectric anisotropy (. DELTA.. di-elect cons.) at 20 ℃ of-2.0 to-8.0, preferably-2.0 to-6.0, more preferably-2.0 to-5.0, more preferably-2.5 to-4.0, and particularly preferably-2.5 to-3.5.

In the compounds constituting the liquid crystal composition of the present invention, the upper limit of the total content of the compounds having alkenyl groups is preferably 10%, preferably 8%, preferably 6%, preferably 5%, preferably 4%, preferably 3%, preferably 2%, preferably 1%, preferably 0%, and the total content of the compounds having alkenyl groups is preferably 0 to 10%, preferably 0 to 8%, preferably 0 to 5%, preferably 0 to 4%, preferably 0 to 3%, preferably 0 to 2%. However, the compound represented by the general formula (NU-01) is not included.

The liquid crystal composition of the present invention preferably contains the compound of the general formula (i) as an essential component, further contains one or more compounds selected from the group consisting of the compounds represented by the general formulae (N-01), (N-02), (N-03), (N-04), (N-05) and (N-06), and further contains one or more compounds selected from the group consisting of the compounds represented by the general formulae (NU-01) to (NU-06), and the upper limit of the total of these contents is preferably 100 mass%, 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 89 mass%, 88 mass%, 87 mass%, 86 mass%, 85 mass%, 84% by mass, the lower limit of the total of these contents is preferably 78% by mass, 80% by mass, 81% by mass, 83% by mass, 85% by mass, 86% by mass, 87% by mass, 88% by mass, 89% by mass, 90% by mass, 91% by mass, 92% by mass, 93% by mass, 94% by mass, 95% by mass, 96% by mass, 97% by mass, 98% by mass, or 99% by mass.

The liquid crystal display element using the liquid crystal composition of the present invention is useful particularly for a liquid crystal display element for active matrix driving, and can be suitably used for liquid crystal display elements such as VA, FFS, IPS, PSA, PSVA, PS-IPS, PS-FFS, NPS, and PI-less.

The liquid crystal display device according to the present invention preferably includes a first substrate and a second substrate which are arranged to face each other, a common electrode provided on the first substrate or the second substrate, a pixel electrode provided on the first substrate or the second substrate and having a thin film transistor, and a liquid crystal layer containing a liquid crystal composition provided between the first substrate and the second substrate. If necessary, an alignment film for controlling the alignment direction of the liquid crystal molecules may be provided on the opposite surface side of at least one of the first substrate and the second substrate so as to be in contact with the liquid crystal layer. As the alignment film, a vertical alignment film, a horizontal alignment film, or the like can be appropriately selected in accordance with the driving mode of the liquid crystal display element, and a known alignment film such as a rubbing alignment film (for example, polyimide), a photo alignment film (for example, decomposed polyimide), or the like can be used. Further, a color filter may be provided on the first substrate or the second substrate as appropriate, or a color filter may be provided on the pixel electrode or the common electrode.

The two substrates of the liquid crystal cell used in the liquid crystal display element according to the present invention may be made of a transparent material having flexibility such as glass or plastic, or may be made of an opaque material such as silicon. The transparent substrate having the 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. The following description will be made by taking as an example a method of manufacturing a color filter by a pigment dispersion method: the curable coloring composition for color filters is applied onto the transparent substrate, subjected to patterning treatment, and 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.

Preferably, the first substrate and the second substrate are opposed to each other so that the common electrode and the pixel electrode layer are located inside.

The interval between the first substrate and the second substrate may be adjusted with a spacer 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 where two polarizing plates are present, the polarizing axes of the respective polarizing plates may be adjusted so that the viewing angle and the contrast are improved. Further, a retardation film for enlarging the viewing angle may be used. Examples of the spacer include glass particles, plastic particles, alumina particles, and photoresist materials. Then, a sealant such as an epoxy 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 heated and cured by heat.

As a method for sandwiching the liquid crystal composition between the two substrates, a general vacuum injection method, ODF method, or the like can be used.

In order to form the alignment state of the liquid crystal display element of the present invention, it is possible to use a liquid crystal composition containing a polymerizable compound in a liquid crystal composition and to polymerize the polymerizable compound in the liquid crystal composition.

As a method of polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention, polymerization at an appropriate polymerization rate is desired in order to obtain good alignment properties of the liquid crystal, and therefore, a method of polymerizing by irradiating active energy rays such as ultraviolet rays or electron rays alone or in combination or sequentially is preferable. When ultraviolet light is used, either a polarized light source or an unpolarized light source may be used. In addition, when the polymerization is performed in a state where the liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must be provided with appropriate transparency to the active energy ray. In addition, the following means may be used: in the light irradiation, only a specific portion is polymerized using a mask, and then the orientation state of the unpolymerized portion is changed by changing the conditions such as an electric field, a magnetic field, or temperature, and further, the polymerization is performed by irradiation with an active energy ray. In particular, when ultraviolet exposure is performed, it is preferable to perform ultraviolet exposure while applying an alternating-current electric field to the liquid crystal composition. The applied alternating electric field is preferably alternating at a frequency of 10Hz to 10kHz, more preferably at a frequency of 60Hz to 10kHz, the voltage being selected in dependence on the desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In the PSVA type liquid crystal display element, the pretilt angle is preferably controlled to 80 degrees to 89.9 degrees from the viewpoints of alignment stability and contrast.

The temperature at the time of irradiation with active energy rays such as ultraviolet rays or electron rays used for polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention is not particularly limited. For example, when the liquid crystal composition of the present invention is applied to a liquid crystal display element having a substrate with an alignment film, the liquid crystal composition is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition is maintained. It is preferable to polymerize the monomer at a temperature close to room temperature, typically 15 to 35 ℃.

On the other hand, for example, when the liquid crystal composition of the present invention is applied to a liquid crystal display element having a substrate without an alignment film, the temperature range may be wider than the temperature range at the time of irradiation applied to the liquid crystal display element having a substrate with an alignment film.

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. The wavelength of the ultraviolet light to be irradiated is preferably ultraviolet light whose irradiation wavelength range is not in the absorption wavelength range of the liquid crystal composition, and the ultraviolet light is preferably used by being filtered (カット) as necessary. The intensity of the ultraviolet ray to be irradiated is preferably 0.1mW/cm²～100W/cm²More preferably 2mW/cm²～50W/cm². The energy of the ultraviolet ray to be irradiated may be suitably adjusted, and is preferably 10mJ/cm²To 500J/cm²More preferably 100mJ/cm²To 200J/cm². When ultraviolet rays are irradiated, the intensity can be changed. The time for irradiating ultraviolet rays may be appropriately selected depending on the intensity of 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 with reference to the following examples, but the present invention is not limited to these examples. In the compositions of examples and comparative examples below, "%" means "% by mass". The compounds described in the examples are as follows.

Unless otherwise specified, the physical property values were measured by the methods described in the standards JEITA ED-2521B of the association of electronic information technology industries, the modification of 3 months in 2009, and the issuance of the association of electronic information technology industries by the community law.

(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-

-F -F

-OCF3 -OCF₃

(linker)

-CF2O- -CF₂-O-

-OCF2- -O-CF₂-

-1O- -CH₂-O-

-O1- -O-CH₂-

-2- -CH₂-CH₂-

-COO- -COO-

-OCO- -OCO-

-single bond

(Ring structure)

[ solution 26]

The properties measured in the examples are as follows.

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

T_→N: temperature of solid phase-nematic phase transition (. degree.C.)

Δ n: refractive index anisotropy at 20 DEG C

Δ ε: anisotropy of dielectric constant at 20 DEG C

γ₁: rotation at 20 deg.CViscosity (mPa. s)

K₁₁: elastic constant K at 20 DEG C₁₁(pN)

K₃₃: elastic constant K at 20 DEG C₃₃(pN)

VHR: voltage holding ratio at 1V, 60Hz and 60 ℃ (%)

(preparation of liquid Crystal composition and evaluation results)

The liquid crystal compositions of example 1 and comparative example 1 were prepared, and the physical property values thereof were measured. In addition, T in the physical property values_NiThe composition ratio is designed so that Δ n and Δ ∈ become similar. The component ratios and physical property values of these liquid crystal compositions are shown in table 1.

[ Table 1]

	Example 1	Comparative example 1
			T_Ni	83.9	84.6
T_→N	G-22	G-27
			Δn	0.1033	0.1018
Δε	-2.97	-2.95
			γ1	99	102
3-Cy-Cy-2	22	19
			3-Cy-Cy-4	6	7
3-Cy-Ph-O1	13	11
			3-Cy-Ph-Ph-2	7	6
3-Cy-Ph-Ph5-O2	8	9
			3-Cy-Ph-Ph5-O3	8	9
3-Cy-Ph-Ph5-O4	8	9
			3-Cy-Ph5-O2	9	15
3-Cy-Cy-Ph5-O2	15	15
			2O-Bd-3	4

Examples 2 to 4 and comparative examples 2 to 4 were prepared in the same manner, and the effects of the present invention were confirmed.

[ Table 2]

	Example 2	Comparative example 2
			T_NI	82.9	83.6
T_→N	G-22	G-25
			Δn	0.1022	0.1002
Δε	-3.04	-3.06
			γ1	99	105
3-Cy-Cy-2	22	19
			3-Cy-Cy-4	8	7
3-Cy-Ph-O1	14	15
			3-Cy-1O-Ph5-O1	6	7
3-Cy-1O-Ph5-O2		3
			3-Cy-Ph-Ph-2	9	9
3-Cy-Ph-Ph5-O2	8	8
			3-Cy-Ph-Ph5-O3	8	8
3-Cy-Ph-Ph5-O4	8	8
			3-Cy-Cy-1O-Ph5-O2	13	16
2O-Bd-3	4

[ Table 3]

	Example 3	Comparative example 3
			T_NI	85.1	84.0
T_→N	G-43	G-56
			Δn	0.1059	0.1051
Δε	-3.21	-3.01
			γ1	94	96
3-Cy-Cy-V	38	31
			V-Cy-Ph-Ph-3	6	6
3-Cy-Ph-Ph-2	5	6
			3-Cy-Ph-Ph-5	4	6
2-Cy-Cy-1O-Ph5-O2	12	12
			3-Cy-Cy-1O-Ph5-O2	12	12
2-Ph-2-Ph-Ph5-O2	6	6
			3-Ph-2-Ph-Ph5-O2	6	6
3-Cy-Ph5-O2	6	15
			2O-Bd-3	5

[ Table 4]

	Example 4	Comparative example 4
			T_NI	87.5	86.9
T_→N	G-18	G-23
			Δn	0.1044	0.1046
Δε	-3.12	-3.13
			γ1	107	116
3-Cy-Cy-2	20	16
			3-Cy-Cy-4	8	5
3-Cy-Cy-V1	9	10
			V-Cy-Ph-Ph-3	5	5
3-Cy-Ph-Ph-2	6	6
			3-Cy-Ph-Ph-5	6	6
2-Cy-Cy-1O-Ph5-O2	11	12
			3-Cy-Cy-1O-Ph5-O2	11	12
2-Ph-2-Ph-Ph5-O2	6	6
			3-Ph-2-Ph-Ph5-O2	5	7
3-Cy-Ph5-O2	8	15
			2O-Bd-3	5

[ solution 27]

As described above, the liquid crystal composition of the present invention has a negative dielectric anisotropy (. DELTA.. di-elect cons.), and a negative Tg_NiHigh, Δ n is large, γ₁Small, K₃₃Large, gamma₁/K₃₃Is small.

Therefore, the following steps are carried out: the values of Δ n and Δ ∈ were almost the same as those of the compositions of examples 1 and 2, but γ 1 was large and deteriorated in comparative examples 1 and 2 of the liquid crystal composition containing no compound represented by the general formula (i). Thus, it was confirmed that: when the compositions of examples 1 and 2 were used to fabricate VA-type and FFS-type liquid crystal display devices, the response time was short and VHR was high. At this time, it was also confirmed that no display failure occurred. On the other hand, VA-type and FFS-type liquid crystal display elements were produced in the same manner for the compositions of comparative examples, and the response times were measured, but the response times were inferior to those of the compositions of examples.

Further, from T_NiThe results for the compositions of examples 3 and 4 with high, increased Δ ∈ are also known: not only improve T_NiAnd Δ ∈, and also suppress the increase in γ 1.

In example 3, the value of Δ ∈ in comparative example 3 was reduced, and the element was not suitable for low-voltage driving. In addition, in comparison of example 4 with comparative example 4, it is clear that: in the liquid crystal composition of the present invention, γ 1 is improved by about 8%.

A polymerizable compound represented by the formula (RM-2) (wherein R is added in an amount of 0.5 mass% based on 99.5 mass% of the liquid crystal composition of example 1) was prepared^M1And R^M2Methyl) was used to prepare a PSA-type liquid crystal display element.

[ solution 28]

In the production of a PSA liquid crystal display device, ultraviolet light having peaks at 313nm and 365nm is irradiated. Measurement conditions of response speed: the Von was 5V, Voff and 0.5V, the measurement temperature was 20 ℃, and DMS703 available from AUTRONIC-MELCHERS was used as a measuring instrument.

Confirming that: t is_NiHigh, Δ n is large, γ₁Small, K₃₃Large, gamma₁Small size and high response speed.

As described above, the present invention has excellent effects.

Claims

1. A liquid crystal composition comprising 1 or 2 or more compounds represented by the general formula (i),

[ solution 1]

Yⁱ¹and Yⁱ²Each independently represents-O-, -CF₂-、-CO-、-CXⁱ³Xⁱ⁴-，Yⁱ¹And Yⁱ²Any one of the above-mentioned groups represents-O-, Xⁱ³、Xⁱ⁴Independently of each other representⁱ¹The same meaning is given to the same person,

[ solution 2]

In the formula, Rⁱ¹Represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms or an alkenyloxy group having 2 to 15 carbon atoms,

Aⁱ¹represents a group selected from the group consisting of:

(a)1, 4-cyclohexylene radical, 1-CH present in this radical₂-or non-contiguous 2 or more-CH₂-may be substituted by-O-or-S-;

(b)1, 4-phenylene in which 1-CH ═ or nonadjacent 2 or more-CH ═ present in the group may be substituted with-N ═ and 1 hydrogen atom present in the group may be substituted with a fluorine atom;

(c)1, 4-cyclohexenyl group, naphthalene-2, 6-diyl group, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl group, decahydronaphthalene-2, 6-diyl group, and a hydrogen atom present in these groups may be substituted by a fluorine atom, and in addition, 1-CH ═ or non-adjacent 2 or more-CH ═ present in naphthalene-2, 6-diyl group or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl group may be substituted by-N ═ or,

nⁱ¹represents 1 or 2, in nⁱ¹Represents 2 and has a plurality of Aⁱ¹And Zⁱ¹They may be the same or different,

Wⁱ¹is represented by the general formula (W)ⁱ¹-1)、(Wⁱ¹-2) or (W)ⁱ¹A group represented by (1) to (3)，

[ solution 3]

Wherein · represents and Lⁱ²Or Yⁱ²＊ denotes a bond with Lⁱ⁵Bonding sites of carbon atoms adjacent to the bonded carbon atom, Lⁱ⁶、Lⁱ⁷And Lⁱ⁸Independently of each other representⁱ¹The same meaning is given to the same person,

Wⁱ²represents a single bond or-CLⁱ⁹Lⁱ¹⁰-，

Lⁱ⁹And Lⁱ¹⁰Independently of each other representⁱ¹The same meaning is given to the same person,

Lⁱ¹、Lⁱ²、Lⁱ³、Lⁱ⁴、Lⁱ⁵、Lⁱ⁶、Lⁱ⁷、Lⁱ⁸、Lⁱ⁹and Lⁱ¹⁰1 of-CH present in₂-or non-contiguous 2 or more-CH₂May be substituted by-C.ident.C-, -O-, -COO-, -OCO-or-CO-, and in addition, the hydrogen atoms present in the alkyl or alkenyl groups may be substituted by fluorine atoms.

2. The liquid crystal composition according to claim 1, wherein the liquid crystal composition comprises 1 or 2 or more compounds selected from the group consisting of compounds represented by the general formula (N-01), the general formula (N-02), the general formula (N-03), the general formula (N-04), and the general formula (N-05),

[ solution 4]

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, 1 or 2 or more-CH groups not adjacent to each other₂-each independently may be substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-, or-OCO-, Z¹Each independently represents a single bond, -CH₂CH₂-、-OCH₂-、-CH₂O-、-COO-、-OCO-、-OCF₂-、-CF₂O-, -CH ═ CH-, -CF ═ CF-or-C ≡ C-, and m each independently represents 1 or 2.

3. The liquid crystal composition according to claim 1 or 2, which comprises 1 or 2 or more compounds selected from the group consisting of compounds represented by general formulae (NU-01) to (NU-06),

[ solution 5]

In the formula, R^NU11、R^NU12、R^NU21、R^NU22、R^NU31、R^NU32、R^NU41、R^NU42、R^NU51、R^NU52、R^NU61、R^NU62Each 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, 1 or 2 or more-CH groups not adjacent to each other₂-each independently may be substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-, or-OCO-.

4. The liquid crystal composition according to claim 3, wherein the compound represented by the general formula (NU-01) has an alkenyl group, and the total content thereof is 0 to 50% by mass.

5. The liquid crystal composition according to any one of claims 3 and 4, wherein the total content of the compound represented by the general formula (i), the compound selected from the group consisting of the compounds represented by the general formulae (N-01) to (N-05), and the compound selected from the group consisting of the compounds represented by the general formulae (NU-01) to (NU-06) is 95 to 100% by mass.

6. The liquid crystal composition according to any one of claims 1 to 5, which comprises 1 or 2 or more polymerizable compounds represented by the general formula (RM),

[ solution 6]

In the formula, R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴、R¹⁰⁵、R¹⁰⁶、R¹⁰⁷And R¹⁰⁸Each independently represents P¹³-S¹³Any one of an alkyl group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, an alkoxy group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, a fluorine atom or a hydrogen atom, P¹¹、P¹²And P¹³Each independently represents a polymerizable group represented by the formula (Re-1) to (Re-9),

[ solution 7]

In the formula, R¹¹、R¹²、R¹³、R¹⁴And R¹⁵Each independently represents an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a hydrogen atom, and m^r5、m^r7、n^r5And n^r7Each independently represents 0, 1 or 2, in m^r5、m^r7、n^r5And/or n^r7When 0 is represented, it represents a single bond,

S¹¹、S¹²and S¹³Each independently represents a single bond or an alkylene group having 1 to 15 carbon atoms, 1-CH in the alkylene group₂-or non-contiguous 2 or more-CH₂May be substituted by-O-, -OCO-or-COO-, and a plurality of P's are present¹³And S¹³Each of them may be the same or different.

7. A liquid crystal display element using the liquid crystal composition according to any one of claims 1 to 6.

8. A liquid crystal display element for active matrix driving, which comprises the liquid crystal composition according to any one of claims 1 to 6.

9. A VA-type, IPS-type, FFS-type, PSA-type or PSVA-type liquid crystal display element using the liquid crystal composition according to any one of claims 1 to 6.